WO2012177138A1 - Procédé de reformage en phase liquide de la lignine en produits chimiques aromatiques et en hydrogène - Google Patents

Procédé de reformage en phase liquide de la lignine en produits chimiques aromatiques et en hydrogène Download PDF

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WO2012177138A1
WO2012177138A1 PCT/NL2012/050446 NL2012050446W WO2012177138A1 WO 2012177138 A1 WO2012177138 A1 WO 2012177138A1 NL 2012050446 W NL2012050446 W NL 2012050446W WO 2012177138 A1 WO2012177138 A1 WO 2012177138A1
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lignin
catalyst
process according
ethanol
liquid
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PCT/NL2012/050446
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Joseph John ZAKZESKI
Pieter Cornelis Antonius BRUIJNINCX
Bert Marc Weckhuysen
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Universiteit Utrecht Holding B.V.
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • C01B2203/107—Platinum catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/802—Diluents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to processes for the conversion of lignin-containing feeds using transition metal catalysts to produce hydrogen, light hydrocarbons and platform aromatic chemicals. More specifically, the present invention relates to a catalytic process for the conversion of lignin-containing feeds into monomeric aromatic chemicals, hydrogen, and light gases, including methane and ethane.
  • Lignin comprises between 15-30% of lignocellulosic biomass by weight and about 40% by energy [12] and consists of methoxylated phenylpropene structures that confer strength and rigidity to plants [13-15].
  • Isolated lignin is usually obtained by deployment of a pretreatment method, such as the kraft and organosolv methods, which degrade the extended polymer to smaller compounds and, depending on the method, causes other chemical transformations such as sulfur incorporation [1 ].
  • aqueous-phase reforming (APR) of biomass-derived oxygenated compounds such as methanol, glycol, glycerol, sorbitol, xylose, and glucose
  • T ⁇ 538°C relatively low temperatures
  • the preferred catalysts for these systems comprise Group VIII transition metals, including alloys and mixtures, with platinum, ruthenium, or rhodium giving the most favorable results as disclosed by U.S. Pat. Nos.
  • the catalyst support is preferably selected from the group consisting of alumina, boron nitride, carbon, ceria, silica, silica-alumina, silica nitride, titania, zirconia, or mixtures thereof, which silica the preferential support [27, 28].
  • alumina boron nitride, carbon, ceria, silica, silica-alumina, silica nitride, titania, zirconia, or mixtures thereof, which silica the preferential support [27, 28].
  • Tokarev et al. [35] described the beneficial effect of co-reforming of the substrates ethanol and sorbitol for the production of hydrogen .
  • One of the objects of the present invention is to provide a process for the valorization of lignin for the production of monomeric aromatic compounds, hydrogen, light alkanes, and other useful components in the biorefinery scheme.
  • Another object of the present invention is to provide a process that operates under milder conditions than thus far employed in this field.
  • Another object of the present invention is to minimize unwanted side-products, such as highly recalcitrant solids formed during conventional aqueous-phase reforming reactions.
  • a process for the liquid-phase reforming of lignin into monomeric, dimeric, and oligomeric aromatic chemicals, hydrogen, and other light gases is provided.
  • the process uses components readily obtained from a second-generation lignocellulosic biorefinery and improves the chemical and energy integration of the biorefinery scheme.
  • lignin obtained from a selected pretreatment method is solubilized in water-containing solvents followed by the catalytic liquid-phase reforming in the optional presence of a co-catalyst.
  • the characteristics of the isolated aromatic components, the gases, and the solvent following the process depend heavily on the reaction conditions employed, particularly the presence of the catalyst and co-catalyst, and therefore the product distribution is highly tunable depending on chemical demand.
  • the aromatic products consist of alkylated phenol, guaiacol, catechol, and syringol monomers, dimers, and oligomers with the particular distribution based on the reaction conditions employed.
