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    • 专利摘要:
    Catalytic process for the depolymerization of lignin. The invention relates to a catalytic process for the depolymerization of lignin, which employs a catalyst consisting of a transition metal and a support selected from the list consisting of metal oxide nanoparticles, a one-dimensional structure and nanoparticles of metal oxides supported on a structure one-dimensional in addition, the invention relates to said catalyst and the use of said catalyst for the depolymerization of lignin. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2642143A1
    申请号:ES201630455
    申请日:2016-04-12
    公开日:2017-11-15
    发明作者:Jimmy Alexander FARIA ALBANESE；Maria Pilar RUIZ RAMIRO；Mercedes LECEA ROMERA；Beatriz GÓMEZ MONEDERO
    申请人:Abengoa Research SL；
    IPC主号:
    专利说明:

    The invention relates to a catalytic process for the depolymerization of lignin,by using a catalyst consisting of a transition metal and a supportselected from the list consisting of nanoparticles based onmetal oxides, a one-dimensional structure, and oxide-based nanoparticlesmetallic and supported in a one-dimensional structure. Furthermore the invention is
    10 refers to said catalyst and the use thereof for the depolymerization of lignin. STATE OF THE ART
    Lignin is one of the main components of all vascular plants and the
    15 second most abundant natural polymer. Lignin can be processed by biological, thermochemical or catalytic routes.
    The main disadvantages of biological conversion are the slow kinetics of the metabolic processes and the complexity of the operation of the process, since the
    Reaction conditions must be carefully controlled to avoid inactivation of microorganisms. On the other hand, in thermochemical routes, thermal energy is used to depolymerize the lignin structure in light, liquid and solid gases, for later use in the production of fuels and energy. Unfortunately, these processes involve radical reactions
    25 free, which makes controlling the selectivity of the depolymerization process difficult. In contrast, chemical depolymerization offers high conversion rates, higher selectivity, robust operation, and easier scalability. This improvement process can be carried out in a cascade process, in which it is possible to purify, depolymerize and convert the lignin fragments into fuels and other
    30 chemicals. DESCRIPTION OF THE INVENTION
    The present invention discloses a catalytic route that manages to depolymerize lignin
    35 selectively breaking specific bonds at high rates and generates oligomers and monomers, which can be separated to produce compounds
    aromatic or transformed into fuels and intermediate compounds for the synthesis of chemical products.
    Therefore, a first aspect of the present invention refers to a process for
    5 the depolymerization of lignin, where the process comprises at least one step a)contact of a lignin stream with a catalyst consisting of a metal oftransition supported,
    where the support selected from the list consisting of: x metal oxide nanoparticles 10 x a one-dimensional structure and x metal oxide nanoparticles supported on a one-dimensional structure and said step is carried out in the presence of x a reducing agent; and
    15 x a solvent selected from the list consisting of water, ethanol, methanol, propanol, butanol, decalin, benzene, toluene, xylene, cyclohexane, gasoline, diesel, and combinations thereof.
    The term "lignin stream" refers herein to a stream comprising lignin. 20 For example, this lignin stream is obtained from the stillage of cellulosic ethanol production processes.
    In a preferred embodiment, the transition metal is selected from the list consisting of Sn, Ga, Mg, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo , Ru,
    25 Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au and a combination thereof. Preferably, the transition metal is selected from the list consisting of Ni, Ru, Pd, Fe, Mo, Co, Cu, Fe, and a combination thereof. Most preferably, the transition metal is selected from Ru, Ni, and a combination thereof.
    In another preferred embodiment, the transition metal is in the form of a metallic aggregate with a particle size between 1 and 100 nm, preferably between 2 and 50 nm, the composition of which has been mentioned above.
    A further embodiment of the present invention relates to a process for the depolymerization of lignin, where the metal oxide nanoparticles are
    selected from the list consisting of SiO2, TiO2, V2O5, Cr2O3, MnO2, MgO, Fe2O3, FeO, CoO, ZnO, Y2O3, ZrO2, Nb2O5, CdO, La2O3, SnO2, HfO2, Ta2O5, WO3, Re2O3, Al , Cs2O and combination thereof. Preferably, the metal oxide nanoparticles are selected from the list consisting of TiO2, V2O5, Cr2O3,
    5 MnO2, ZrO2, CeO2 and combination thereof. More preferably, theMetal oxide nanoparticles are selected from the list consisting of TiO2,V2O5, MnO2, ZrO2, CeO2 and combination thereof.
    The term "one-dimensional structure" refers here to filaments, wires, fibers,
    10 hairs, rods, ribbons and tubes whose lateral dimensions are within the range of 50 to 5000 nm.
    In a preferred embodiment, the one-dimensional structure is selected from the list consisting of C nanotubes, TiO2 nanotubes, V2O5 nanotubes, nanotubes
    15 of MnO2, ZrO2 nanotubes, carbon fibers, graphene sheets and a combination thereof.
    Preferably, the one-dimensional carbon structure is C nanotubes, that is, carbon nanotubes. Most preferably, carbon nanotubes have a
    20 aspect ratio length: diameter (L / D) between 5 and 2000 and lengths between 50 and 5000 nm.
    In a preferred embodiment, the one-dimensional structure comprises magnetic nanoparticles on its surface.
    25 Preferably the magnetic nanoparticles are nanoparticles of Fe oxides
    (III) as Fe2O3, NiOFe2O3, CuOFe2O3, MgOFe2O3 and combination thereof; These magnetic nanoparticles facilitate the extraction and separation of the catalyst from the reaction mixture after reaction, through the use of a unit of
    30 electromagnetic separation.
    In a preferred embodiment, the percentage by weight of the Fe (III) oxide magnetic nanoparticles in the one-dimensional structure is in the range of 5 to 60% by mass. Preferably, the weight percent of the nanoparticles
    The magnetic oxide of Fe (III) in the one-dimensional structure is between 10% and 50%, and more preferably between 20% and 40%.
    As mentioned above, step a) of the lignin depolymerization process is
    performs in the presence of x a reducing agent; and x a solvent selected from the list consisting of water, ethanol,
    5 methanol, propanol, butanol, decalin, benzene, toluene, xylene, cyclohexane,gasoline, diesel and combinations thereof.
    In a preferred embodiment, the reducing agent is selected from the list consisting of hydrogen, formic acid, ethanol, methanol, and combinations thereof.
    In another preferred embodiment, step a) is carried out at pressures between 10 bar and 100 bar and temperatures between 150 ° C and 400 ° C.
    Preferably, step a) is carried out at pressures between 10 bar and 70 bar, preferably at pressures between 30 bar and 60 bar and, more preferably between 40 bar and 60 bar.
    Preferably, step a) is carried out at temperatures between 150 ° C and 300 ° C, preferably at temperatures between 150 ° C and 250 ° C, and more preferably between 180 ° C and 200 ° C.
    A further embodiment of the present invention provides a process for the depolymerization of lignin, where the lignin stream previously used in step a) has been previously purified.
    In another preferred embodiment, the pH of the lignin current of step a) is between 4 and 8, preferably between 4 and 6.
    Furthermore, another preferred embodiment of the present invention refers to the above
    A process that also comprises a stage b) for recovering the catalyst. Preferably, the recovery of the catalyst is carried out by filtration, for example using a hydrocyclone or a particulate filter. In a further embodiment, step b) is followed by a step b ') that comprises the recovery of the catalyst by applying a magnetic field between 0.1 Teslas and 5 Teslas, said
    35 catalyst comprises a one-dimensional structure comprising nanoparticles
    magnetic on its surface. For example, an electromagnetic cyclone can be used.
    In another preferred embodiment, the aforementioned process further comprises a step c)
    5 of purification of the stream obtained in stage b) or in stage b ') by means ofseparation of a stream consisting of a solvent and a lignin streamnot depolymerized from a stream consisting of aromatic compoundsderived from lignin. For example this separation is a distillation of the currentobtained in step b) or in step b ').
    Another aspect of the present invention refers to the process for obtaining ethanol and / or butanol comprising
    x steps a) to c) of the depolymerization of lignin according to the process described above; and
    15 x a stage d) of contact between genetically modified microorganisms and the aromatic compounds derived from lignin obtained during stage c).
    Preferably, the genetically modified microorganisms are selected from
    20 the list consisting of fungi basidiomycetes, chrysosporium phanerochaete, and streptomyces spp.
    A third aspect of the invention refers to a catalyst consisting of a transition metal and a support, where the support is formed by nanoparticles of
    25 metal oxides supported in a one-dimensional structure.
    In a preferred embodiment, the transition metal is chosen from a list consisting of Sn, Ga, Mg, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo , Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au and combination thereof. Preferably, the
    The transition metal is selected from the list consisting of Ni, Ru, Pd, Fe, Mo, Co, Cu, Fe, and a combination thereof. Most preferably, the transition metal is selected from Ru, Ni and a combination thereof.
    In another preferred embodiment, the transition metal is in the form of a metallic aggregate with a particle size between 1 and 100 nm, preferably
    between 2 and 50 nm, and more preferably between 2 and 5 nm, the composition of which is mentioned above.
    A further embodiment of the catalyst refers to nanoparticles of oxides
    5 metals selected from the list consisting of SiO2, TiO2, V2O5, Cr2O3, MnO2,MgO, Fe2O3, FeO, CoO, ZnO, Y2O3, ZrO2, Nb2O5, CdO, La2O3, SnO2, HfO2, Ta2O5,WO3, Re2O7, Al2O3, CeO2, Cs2O and combination thereof. Preferably, theMetal oxide nanoparticles are selected from the list consisting of TiO2,V2O5, Cr2O3, MnO2, ZrO2, CeO2 and combination thereof. More preferably,
    The metal oxide nanoparticles are selected from the list consisting of TiO2, V2O5, MnO2, ZrO2, CeO2, and a combination thereof.
    Another embodiment of the catalyst refers to a one-dimensional structure, selected from the list consisting of C nanotubes, TiO2 nanotubes,
    15 V2O5 nanotubes, MnO2 nanotubes, ZrO2 nanotubes, carbon fibers, graphene sheets and a combination thereof.
    Preferably, the one-dimensional structure is carbon nanotubes. Most preferably, the carbon nanotubes have a length: aspect ratio.
    20 diameter (L / D) between 5 and 2000 with lengths between 50 and 5000 nm.
    In a preferred embodiment, the one-dimensional structure comprises magnetic nanoparticles on its surface. Preferably the magnetic nanoparticles are nanoparticles of Fe (III) magnetic oxides such as Fe2O3, NiOFe2O3,
    25 CuOFe2O3, MgOFe2O3, and a combination thereof.
    In a preferred embodiment, the percentage by weight of the Fe (III) oxide magnetic nanoparticles in the one-dimensional structure varies between 5 and 60%. Preferably, the percentage by weight of the Fe (III) oxide nanoparticles in
    The one-dimensional structure varies between 10 and 50%, more preferably between 20 and 40%.
    The last aspect of the invention is related to the use of the catalyst mentioned above for the depolymerization of lignin.
    Unless defined otherwise, all technical and scientific terms usedin this document they have the same meaning that is commonly understoodby one of ordinary skill in the art to which the present invention belongs.Procedures and materials similar or equivalent to those described in the5 herein can be used in the practice of the present invention. In all thedescription and claims, the word "comprises" and its variations are not intended toexclude other technical characteristics, additives, components or stages. Objectives,Additional advantages and features of the invention will be apparent to thosesubject matter experts upon examination of the description or may be learned by
    10 practice of the invention. The following examples and drawings are provided by way of illustration and are not intended to be limiting of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS
    15 FIG. 1 Scheme of the cascade process for the isolation, purification and depolymerization of lignin streams using heterogeneous catalysts.
    FIG. 2 Scheme of the cascade process for the isolation, purification and depolymerization of lignin streams using heterogeneous catalysts.
    20 FIG. 3 GC-MS chromatogram of the main products identified in Example 1; 1) 4-ethylphenol, 2) 2,3-dihydro-1-benzofuran, 3) 1- (2-methoxyphenyl) ethanol, 4) 2,6-dimethoxy-4- (prop-2-en-1-yl) phenol, 5) methyl (2E) -3- (4-hydroxyphenyl) prop-2-enoate.
    FIG 4 Inverse correlation spectrum of 1H-13C (HSQC) measured in DMSO-d6 at 25 ° C of dry stillage (lignin-containing material) derived from cellulosic bioethanol before catalytic depolymerization.
    FIG 5 Inverse correlation spectrum of 1H-13C (HSQC) measured in DMSO-d6 at 25 ºC
    30 of dry stillage (material with lignin content) derived from cellulosic bioethanol after treatment in methanol for 4 h at 200 ºC, 750 rpm and 25 bar of H2 in the absence of catalyst.
    FIG. 6 GC-MS chromatogram of major products identified in Example 2; 1) 4-ethylphenol, 2) 2,3-dihydro-1-benzofuran, 3) 1- (2-methoxyphenyl) ethanol, 4) 2,6-dimethoxy-4- (prop-2-en-1-yl) phenol, 5) methyl (2E) -3- (4-hydroxyphenyl) prop-2-enoate.
    FIG 7: Inverse correlation spectrum of 1H-13C (HSQC) measured in DMSO-d6 at 25 ºC of dry lignin derived from the production of cellulosic bioethanol after 4 h of reaction at 200 ° C, 25 bar of H2 and 750 rpm stirring in the presence of 50 mg of a 5% Ru / ZrO2 catalyst. The initial mass of lignin was approximately 500
    5 mg and 20 ml of methanol was used as the solvent.
    FIG 8: GC-MS chromatogram of the main products identified in Example 3; 1) 4-ethylphenol, 2) 2,3-dihydro-1-benzofuran, 3) 1- (2-methoxyphenyl) ethanol, 4) 2,6-dimethoxy-4- (prop-2-en-1-yl) phenol, 5) methyl (2E) -3- (4-hydroxyphenyl) prop-2-enoate.
    FIG 9: GC-MS chromatogram of the main products identified in Example 4; 1) 4-ethylphenol, 2) 2,3-dihydro-1-benzofuran, 3) 1- (2-methoxyphenyl) ethanol, 4) 2,6-dimethoxy-4- (prop-2-en-1-yl) phenol, 5) methyl (2E) -3- (4-hydroxyphenyl) prop-2-enoate.
    15 FIG 10: Inverse correlation spectrum of 1H-13C (HSQC) measured in DMSO-d6 at 25 ºC of dry lignin derived from the production of cellulosic bioethanol after 4 h of reaction at 200 ° C, 25 bar of H2 and 750 stirring rpm in the presence of 50 mg of a 5% Ru / ZrO2 / MWCNT catalyst. The initial mass of lignin was approximately 500 mg and 20 ml of methanol was used as the solvent. EXAMPLES
    A cascade process for the isolation, purification and depolymerization of lignin streams using a heterogeneous catalyst is described below.
    25 Figure 1 shows the detailed process diagram for the isolation, purification and depolymerization of lignin streams, ex. stillage from the production of cellulosic bioethanol. Initially, the lignin stream (1) is fed into the purification unit (19) operating at temperatures between 298 K and 373 K, in which an aqueous acidic solution is added via stream (6). In this unit of
    30 purification (19) any cellulose and / or hemicellulose residue present in stream (1) is solubilized, while the lignin polymers selectively precipitate.
    The resulting stream (2) is fed to the separation unit (20), in which the
    Solids comprising lignin polymers are separated in stream (7) and the liquid fraction, stream (3), is sent to the acid recovery unit (21). The
    Recovery unit (21) separates any solid and additional organic material from the acid solution, obtaining a stream rich in acid (6) that is recycled to unit (19), while the stream enriched in impurities (5) is sent to the water treatment facility. In order to keep the pH constant in the
    5 unit (19), fresh acid is added to the process through stream (4), consistentin concentrated acid.
    The lignin stream (7) is fed to the unit (22) to adjust its pH and carry out the final conditioning. Stream (9) can be either a dilute aqueous solution
    10 with basic pH, or a stream of water with neutral pH. The stream (8) containing the liquid fraction is sent to the wastewater treatment plant, while the solid stream (10) containing the purified lignin is sent to the reactor (23) containing the catalyst. Alternatively, the lignin stream produced in unit (20) can be sent directly to reaction unit (23) by means of
    15 current (11), bypassing or bypassing the pH adjustment unit (22). In another alternative, the lignin stream (1) can be fed directly into the reactor (23) by the stream (18) bypassing or bypassing the units (19), (20) and (22); if the purity of the lignin stream is high enough, i. and. it has a low ash and cellulose content.
    The reactor (23) can be operated in a simple liquid phase or in a biphasic liquid phase depending on the concentration of water in the input lignin stream: streams (10), (11) and (18).
    In one embodiment, the reactor (23) operates in a single phase comprising water or dilute alcohols (26), lignin macromolecules, the hydrogenation catalyst (A), and a reducing agent stream (12).
    In another embodiment, the reactor (23) operates in liquid phase biphasic mode, which includes
    30 aqueous phases (eg water, alcohols or mixtures thereof) and organic phases (eg aromatic compounds derived from lignin, gasoline, diesel or toluene) with volumetric ratios of aqueous to organic phase between 0.1: 1 and 10: 1 .
    The product of the depolymerization of lignin (14) is fed to the separation unit (24) which separates the solvent and the non-depolymerized lignin to be
    recycled in stream (13) from the aromatics stream derived from lignin in stream (15).
    Alternatively, the purified aromatic compounds separated in the unit of
    5 process (24) are fed to the reactor (25), in which they are converted into products ofadded value (eg ethanol, butanol) (17) using modified microorganismsgenetically to metabolize aromatic compounds.
    Figure 2 shows in detail an alternative process diagram for insulation,
    10 purification and depolymerization of lignin streams, ex. stillage from the production of cellulosic bioethanol using a catalyst with magnetic properties. In this process, an outlet stream (27) from the reactor (23) reaches an electromagnetic separator (28) that recovers the catalyst by applying a magnetic field. The purified stream (30) is fed back to the reactor (23).
    Furthermore, the use of an electromagnetic separator allows the extraction of partially depolymerized lignin (stream 29) from the catalyst retained in the electromagnetic separator and the monomers (stream 31). Stream (31) is fed to process unit (24) for subsequent fractionation of phenolic compounds.
    The most critical stage of the cascade process described by Figures 1 and 2 is the depolymerization of the lignin streams using the reactor (23), which operates in a single phase.
    To evaluate this critical stage the following catalysts were synthesized (see Table 1):
    Sample A: 5% M / ZrO2 nanoparticles, where M = transition metal
    Zirconia (ZrO2 nanoparticles) was synthesized by precipitation of zirconium hydroxide. First, 37.53 g of hydrated Zr (IV) oxynitrate were added to
    405.7 ml of deionized water and the mixture was stirred for 2 hrs until the salt was completely dissolved. Then an ammonium solution was added dropwise to initiate the precipitation, until reaching a pH of 10. Once precipitated, the solid was aged at room temperature between 65 and 72 hours, controlling and adjusting the pH
    35 when necessary to ensure that the pH was maintained at 10 throughout the process. The resulting solid was filtered and washed with deionized water, until the pH of the
    Wash water was equal to 7. This solid was washed 3 times with ethanol to remove additional impurities. The solid was dried in an oven for 12 h and calcined in a muffle at 500 ° C for 10 h. The final mass of ZrO2 was 12.87 g.
    5 Sample A1: the 5% Ru / ZrO2 catalyst was synthesized by impregnation inexcess. For this synthesis, a certain amount of the precursor salt (RuCl3) isdissolved in deionized water, in order to obtain a solution that would allowproduce a catalyst with 5% by weight of the active metal on the support. TheThe solution was impregnated on the desired support and the catalyst was dried in an oven at
    10 100 ºC overnight. The resulting catalyst was calcined in a muffle in an air atmosphere, with a temperature ramp of 2 hours until reaching 400ºC and then the catalyst was kept at 400ºC for 4h.
    Sample A2: the 5% Ni / ZrO2 catalyst was synthesized following the same procedure
    15 than for the previous catalyst, but the active metal was impregnated by impregnation at incipient humidity, the precursor being Ni (NO3) 2.
    Sample B: 5% X / MWCNT, where X = transition metal or ZrO2 nanoparticles
    5 g of MWCNT-MgO-Al2O3 were prepared by chemical vapor phase deposition of carbon on an FeCo catalyst. The following precursors were dissolved in 35 ml of deionized water: 8.97 g of Mg (NO3) 2.6H2O, 31.35 mg of (NH4) 6Mo7O24.4H2O, 870 mg of Fe (NO3) 3.9H2O and 5.54 g of Al (NO3) 3.9 H2O. The salts were mixed with 5 g of citric acid. The dry solid was calcined for 3 h at 773 K.
    To grow the MWCNTs, 500 mg of FeCo-MgO-Al2O3 was placed inside a flow reactor heated to 773 K in a continuous flow of H2 for 30 minutes. Then the temperature was raised to 973 K in He flow for 20 minutes. Finally, a flow of C2H4 in He was fed with a volumetric ratio of 1: 3 (C2H4: He) for 10 min at 973 K to obtain MWCNT-MgO-Al2O3. Then the MgO
    30 Al2O3 used as support was eliminated: 5 g of MWCNT-MgO-Al2O3 were treated in a 10% HF solution for 1 h and at 323 k to eliminate the support of metal oxides (MgO and Al2O3), obtaining the MWCNT. The resulting material was washed with distilled water until it reached a neutral pH. Then, 1 g of purified MWCNT was treated with 50 ml of nitric acid (HNO3, 16M) while stirring.
    35 for 3 h at 393 K. The resulting product was cooled to room temperature and then filtered using nylon filters with a pore size of 0.22 µm. The solids
    recovered were repeatedly washed with deionized water until a pH of
    7. The oxidized carbon nanotubes (MWCNT-COOH, acid treated) were dried at 343 K overnight in a vacuum oven. Then, 1 g of MWCNT-COOH was added to a mixture of 20 ml of sulfuric acid (H2SO4, 18 M) and 300 ml of
    5 acetic anhydride ((CH3-CO) 2O), under constant stirring at 353 K. After 2 h, the reaction mixture was cooled to room temperature and the thick mixture obtained was filtered and washed with deionized water to remove any residual acid, and then dried overnight in a 343K vacuum oven.
    10 Sample B1: the 5% Ru / MWCNT catalyst was synthesized by the early moisture impregnation method. A certain amount of the precursor salt (RuCl3) was dissolved in a mixture with a 1: 1 ratio (v / v) of methanol and deionized water, in order to obtain a solution that allows to obtain a catalyst with 5% by weight of the active metal in the support. The solution soaked into the
    15 desired support and then the catalyst was dried in an oven at 100 ° C overnight. Then, the calcination of the catalyst was carried out in a quartz tubular reactor, with a vertical flow of nitrogen of 20 ml / min. A temperature ramp of 3 ° C / min was established until reaching 400 ° C and then the catalyst was kept at this temperature for 4 h under nitrogen flow.
    20 Sample B2: the 5% Ni / MWCNT catalyst was synthesized following the same procedure as for the previous catalyst, but the precursor used was Ni (NO3) 2.
    Sample B3: The 50% ZrO2 / MWCNT catalyst was prepared using a 70 vol. Zirconium propoxide solution. % in propanol (C12H28O4Zr) obtained from Sigma-Aldrich to prepare an impregnation solution of the precursor in isopropanol