  • the invention provides a catalytic process for the liquid-phase reforming of lignin to monomeric aromatic compounds, hydrogen, light alkanes, and other useful chemicals that readily integrate into the biorefinery scheme.
  • the one-step process of the invention involves the solubilization of lignin in water-containing solvents and contacting with a group VIII transition metal catalyst. Surprisingly, it was been found that the presence of a water-alcohol solvent mixture in the process of the invention suppresses side reactions and produces lignin solutions with very little residual solid material compared to conventional processes of aqueous phase reforming.
  • the invention pertains to a process for treating a lignin- containing feed with a transition metal catalyst in a water-alcohol containing solvent.
  • the process has the advantage of providing a convenient and efficient one-step, one- pot conversion of lignin into aromatics and gases without the need for separating intermediate products.
  • the process has the advantage of using components readily obtained in the lignocellulosic biorefinery scheme to produce valuable platform chemicals (i.e. chemicals that can be used as a starting point for other chemicals) thereby increasing the chemical and energy integration of the biorefinery scheme.
  • the process operates under conditions milder than that used in gasification or pyrolysis, with temperatures of approximately 498 K.
  • the lignin-containing feed can be in its broadest form from any lignin source, but is preferably selected from the group consisting of kraft lignins, organosolv lignins, lignins obtained from agricultural products or waste, and lignins obtained from sugarcane bagasse, and combinations thereof.
  • the nature of the lignin used as a feed during the liquid-phase reforming process may vary. There is a preference for isolated lignin.
  • the structure of lignin varies considerably from plant to plant, especially with regards to the number of methoxy groups present on the aromatic ring along with the type and abundance of the many linkages present in the lignin polymer.
  • Lignin obtained from hardwoods tends to constitute approximately equal proportions of coniferyl and sinapyl alcohols.
  • lignin obtained from softwoods contains approximately 90% of coniferyl alcohols whereas lignin from grasses contains mostly p-coumaryl alcohols.
  • the pretreatment method used to obtain extracted lignin drastically influences the functional groups and linkages present in the isolated polymer.
  • the kraft process which is extensively deployed throughout the pulp and paper industry and thus exhibits infrastructural advantages relative to other processes, yields abundant, readily available, renewable, accessible, but also recalcitrant kraft lignin.
  • lignin Other sources of lignin, such as those obtained from the organosolv pretreatment method, confer different properties to the extracted lignin, including the nature of the linkages and functional groups present in the extracted lignin and the extent of sulfur and other elemental incorporation into the lignin polymer.
  • the type and variety of lignin received by the biorefinery will vary considerably depending on geographical location. A general and readily deployable process capable of procurzing such broad feed distributions is therefore advantageous.
  • the catalyst can consist of materials generally used for aqueous-phase reforming, including but not limited to precious (e.g. Pt, Rh, Ru, Ir) and non-precious metals (e.g. Ni, Co) supported (on, for example, AI2O3 or C) or unsupported, pelletized or powdered.
  • precious e.g. Pt, Rh, Ru, Ir
  • non-precious metals e.g. Ni, Co
  • any catalyst used in the liquid- phase reforming can be used, with preference for catalysts containing group VIII elements, in particular selected from the group of consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, including alloys and mixtures thereof, preferably platinum, ruthenium, or rhodium and mixtures thereof.
  • the transition metal catalyst is present in an amount of 0.01 to 25 wt% relative to the feed, preferably from 0.1 to 15 wt%, more preferably from 0.5-10 wt%
  • the catalyst material used in the present invention may be a heterogeneous catalyst.
  • the use of a heterogeneous catalyst allows easier processing or regeneration of the catalyst or the use of a heterogenous catalyst allows for an easier recycling, for instance in a continuous process.
  • the catalyst may be provided on a carrier.
  • Preferred carriers for catalysts to be used in the process of the invention are selected form the group consisting of alumina, boron nitride, carbon, ceria, silica, silica-alumina, silica nitride, titania, zirconia, and mixtures thereof. There is a preference for a Pt/AI 2 O3 or Pt/C catalyst-carrier combination.
  • the alcohol used in the process of the present invention can be any alcohol that is miscible with water.
  • the lower alkanols preferably selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, 2- butanol, tert-butanol and mixtures thereof, more preferably ethanol and mixtures of ethanol with other lower alkanols.
  • ethanol can be used in the form of bioethanol which adds to the green character of the present invention.
  • Other solvents that are possible are solvents that are formed during the reaction, such as diethyl ether.
  • the lignin-containing feed is preferably mixed with the water/alcohol combination in about 1 wt-% to about 200 wt-% water/solvent with respect to the weight of the lignin material.
  • the process involves the solubilization of the lignin component in aqueous alcohol (composed of water and alcohol) mixtures.
  • the mixtures consist of from 0%-100% alcohol ('from 0%' thus excluding 0 as a value), preferably from 5 to 95% alcohol by weight (and hence 95 to 5% water, respectively), more preferably from 25 to 75% and a higher preference for about 40-60% alcohol.
  • a solvent ethanol being most preferred and preferably at a range of 40-60% by weight.
  • the water and alcohol content of the solvent in certain embodiments is based on added solvent, preferably not including water and or alcohol that is present in the feed or in cocatalyst such as sulfuric acid,
  • cocatalyst such as sulfuric acid
  • the advantages of this process in the biorefinery scheme is that the lignin used as a feed need not be dry, and the alcohol (such as ethanol) need not be pure, as the preferred alcohol content (ethanol) is far from the azeotrope point and thus readily obtained in the lignocellulosic biorefinery scheme.
  • a co-catalyst can be used.
  • the solubilized lignin is subjected to the liquid-phase reforming in the presence of a reforming catalyst and a co-catalyst.
  • co-catalyst present during the liquid-phase reforming reaction aids in the hydrolysis or general disruption of the linkages present in the lignin polymer.
  • These co-catalysts can comprise superacids, acids, or bases depending on the distribution of products desired during the reforming of the lignin. Examples of each category include phosphotungstic acid, mineral acids such as sulfuric acid, and bases including NaOH.
  • the co-catalyst can be selected from the group consisting of a superacid, an acid, and a base co-catalyst.
  • the superacid co-catalyst can comprise phosphotungstic acid.
  • the acid co-catalyst can comprise sulfuric acid. When sulfuric acid is used as cocatalyst, it can be added in the form of oleum, or the water content of the sulfuric acid is not taken into account in the alcohol-water ratio of the solvent.
  • the base co- catalyst can be an alkaline or earth alkaline hydroxide base, preferably an alkaline hydroxide, more preferably selected from the group consisting of sodium, potassium, cesium, calcium or lithium hydroxide.
  • solid superbases can be used such as high-temperature treated MgO, MgO-Na 2 0, CsX-type zeolite, and combinations thereof.
  • the cocatalyst can be present in an amount up to 6 wt%, preferably up to 3 wt% based on the feed, i.e. lignin source.
  • the process can be performed in a continuous or batch mode.
  • the process is preferably performed in a temperature range from about 100 to about 250°C, preferably from about 150 to about 240°C, more preferably from about 200 to about 230°C.
  • the process can be performed under autogeneous pressure in a batch reactor or it can be performed under additional pressure.
  • the process can be performed semi- batch at a pressure of 50-60 bar.
  • additional pressure can be provided by a gas that is selected form the group consisting of helium, argon, carbon dioxide or nitrogen.
  • the reaction time for the process of the invention is preferably from about 30 s to about 90 min in batch mode.
  • the process provides isolated monomeric aromatic chemicals, which consist of alkylated phenols and alkylated alkoxyphenols, and catechol, alkylated catechols, and alkylated alkoxycatechols with the characteristics of the alkyl side-chain depending on the co-catalyst employed.