    (99.99% from Sigma-Aldrich). To impregnate 200 mg of MWCNT-purified (supplied by SouthWest NanoTechnologies), 0.49 ml of 70 vol. Zirconium isopropoxide. % propanol were dissolved in 0.31 ml of isopropanol. The solution was impregnated by impregnation at incipient humidity in an inert atmosphere. The impregnated material was dried in an oven at 100 ° C overnight. The solids were then calcined in a plug flow reactor with a vertical nitrogen flow of 20 ml / min. A temperature ramp of 3 ºC / min was established until
    35 reach 400 ° C and then the catalyst was kept at this temperature for 4 hours under nitrogen flow.
    Sample C: 5% M / ZrO2 / MWCNT, where M = transition metal
    Sample C1: the 5% Ru / ZrO2 / MWCNT catalyst was synthesized by the incipient moisture impregnation method. A certain amount of the precursor salt 5 (RuCl3) was dissolved in a certain amount of a 1: 1 (v / v) mixture of methanol and water, in order to obtain a solution that would allow to obtain a catalyst with 5% by weight of the active metal in the support. The support used for this catalyst was the 50% ZrO2 / MWCNT catalyst described above. The solution was impregnated on the desired support and then the catalyst was dried in an oven at 100
    10ºC overnight. Then, the calcination of the catalyst was carried out in a quartz tubular reactor, with a vertical flow of nitrogen of 20 ml / min. A temperature ramp of 3 ° C / min was established until reaching 400 ° C, keeping the catalyst at this temperature for 4 hours under nitrogen flow.
    15 Sample D: 5% M / ZrO2 / MWCNT- magnetic Fe2O3 nanoparticles, where M = transition metal
    Sample D1: the catalyst of M / ZrO2 / MWCNT- magnetic nanoparticles of Fe2O3 with magnetic properties was synthesized according to the following steps:
    20 The first step consisted of the oxidation of the carbonaceous support (MWCNT) to generate oxygenated functional groups. These functional groups should anchor the magnetic Fe2O3 nanoparticles. For the oxidation of the carbonaceous support (MWCNT), a certain amount of carbon nanotubes was added to a
    25 solution of 60% v / v of HNO3, stirring at 65ºC for 3 hours and at 300 rpm. Then, the mixture was neutralized, first by dilution with deionized water and then slowly adding ammonia until the pH was equal to 7. The neutralized mixture was filtered with a Büchner and the solid obtained was washed with deionized water. Said solid was dried in an oven at 80ºC overnight.
    The second step consisted of anchoring the Fe2O3 magnetic nanoparticles on the surface of the support (MWCNT) by means of deposition methods such as impregnation in excess and / or impregnation with incipient humidity. For the incorporation of the magnetic particles, first a solution of FeN3O9.H2O was prepared. The
    35 oxidized carbon nanotubes from the previous step were added to this solution and the mixture was kept stirred for 3 hours and then the solution was evaporated
    maintaining agitation. The solids were recovered and dried in an oven at 100 ° C overnight. The solid was then heat treated at 750 ° C for 3 hours in a flow of 100 ml / min of nitrogen, to form the magnetic species of iron. The solid obtained was sieved and the fraction with a particle size per
    5 below 100 µm was recovered for use as a magnetic support.
    The third step consisted of impregnation with ZrO2 and Ru of the MWCNT support comprising Fe2O3 magnetic particles in the same way as with sample C1.
    The following Table 1 summarizes the synthesis of the catalysts.
    Table 1: Catalysts used in the depolymerization of lignin streams
    Sample A Nanoparticles 5% M / ZrO2 Sample B Nanoparticles 5% X / MWCNT X = M or ZrO2Sample C 5% M / ZrO2 / MWCNTSample D 5% M / ZrO2 / MWCNT Fe2O3 magnetic nanoparticles
    Sample A1 Nanoparticles 5% Ru / ZrO2 Sample B1 5% Ru / MWCNTSample C1 5% Ru / ZrO2 / MWCNT nanoparticlesSample D1 5% Ru / ZrO2 / MWCNT Fe2O3 magnetic nanoparticles
    Sample A2 Nanoparticles 5% Ni / ZrO2 Sample B2 5% Ni / MWCNT
    Sample B3 5% ZrO2 / MWCNT nanoparticles
    In order to demonstrate the performance of the catalysts described above, a series of examples were carried out. Table 2 mentions the number of the example made using the different catalysts.
    Table 2: Example number versus the catalyst used
    Catalyst
    Example 1: Comparative No catalyst
    Example 2 Sample A1 Nanoparticles 5% Ru / ZrO2
    Example 3 Sample B1 5% Ru / MWCNT
    Example 4: Sample C1 5% Ru / ZrO2 / MWCNT nanoparticles
    Example 5: Comparative Ru / C
    The characterization methods used in each example were the following:
    5 In order to identify the products obtained in each example, 1 ml of the liquid product was extracted and filtered to be analyzed by gas chromatography with a mass spectrometer (GC-MS) equipped with an HP-5 chromatographic column (Agilent ) with a diameter of 0.32 µm and 30 m in length. The rest of the mix
    The reaction was centrifuged at 9000 rpm for 30 minutes to precipitate the dispersed solids. The liquid fraction was collected in a flask for further analysis and the solids were washed with 15 ml of a methanol: ethyl acetate mixture (2: 1) and then centrifuged again at 9000 rpm for 30 minutes. The liquid obtained after the second centrifugation was separated from the solids and added to the first fraction.
    15 liquid collection. The final liquid fraction was concentrated by means of a rotary evaporator, removing methanol and ethyl acetate from the reaction medium and the washing process.
    The catalytic and selective breaking of the C-O-C bonds of the lignin was carried out to
    20 depolymerize lignin effectively. Catalysts were selected for the hydrogenolysis of the C-O bonds of the lignin (see Table 1) seeking to achieve at the same time a minimum hydrogenation of the aromatic rings.
    2D NMR spectra of lignin were analyzed to quantify the degree of
    25 depolymerization of lignin, by determining the concentration of ȕ-O-4 bonds.
    The preparation of the samples for 2D NMR involved an acetalization process in a solution of acetic acid: pyridine (1: 1, v / v) stirred at room temperature for 48 hours. The reaction mixture was then concentrated in vacuo, the resulting residue was dissolved in DMSO, centrifuged, and the supernatant (acetylated lignin) was
    5 lyophilized. The NMR spectra of the acetylated samples were performed inDMSO-d6, to avoid fractionation of the sample before NMR analysis andto increase both the solubility and dispersion of the chemical shiftof the side chains.
    The 1H-13C inverse correlation spectra (HSQC) were measured at 25 ° C on a Bruker AVANCE III 700 MHz instrument equipped with a 5mmTCI cryogenically cooled gradient probe with inverse geometry, the proton coil closer to the sample. The HSQC (heteronuclear single quantum coherence) experiments were performed using the Brukers pulse program "hsqcetgpsisp2.2"
    15 (pulsed adiabatic version) with spectrum widths of 5000 Hz (from 10 to 0 ppm) and 20843 Hz (from 165 to 0 ppm) for dimensions 1H- and 13C. The number of complex points recorded was 2048 for dimension 1H with a recycling delay of 1.5 s. The number of transients was 64, and 256 time increments were recorded in dimension 13C in all cases. A 145 Hz 1JCH was used.
    20 processing employed a typical combined Gaussian apodization in dimension 1H and a squared cosine window apodization in dimension 13C. Before performing the Fourier transform, the data matrices were filled with zeros up to 1024 points in dimension 13C to have a continuous series of data. The central peak of the solvent was used as an internal reference (įC 39.5; įH 2.49). They were used
    Long-range J-coupling evolution times of 66 and 80 ms in different heteronuclear multiple binding correlations (heteronuclear multiple binding correlation, HMBC) for the acquisition experiments. The peaks were assigned by comparison with literature.
    30 The examples carried out are the following:
    Example 1: Depolymerization of lignin without catalyst
    In this experiment, 502.4 mg of lignin were placed inside the reactor (23)
    35 without catalyst. Then, 30 ml of methanol was added to the reactor before closing it and performing a leak test with N2. The reactor was purged three times with H2 to remove
    any remaining N2 and O2 present in the medium, and then pressurized to 25 bar with H2. The stirring speed was set at 750 rpm and the temperature was raised from room temperature to 200 ° C in 120 min. Once the desired temperature was reached, the reaction started. After 4 h of reaction, the
    5 heating and stirring and the reactor was cooled in an ice bath. When the reactor temperature was below 20 ° C, the reactor was carefully depressurized.
    The analysis of the samples revealed the following results: the organics recovered
    10 in the flask amounted to 242 mg. The recovered solids were weighed, obtaining 262.1 mg, which correspond to solid lignin.
    The closing of the material balance was 100.3%, with 48.2% corresponding to lignin converted into liquid products and 52.2% in solid products
    15 Figure 3 shows the GC-MS chromatogram obtained, in which the total area of the products obtained is 1.0 x 107 and the main products identified were: 1) 4-ethylphenol, 2) 2,3-dihydro-1 -benzofuran, 3) 1- (2-methoxyphenyl) ethanol, 4) 2,6-dimethoxy-4- (prop-2-en-1-yl) phenol, 5) methyl (2E) -3- (4-hydroxyphenyl) prop -2-enoate.
    Figure 4 shows the HSQC spectrum obtained for the dry stillage from the bioethanol production process, which contains macromolecular lignin in high concentrations. In this figure it is possible to identify ferulate, p-coumarate, coumaril, guaiacil, syringil, ȕ-O-ȕ ', ȕ-O-4, ȕ-O-5', -CH3, and -OCH3. In addition, it was possible to detect
    25 signals corresponding to oligosaccharides, which may be due to residual cellulose from the enzymatic hydrolysis and fermentation process. In this sample, the ȕ-O-4 bond represents around 42% of the lignin bonds, a value similar to those found in the literature.
    Figure 5 shows the HSQC results obtained for the same lignin sample after being treated in methanol for 4 h at 200 ° C, 750 rpm, and 25 bar of H2 in the absence of catalyst. Various functional groups can be identified, as well as lignin monomers such as ferulate, p-coumarate, coumaril, guaiacil, syringil, ȕO-ȕ ', ȕ-O-4, ȕ-O-5', -CH3, and -OCH3. In addition, signals could be detected
    35 corresponding to oligosaccharides, which may be due to residual cellulose from the enzymatic hydrolysis and fermentation process. In this sample the links ȕ-O-4
    they represented 37% of the total, which indicates that only 12% of the bonds were degraded after this treatment.
    Example 2: Depolymerization of lignin using nanoparticles of a catalyst5 5% Ru / ZrO2 (Sample A1)
    In this experiment, 50.5 mg of 5% Ru / ZrO2 were placed inside the reactor
    (23) along with 500.7 mg of lignin. Then, 30 ml of methanol was added to the reactor before closing the system and performing a leak test with N2. The reactor was purged three times with H2 to remove any remaining N2 and O2 present in the medium, and then pressurized to 25 bar with H2. The stirring speed was set at 750 rpm and the temperature was raised from room temperature to 200 ° C in 120 min. Once the desired temperature was reached, the reaction started. After 4 h of reaction, the heating and stirring were turned off and the reactor was cooled in a bath.
    15 ice. When the reactor temperature was below 20 ° C, the reactor was carefully depressurized.
    Analysis of the samples revealed the following results: the organics recovered in the flask amounted to 309.7 mg. The recovered solids were weighed,
    20 obtaining 312.2 mg, which correspond to solid lignin and the catalyst.
    The closing of the material balance was 114.2%, with 52.4% corresponding to lignin converted into liquid products and 61.9% in solid products
    25 Figure 6 shows the GC-MS chromatogram obtained, in which the total area of the products obtained is 1.1 x 107 and the main products identified were: 1) 4-ethylphenol, 2) 2,3-dihydro-1 -benzofuran, 3) 1- (2-methoxyphenyl) ethanol, 4) 2,6-dimethoxy-4- (prop-2-en-1-yl) phenol, 5) methyl (2E) -3- (4-hydroxyphenyl) prop -2-enoate.
    30 Figure 7 shows the HSQC results obtained from the dry stillage of the bioethanol production process, which contains macromolecular lignin in high concentrations, the same sample used in Example 1, after being treated in methanol for 4 h at 200 ° C, 750 rpm, and 25 bar of H2 in the presence of 5% Ru / ZrO2 catalyst nanoparticles (Sample A1). Various functional groups
    35 can be identified, as well as lignin monomers such as ferulate, p-coumarate, coumaril, guaiacil, syringil, ȕ-O-ȕ ', ȕ-O-4, ȕ-O-5', -CH3, and -OCH3. In addition, they could
    detect signals corresponding to oligosaccharides, which may be due to residual cellulose from the enzymatic hydrolysis and fermentation process. In this sample the ȕ-O-4 bonds represented 25% of the total, which indicates that only 60% of the bonds were degraded after this treatment.
    5Example 3: Depolymerization of lignin using the catalyst 5% Ru / MWCNT(Sample B1)
    In this experiment, 50.0 mg of 5% Ru / MWCNT was placed inside the
    10 reactor (23) together with 500.0 mg of lignin. Then, 30 ml of methanol was added to the reactor before closing the system and performing a leak test with N2. The reactor was purged three times with H2 to remove any remaining N2 and O2 present in the medium, and then pressurized to 25 bar with H2. The stirring speed was set at 750 rpm and the temperature was raised from room temperature to 200 ° C in 120 min. A
    Once the desired temperature was reached, the reaction started. After 4 h of reaction the heating and stirring were turned off and the reactor was cooled in an ice bath. When the reactor temperature was below 20 ° C, the reactor was carefully depressurized.
    The analysis of the samples revealed the following results: the organics recovered in the flask amounted to 260.7 mg. The recovered solids were weighed, obtaining 312.2 mg, with 52.1% of lignin converted into liquid products.
    Figure 7 shows the GC-MS chromatogram obtained, in which the total area of
    25 the products obtained is 2.4 x 107 and the main products identified were: 1) 4-ethylphenol, 2) 2,3-dihydro-1-benzofuran, 3) 1- (2-methoxyphenyl) ethanol, 4) 2,6-dimethoxy -4- (prop-2-en-1-yl) phenol, 5) methyl (2E) -3- (4-hydroxyphenyl) prop-2-enoate.
    Example 4: Depolymerization of lignin using the catalyst 5% 30 Ru / ZrO2 / MWCNT (Sample C1)
    In this experiment, 50.6 mg of 5% Ru / ZrO2 / MWCNT were placed inside the reactor (23) together with 500.4 mg of lignin. Then, 30 ml of methanol was added to the reactor before closing the system and performing a leak test with N2. The reactor was purged three times with H2 to remove any remaining N2 and O2 present in the medium, and then pressurized to 25 bar with H2. The stirring speed was set at 750
    rpm and the temperature was raised from room temperature to 200 ° C in 120 min. Once the desired temperature was reached, the reaction started. After 4 h of reaction the heating and stirring were turned off and the reactor was cooled in an ice bath. When the reactor temperature was below 20 ° C, the reactor was
    5 carefully depressurized.
    Analysis of the samples revealed the following results: organics recovered in the flask amounted to 280.4 mg. The recovered solids were weighed, obtaining 235.2 mg, corresponding to solid lignin and the catalyst.
    10 The closing of the material balance was 92.93%, with 56.04% corresponding to lignin converted into liquid products and 36.89% in solid products
    Figure 9 shows the GC-MS chromatogram obtained, in which the total area of
    15 the products obtained is 8.4 x 105 and the main products identified were: 1) ethyl 3- (4-hydroxy-3-methoxyphenyl) propanoate, 2) methyl-3- (4-hydroxyphenyl) acrylate, 3) 2.3 -dihydro-1-benzofuran, 4) 4-ethylphenol and 5) methyl (2E) -3- (4-hydroxyphenyl) prop-2enoate.
    20 Figure 10 shows the HSQC results obtained for the same lignin sample, after being treated in methanol for 4 h at 200 ° C, 750 rpm, and 25 bar of H2 in the presence of nanoparticles of the catalyst 5% Ru / ZrO2 / MWCNT. Various functional groups can be identified, as well as lignin monomers such as ferulate, p-coumarate, coumaril, guaiacil, syringil, ȕ-O-ȕ ', ȕ-O-4, ȕ-O-5', -CH3, and -OCH3 .
    Furthermore, signals corresponding to oligosaccharides could be detected, which may be due to residual cellulose from the enzymatic hydrolysis and fermentation process. In this sample the ȕ-O-4 bonds represented 8.1% of the total, which indicates that a
    80.7% of the bonds were degraded after this treatment.
    30 Example 5: Depolymerization of lignin using a 5% Ru / C catalyst
    In this experiment, 50.4 mg of 5% Ru / C was placed inside the reactor (23) along with 500.1 mg of lignin. Then, 30 ml of methanol was added to the reactor before closing the system and performing a leak test with N2. The reactor was purged three times with H2 to remove any remaining N2 and O2 present in the medium, and then pressurized to 25 bar with H2. The stirring speed was set at 750
    rpm and the temperature was raised from room temperature to 200 ° C in 120 min. Once the desired temperature was reached, the reaction started. After 4 h of reaction the heating and stirring were turned off and the reactor was cooled in an ice bath. When the reactor temperature was below 20 ° C, the reactor was
    5 carefully depressurized
    GC-MS analysis revealed the following results: the organics present in the flask were weighed, assuming 278.3 mg. The solids previously separated were also collected in a flask and dried on a rotary evaporator to remove any
    10 remainder of solvent. The recovered solids were weighed, obtaining 278 mg, corresponding to solid lignin and the catalyst.
    The closing of the material balance was 101.2%, with 55.6% of lignin converted to liquid products and 45.5% to solid products. The main products
    15 identified were: 1) 4-ethylphenol, 2) 2,3-dihydro-1-benzofuran, 3) 1- (2-methoxyphenyl) ethanol, 4) 2,6-dimethoxy-4- (prop-2-en-1- yl) phenol, 5) methyl (2E) -3- (4-hydroxyphenyl) prop-2-enoate.
    Main results
    The reaction results are summarized in Table 3 where it can be identified that the mass percentage of liquid produced using catalysts was increased compared to the blank (experiment without catalyst). It is possible to identify that when a catalyst is not used in the process the mass of
    25 organic liquids is significant (48%) when compared with the results observed when Ru / C and Ru / MWCNT are used as catalysts, in which the liquid fraction represents 56% and 62%, respectively. It is important to consider that the fraction of liquids obtained after reaction does not necessarily correlate with the degree of depolymerization since the liquid contains a
    30 mixture of oligomers that can be produced through the breaking of non-objective bonds such as -OH, O-CH3, C-C, and C = O, which lead to the formation of monomers. In contrast, 2D NMR can inform the true degree of depolymerization since it is possible to determine the relative concentration of the target bonds (C-O of the ɴ-O-4 type) in the lignin after reaction.
    Table 3: Balance of matter, organic liquid and solid fractions obtained after the depolymerization reaction of stillage (lignin current) of examples 1
    5:
    Example CatalystRecovered mass of organic liquid (%)Recovered mass of solids (%)Material balance close (%)
    1 No catalyst4852100
    2 Sample A1: Nanoparticles of 5% Ru / ZrO26252114
    3 Sample B1: 5% Ru / MWCNT52--
    4 Sample C1: 5% Ru / ZrO2 / MWCNT563793
    5 5% Ru / C534295
    The results obtained in the different inverse correlation spectra of 1H-13C (HSQC) measured are shown in Table 4. The C-O bonds represent 60% of the total bonds in lignin. Specifically, ɴ-O-4 bonds represent approximately 40% of the total C-O bonds in lignin, which have been
    10 considered as the target links. For this reason, the percentage of depolymerization of lignin was estimated using the relative change in the concentration of the ɴ-O-4 bonds in the lignin (see Equation 1) after reaction.
    ሾ Ψ ఉ ି ை ିସ ሿ ೔೙೔೎೔ೌ೗ ି ሾ Ψ ఉ ି ை ିସ ሿ ೑೔೙ೌ೗
    15 Eq. 1
    Ψ ஽௘௦௣௢௟௜௠௘௥௜௭௔௖௜ × ௡ ൌ ሾ Ψ ఉ ି ை ିସ ሿ
    ೔೙೔೎೔ೌ೗
    The quantification of ɴ-O-4 bonds in lignin was based on the C2-H (G2) signals of guaiacil (G) as an internal standard, since the C2 position of the guaiacil unit is never substituted, and is easily identifiable. in the HSQC spectrum (Eq. 2) and
    20 where S is the area under the surface (HSQC). െ
    ܱ Ψ ߚ െ
    ஺௥௘௔ ഁ ష ೀ షర
    Eq. 2 ͳͲͲ כ ൌ Ͷ
    ቆ ஺௥௘௔ ഁ ష ೀ షర ା ஺௥௘௔ ೄ మ ା ஺௥௘௔ మ ಸ ቇ ల
    Table 4: Degree of depolymerization of ȕ-O-4 obtained from the inverse correlation spectrum of 1H-13C (HSQC) measured in DMSO-d6 at 25 ° C for the lignin stillage of the bioethanol production process, using methanol as solvent.
    Example CatalystReaction volume (ml)% of ȕ-O-4% depolymerization of ȕ-O-4
    1 No catalystfifty33.6%19.8%
    2 Sample A1: 5% Ru / ZrO2fifty23.4%44.0%
    3 Sample B1: 5% Ru / MWCNTfifty10.6%74.7%
    4 Sample C1: 5% Ru / ZrO2 / MWCNTfifty8.1%80.7%
    5 5% Ru / Cfifty17.6%57.9%
    The catalytic activity towards the depolymerization of the ȕ-O-4 bonds of lignin varies significantly from one catalyst to another. For example, when the reaction is carried out using the Ru / ZrO2 nanoparticle catalyst (Sample A1), the degree of depolymerization reached values of 44%. On the contrary, when the catalysts Ru / ZrO2 / MWCNT or Ru / MWCNT were used, the concentration of ȕ-O-4 decreased by 80.7% and 74%, respectively. It is clear that making the catalyst more accessible to the bulk of the polymeric structure of the lignin
    Increasing the catalytic surface area that interacts with the lignin is critical to maximize the efficiency of the catalyst and therefore the degree of depolymerization of the lignin.
    However, when a high surface area material with high microporosity
    20 (i.e. pore size less than 2 nm) as active carbon is used as Ru support, the degree of depolymerization only reaches values between 57.9 and 70%,
    depending on the volume of the reactor used. This indicates the strong dependence of the system on the accessibility of lignin to the active site. Lignin is a macromolecule that forms large agglomerates in solution (D = 0.1 μm - 2 μm) with a high diffusion radius, which makes it difficult to access the internal surface
    5 of a material with small pore size (2 nm - 50 nm). Therefore, when activated charcoal is used, the lignin is not able to diffuse efficiently through the porous structure of the support to reach the active sites. Instead, only small fragments (eg oligomers, dimers, and monomers) diffuse into the porous structure of activated carbon, limiting its catalytic activity.
    权利要求:
    Claims (45)
    [1]
    1. A process for the depolymerization of lignin, where the process comprises at least one step a) of contact between a stream containing lignin with a catalyst consisting of a transition metal and a support,
    where support is selected from the list consisting of
    x metal oxide nanoparticles
    x a one-dimensional structure
    x nanoparticles of metal oxides supported in a one-dimensional structure
    and said step (a) is carried out in the presence of
    x a reducing agent; and
    x a solvent selected from the list consisting of water, ethanol,
    methanol, propanol, butanol, decalin, benzene, toluene, xylene, cyclohexane, gasoline, diesel, and a combination thereof.
    [2]
    The process according to claim 1, wherein the transition metal is selected from the list consisting of Sn, Ga, Mg, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au and combination of the
    20 themselves.
    [3]
    3. The process according to claim 2, wherein the transition metal is selected from the list consisting of Ni, Ru, Pd, Fe, Mo, Co, Cu, Fe and a combination thereof.
    [4]
    Four. The process according to claim 3, wherein the transition metal is selected from Ru, Ni and a combination thereof.
    [5]
    5. The process according to any one of claims 1 to 4, wherein the metal of
    The transition is in the form of a metallic aggregate with a particle size between 1 and 100 nm.
    [6]
    6. The process according to claim 5, wherein the transition metal is in
    form of a metallic aggregate with a particle size between 2 and 50 nm. 35