  • light molecules including hydrogen, methanol, and light alkanes, such as methane and ethane, are produced.
  • the ethanol component of the solution is retained, converted to ethyl ether, or converted to useful higher alcohols, such as butanol and hexanol.
  • FIG. 1 The principle features of the process of the invention for the integrated lignin valorization process for the lignocellulosic biorefinery scheme are shown in the schematic diagram, which is discussed in further detail below.
  • lignocellulosic biomass is received and processed in the first component of the process.
  • a pretreatment step which may depend on existing infrastructure and available technology, separates the biomass into cellulose, hemicellulose, and lignin component streams. Valorization of the cellulose and hemicellulose components yields valuable chemicals and fuels including ethanol, a portion of which is diverted for the solubilization of the lignin component in
  • the lignin is mixed into the ethanol/water solution and subjected to heating to 40-225°C until the lignin material dissolves. Small quantities of residual solid can be removed by decantation and filtration before further processing. Following the solubilization, the dissolved lignin can be mixed with a specified quantity of co-catalyst consisting of superacids, acids, or bases, including but not limited to H 2 S0 4 , polyphosphoric tungstic acid, or NaOH. Additional details including the quantities of co-catalyst added to the
  • the components of the reaction mixture can be introduced to the ethanol/water solution in the reactor sequentially and in any order.
  • the ethanol component of the solvent is preferably mixed with water before introduction of other materials to enhance solubility and suppress lignin side reactions (e.g. recondensation).
  • the lignin used in this process may originate from
  • lignocellulosic plant materials including but not limited to grasses, softwoods or hardwoods from trees or shrubs, sugarcane, mixtures of these categories and combinations thereof.
  • the lignin may be isolated through a pretreatment process including but not limited to the kraft, lignosulfonate, or organosolv lignin processes.
  • the reaction solution and catalyst can be charged to an enclosed reaction vessel, which can be sealed to collect gases produced during the process or equipped with a back-pressure regulator to allow continuous, semi-batch collection of gaseous products.
  • the enclosed reaction mixture consisting of lignin, ethanol, water, catalyst, and co-catalyst can be heated at a rate of 5-15°C/min to a specified reaction temperature, preferably 225°C, and held approximately or precisely at this
  • the autoclave can be pressurized with an inert gas (such as helium, argon or nitrogen) to preferably 55-58 bar to prevent evaporation and loss of the solvent.
  • the enclosed vessel can be equipped with a stirring mechanism to enhance contact of the solubilized lignin with the catalyst.
  • the reaction vessel will consist of devices to record temperature and pressures, such as thermocouples, thermistors, gauges, or pressure transducers and external heating mechanisms.
  • the vessel can also contain gas and liquid sampling valves for introduction or removal of reactants or products to or from the reaction vessel, respectively, during either semi-batch or continuous processing.
  • Figure 2 provides a schematic overview of the lignin valorization.
  • the alcell lignin (66.47% C, 5.96% H, 0.15% N, 27.43% O by difference) was isolated by the organosolv extraction method and obtained from Wageningen University.
  • the INDULIN AT kraft lignin (63.25% C, 6.05% H, 0.94% N, 1 .64% S, 28.12% 0 by difference), provided by ECN, was obtained from pine and is free from all hemicellulosic materials.
  • the lignin from sugarcane bagasse (58.90% C, 4.90% H, 0.14% N, 1.53% S, 34.53% O by difference) is derived from Brazilian sugarcane and was obtained from the Dow Chemical Company.
  • lignin solubilization studies were conducted in a semi-batch 200 ml_ autoclave equipped with quartz windows, thermocouple, pressure gauge and transducer, magnetic driver (750 rpm), and back-pressure regulator set at 58 bar. Lignin samples were stored in a desiccator prior to use. During a typical treatment, 0.200 g lignin (either kraft, alcell, sugarcane bagasse, or soda) was added to the autoclave with 100 ml_ H 2 0 and 100 ml_ ethanol. The autoclave was then sealed, purged and charged with 58 bar He, and finally heated at approximately 4 K/min to 498 K.