    [7]
    7. The process according to claim 6, wherein the transition metal is inform of a metallic aggregate with a particle size between 2 and 5 nm.
    [8]
    8. The process according to any of claims 1 to 7, wherein the nanoparticlesof metal oxides are selected from the list consisting of SiO2, TiO2, V2O5,Cr2O3, MnO2, MgO, Fe2O3, FeO, CoO, ZnO, Y2O3, ZrO2, Nb2O5, CdO, La2O3, SnO2,HfO2, Ta2O5, WO3, Re2O7, Al2O3, CeO2, Cs2O and combination thereof.
    [9]
    9. The process according to claim 8, wherein the metal oxide nanoparticlesis selected from the list consisting of TiO2, V2O5, Cr2O3, MnO2, ZrO2, CeO2 andcombination thereof.
    [10]
    10. The process according to claim 9, wherein the metal oxide nanoparticles are selected from the list consisting of TiO2, V2O5, MnO2, ZrO2, CeO2 and a combination thereof.
    [11]
    eleven. The process according to any of claims 1 to 10, wherein the one-dimensional structure is selected from the list consisting of C nanotubes, TiO2 nanotubes, V2O5 nanotubes, MnO2 nanotubes, ZrO2 nanotubes, carbon fibers, graphene sheets and combination thereof.
    [12]
    12. The process according to claim 11, wherein the one-dimensional structure is nanotubes of C.
    [13]
    13. The process according to claim 12, wherein the C nanotubes have a length: diameter aspect ratio that varies between 5 and 2000 with lengths between 50 and 5000 nm.
    [14]
    14. The process according to any of claims 11 to 13, wherein the one-dimensional structure comprises magnetic nanoparticles on its surface.
    [15]
    fifteen. The process according to claim 14, wherein the magnetic nanoparticles are Fe (III) oxide nanoparticles.


    [16]
    16. The process according to claim 15, wherein the percentage by weight of the Fe (III) metal oxide nanoparticles in the one-dimensional structure varies between 5% and 60% by weight.
    The process according to claim 16, wherein the percentage by weight of theFe (III) metal oxide nanoparticles in one-dimensional structure variesbetween 10% and 50% by weight.
    [18]
    18. The process according to claim 17, wherein the percentage by weight of the
    10 Fe (III) metal oxide nanoparticles in the one-dimensional structure varies between 20% and 40% by weight.
    [19]
    19. The process according to any one of claims 1 to 18, wherein the agent
    Reducer is selected from the list consisting of hydrogen, formic acid, ethanol, methanol, and a combination thereof.
    [20]
    20. The process according to any of claims 1 to 19, wherein step a) is carried out at pressures between 10 bar and 100 bar and temperatures between 150 ° C and 400 ° C.
    [21]
    21. The process according to claim 20, wherein step a) is carried out at pressures between 10 bar and 70 bar.
    [22]
    22. The process according to claim 21, wherein step a) is carried out at pressures between 30 bar and 60 bar.
    [23]
    23. The process according to claim 22, wherein step a) is carried out at pressures between 40 bar and 60 bar.
    24. The process according to any of claims 20 to 23, wherein step a) is carried out at temperatures between 150 ° C and 300 ° C.
    [25]
    25. The process according to claim 24, wherein step a) is carried out at temperatures
    between 150 ºC and 250 ºC. 35