  • Lignin samples were stored in a desiccator prior to use.
  • 0.125 g lignin either kraft, alcell, or sugarcane bagasse
  • 0.125 g Pt/Al 2 0 3 (1 % Pt) was added to the autoclave along with 0.125 g Pt/Al 2 0 3 (1 % Pt), 5.5 g H20, 5.5 g ethanol, and either 0.58 g H 2 S0 4 , 0.3 g phosphotungstic acid hydrate (Sigma-Aldrich,
  • the autoclave was then sealed, purged with He, and then 58 bar He was charged to the autoclave.
  • the autoclave was then rapidly heated to 498 K in the course of about 15 min. Gas sampling was conducted using a dual-column Galaxie micro gas chromatography unit. After the designated time (typically 1 .5 h), the autoclave was cooled in an ice water bath and vented. At the conclusion of the reactions, the autoclaves were vented, the liquid phase was separated from solids, and finely dispersed solids were isolated by centrifugation if necessary.
  • the liquid-phase reforming reactions were conducted with a Pt/AI 2 0 3 reforming catalyst in the presence of either acid or base co-catalysts.
  • guaiacol was the most abundant isolated monomeric aromatic product followed by ethylcatechol and methanol, which were formed via the acid-catalyzed hydrolysis of ethylguaiacol.
  • the proportion of isolated monomeric aromatic products obtained via the liquid-phase reforming of lignin in ethanol/water mixtures exceeded by an order of magnitude that obtained from similar conditions with just water as the solvent, with up to 17.6% of the original lignin mass converted to monomeric isolated products.
  • reaction pathways for the formation of alkanes are favorable under the reaction conditions employed and may include the Bransted acid-catalyzed
  • 1 -Butanol which has a high energy content, low miscibility with water, low volatility and can replace or be blended into gasoline without the need to modify engine technology, was obtained as the primary product along with lesser quantities of 1 -hexanol, 1 -but-3-enol, and similar products, thus representing a method to produce transportation fuels simultaneously during the lignin valorization.
  • HPA tungstophosphoric aci
  • tungstophosphoric acid was used as the co-catalyst, similar aromatic product distributions were obtained relative to the case in which H 2 S0 4 was used as the co- catalyst, although no hydrogen was detected in the autoclave headspace.
  • Light alkanes consisting of methane and ethane, were detected, although hydrogen was not detected during the process.
  • Use of NaOH as the co-catalyst resulted in the lowest quantity of isolated aromatic products, which consisted of ethylphenol, methylacetophenone, and ethoxyphenol as the most abundant products with total isolated monomeric yields corresponding to about 2% based on the quantity of lignin starting material.
  • Hydrogen and light alkanes consisting of methane, ethane, and propane, were obtained. Butanol and hexanol were observed in similar concentrations as that given in Experimental Example 1 .
  • HPA tungstophosphoric acid

Abstract

La présente invention concerne un procédé de reformage en phase liquide de la lignine en produits chimiques aromatiques monomères, dimères, et oligomères, en hydrogène, et en d'autres gaz légers en utilisant des composants provenant d'une bioraffinerie lignocellulosique de seconde génération au sein de laquelle une charge d'alimentation contenant de la lignine est solubilisée dans des solvants contenant de l'eau et de l'alcool, puis le produit est reformé en phase liquide éventuellement en présence d'un superacide, d'un acide, ou d'un co-catalyseur basique. Les composants aromatiques isolés résultants, les gaz, et les solvants obtenus à la fin du procédé peuvent être réglés en fonction des conditions de la réaction, en particulier selon le catalyseur et le co-catalyseur, et donc la distribution des produits peut être réglée de manière très large selon la demande en produits chimiques. Les produits aromatiques consistent en des monomères, des dimères et des oligomères de phénol alkylé, de gaïacol, de catéchol, et de syringol, et le solvant éthanolique peut être récupéré soit sous la forme d'éthanol, d'éther d'éthyle, ou d'alcools de poids moléculaires élevés comprenant le n-butanol ou le n-hexanol, dont la distribution particulaire dépend des conditions de réaction utilisées.