    [26]
    26. The process according to claim 25, wherein step a) is carried out at temperatures between 180 ° C and 200 ° C.
    [27]
    27. The process according to any of claims 1 to 26, wherein the current that5 contains lignin used in step a) has been previously purified.
    [28]
    28. The process according to any of claims 1 to 27, wherein the pH of the stream containing lignia from step a) is between 4 and 8.
    29. The process according to claim 28, wherein the pH of the lignin-containing stream of step a) is between 4 and 6.
    [30]
    30. The process according to any of claims 1 to 29, comprising a
    step b) recovery of the catalyst. fifteen
    [31]
    31. The process according to claim 30, wherein step b) of catalyst recovery is carried out by filtering.
    [32]
    32. The process according to any of claims 30 or 31, comprising a
    20 step b ') of recovery of the catalyst by applying a magnetic field of between 0.1 Teslas and 5 Teslas, where said catalyst comprises a one-dimensional structure comprising magnetic nanoparticles on its surface.
    33. The process according to any of claims 1 to 32, comprising a step c) of purification of the stream obtained in steps b) or b ') by separating a stream consisting of a solvent and a stream that It contains non-depolymerized lignin from another stream consisting of aromatic compounds derived from lignin.
    [34]
    34. A process for obtaining ethanol and / or butanol comprising x steps a) to c) of depolymerization of lignin according to any of claims 1 to 33; and x a stage d) of contact between genetically microorganisms
    35 modified with the aromatic compounds derived from lignin in step c).


    [35]
    35. The process according to claim 34, wherein the genetically modified microorganisms is selected from the list consisting of fungi basidiomycetes, chrysosporium phanerochaete, and streptomyces spp.
    [36]
    36. A catalyst comprising a transition metal and a support, where the support consists of metal oxide nanoparticles supported in a one-dimensional structure.
    37. The catalyst according to claim 36, wherein the transition metal is selected from the list consisting of Sn, Ga, Mg, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y , Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au and a combination thereof.
    38. The catalyst according to claim 37, wherein the transition metal is selected from the list consisting of Ni, Ru, Pd, Fe, Mo, Co, Cu, Fe and combination thereof.
    [39]
    39. The catalyst according to claim 38, wherein the transition metal is selected from Ru, Ni and combinations thereof.
    [40]
    40. The catalyst according to any of claims 36 to 39, wherein the transition metal is in the form of a metallic aggregate with particle sizes between 1 nm and 100 nm.
    [41]
    41. The catalyst according to claim 40, wherein the transition metal is in the form of a metallic aggregate with particle sizes between 2 nm and 50 nm.
    42. The catalyst according to claim 41, wherein the transition metal is in the form of a metallic aggregate with particle sizes between 2 and 5 nm.
    [43]
    43. The catalyst according to any of claims 36 to 42, wherein the
    35 metal oxide nanoparticles are selected from the list consisting of SiO2, TiO2, V2O5, Cr2O3, MnO2, MgO, Fe2O3, FeO, CoO, ZnO, Y2O3, ZrO2, Nb2O5, CdO,