PCT/NL2012/050446 2011-06-23 2012-06-25 Procédé de reformage en phase liquide de la lignine en produits chimiques aromatiques et en hydrogène WO2012177138A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015080660A1 (fr) 2013-11-27 2015-06-04 Kat2Biz Ab Dépolymérisation de lignine dans une biomasse
WO2016023563A1 (fr) * 2014-08-14 2016-02-18 Inbicon A/S Composition de fluide comprenant de la lignine
CN105542883A (zh) * 2015-12-20 2016-05-04 高大元 一种建筑废弃木头水热转化制备生物质油的方法
WO2016195599A1 (fr) * 2015-06-03 2016-12-08 Nanyang Technological University Procédé et système de conversion de biomasse en produits combustibles
WO2017108055A1 (fr) * 2015-12-21 2017-06-29 Inbicon A/S Composition de fluide comprenant de la lignine et de la vinasse
CN109796999A (zh) * 2019-01-31 2019-05-24 盐城工学院 一种生物质催化热解方法
CN111849526A (zh) * 2020-07-22 2020-10-30 中国电力工程顾问集团西北电力设计院有限公司 一种热解生物质联产焦炭和苯酚的方法
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WO2021145968A1 (fr) * 2019-12-02 2021-07-22 Casad Robert C Jr Procédés de valorisation de solides riches en lignine à partir de digestat anaérobie
CN113355125A (zh) * 2021-06-11 2021-09-07 厦门大学 一种从废生物油脂选择性加氢制备长链烷烃的方法
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CN114177930A (zh) * 2021-11-09 2022-03-15 华南理工大学 一种分子筛负载钌镍催化剂催化木质素加氢解聚的方法
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CN117383999A (zh) * 2023-12-12 2024-01-12 北京林业大学 利用木质素制备苯乙烯的方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6172272B1 (en) 1998-08-21 2001-01-09 The University Of Utah Process for conversion of lignin to reformulated, partially oxygenated gasoline
US6699457B2 (en) 2001-11-29 2004-03-02 Wisconsin Alumni Research Foundation Low-temperature hydrogen production from oxygenated hydrocarbons
US6953873B2 (en) 2002-05-10 2005-10-11 Wisconsin Alumni Research Foundation Low-temperature hydrocarbon production from oxygenated hydrocarbons
US20080103344A1 (en) 2006-09-01 2008-05-01 Jones Christopher W Hydrogen Production From Biomass
US20090218061A1 (en) 2008-02-28 2009-09-03 Texaco Inc. Process for generating a hydrocarbon feedstock from lignin
US20090218062A1 (en) 2008-02-28 2009-09-03 Texaco Inc. Process for generating a hydrocarbon feedstock from lignin
US7618612B2 (en) 2001-11-29 2009-11-17 Wisconsin Alumni Research Foundation Low-temperature hydrogen production from oxygenated hydrocarbons
WO2010037178A1 (fr) * 2008-10-01 2010-04-08 Licella Pty Ltd Procédé de production d'huile biologique
WO2011123897A1 (fr) * 2010-04-07 2011-10-13 Licella Pty Ltd. Procédés pour la production de biocarburants

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6172272B1 (en) 1998-08-21 2001-01-09 The University Of Utah Process for conversion of lignin to reformulated, partially oxygenated gasoline