    La2O3, SnO2, HfO2, Ta2O5, WO3, Re2O7, Al2O3, CeO2, Cs2O and combination thereof.
    [44]
    44. The catalyst according to claim 43, wherein the oxide nanoparticles
    5 metals are selected from the list consisting of TiO2, V2O5, Cr2O3, MnO2, ZrO2,CeO2 and combination thereof.
    [45]
    45. The catalyst according to claim 44, wherein the oxide nanoparticles
    Metals are selected from the list consisting of TiO2, V2O5, MnO2, ZrO2, CeO2 and combination thereof.
    [46]
    46. The catalyst according to any of claims 36 to 45, wherein the one-dimensional structure selected from the list consisting of C nanotubes, TiO2 nanotubes, V2O5 nanotubes, MnO2 nanotubes, ZrO2 nanotubes,
    15 carbon fibers, graphene sheets, and a combination thereof.
    [47]
    47. The catalyst according to claim 46, wherein the one-dimensional structure is nanotubes of C.
    48. The catalyst according to claim 47, wherein the C nanotubes have a length: diameter aspect ratio ranging between 5 and 2000 with lengths between 50 and 5000 nm.
    [49]
    49. The catalyst according to claim 48, wherein the one-dimensional structure 25 comprises magnetic nanoparticles on its surface.
    [50]
    50. The catalyst according to claim 49, wherein the magnetic nanoparticles are magnetic nanoparticles of Fe (III) oxide.
    51. The catalyst according to claim 50, wherein the percentage by weight of the magnetic nanoparticles of Fe (III) in the one-dimensional structure varies between 5% and 60% by weight.
    [52]
    52. The catalyst according to claim 51, wherein the percentage by weight of the
    Magnetic nanoparticles of Fe (III) oxides in the one-dimensional structure vary between 10% and 50% by weight.


    [53]
    53. The catalyst according to claim 52, wherein the percentage by weight of the magnetic nanoparticles of Fe (III) oxides in the one-dimensional structure varies between 20% and 40% by weight.
    [54]
    54. Use of the catalyst described in any of claims 36 and 53 for the depolymerization of lignin.

    FIG 1

    FIG 2
    14 15
    3. 4

    FIG 3
    35

    FIG 4
    36

    FIG 5
    37

    FIG 6
    38

    FIG 7
    39

    FIG 8
    40

    FIG 9
    41

    FIG 10
    42
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    公开号 | 公开日
    ES2642143B1|2018-09-06|
    WO2017178686A1|2017-10-19|
    引用文献:
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    CN112072085A|2020-08-20|2020-12-11|华南理工大学|Nano lignin zinc oxycarbide composite material and preparation method and application thereof|
    WO2018119152A1|2016-12-22|2018-06-28|National Technology & Engineering Solutions Of Sandia, Llc |Synthesis of bioproducts from lignin-derived aromatics by genetically modified microorganisms|
    CN111072477B|2019-12-31|2021-03-30|华南理工大学|Method for preparing p-hydroxycinnamate by carrying out copper-catalyzed depolymerization on lignin|
    CN111170402B|2020-02-12|2021-07-02|东华大学|Method for removing perfluorooctanoic acid in water body by using lignin-based carbon nano tube|
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