US6699457B2 (en) 2001-11-29 2004-03-02 Wisconsin Alumni Research Foundation Low-temperature hydrogen production from oxygenated hydrocarbons
US6964758B2 (en) 2001-11-29 2005-11-15 Wisconsin Alumni Research Foundation Low-temperature hydrogen production from oxygenated hydrocarbons
US7618612B2 (en) 2001-11-29 2009-11-17 Wisconsin Alumni Research Foundation Low-temperature hydrogen production from oxygenated hydrocarbons
US6953873B2 (en) 2002-05-10 2005-10-11 Wisconsin Alumni Research Foundation Low-temperature hydrocarbon production from oxygenated hydrocarbons
US20080103344A1 (en) 2006-09-01 2008-05-01 Jones Christopher W Hydrogen Production From Biomass
US20090218061A1 (en) 2008-02-28 2009-09-03 Texaco Inc. Process for generating a hydrocarbon feedstock from lignin
US20090218062A1 (en) 2008-02-28 2009-09-03 Texaco Inc. Process for generating a hydrocarbon feedstock from lignin
WO2010037178A1 (fr) * 2008-10-01 2010-04-08 Licella Pty Ltd Procédé de production d'huile biologique
WO2011123897A1 (fr) * 2010-04-07 2011-10-13 Licella Pty Ltd. Procédés pour la production de biocarburants

Non-Patent Citations (28)

* Cited by examiner, † Cited by third party
Title
E. DORRESTIJN; L.J.J. LAARHOVEN; I.W.C.E. ARENDS; P. MULDER, J. ANAL. APPL. PYROLYSIS, vol. 54, pages 153 - 192
F. S. CHAKAR; A. J. RAGAUSKAS, IND. CROPS PROD., vol. 20, 2004, pages 131 - 141
F. TALEBNIA; D. KARAKASHEV; ANGELIDAKI, BIORES. TECHNOL., vol. 101, 2010, pages 4744 - 4753
G. W. HUBER; J. A. DUMESIC, CATAL. TODAY, vol. 111, 2006, pages 119 - 132
G. W. HUBER; S. IBORRA; A. CORMA, CHEM. REV., vol. 106, 2006, pages 4044 - 4098
G.W. HUBER; R.D. CORTRIGHT; J.A. DUMESIC, ANGEW. CHEM. INT. ED. ENGL., vol. 43, 2004, pages 1549 - 1551
HASEGAWA, Y. FUJII; K. YAMADA; C. KARIYA; T. TAKAYAMA, J. APPL. POLYM. SCI., vol. 73, 1999, pages 1321 - 1328
J. Q. BOND; D. M. ALONSO; D. WANG; R. M. WEST; J. A. DUMESIC, SCIENCE, vol. 327, 2010, pages 1110 - 1114
J. R. REGALBUTO, SCIENCE, vol. 325, 2009, pages 822 - 824
J. ZAKZESKI; B. M. WECKHUYSEN, CHEMSUSCHEM, vol. 4, 2011, pages 369 - 378
J. ZAKZESKI; P.C.A. BRUIJNINCX; A.L. JONGERIUS; B.M. WECKHUYSEN, CHEM. REV., vol. 110, 2010, pages 3552 - 3599
J.-P. LANGE, BIOFUELS, BIOPROD. BIOREF., vol. 1, 2007, pages 39 - 48
M. J. TAHERZADEH; K. KARIMI, INT. J. MOL. SCI., vol. 9, 2008, pages 1621 - 1651
M. MISSON; R. HARON; M.F.A. KAMARODDIN; N.A.S. AMIN, BIORESOUR. TECHNOL., vol. 100, 2009, pages 2867 - 2873
M.B. VALENZUELA; C.W. JONES; P.K. AGRAWAL, ENERGY FUELS, vol. 20, 2006, pages 1744 - 1752
MARIEFEL B. VALENZUELA ET AL: "Batch Aqueous-Phase Reforming of Woody Biomass", ENERGY & FUELS, vol. 20, no. 4, 1 July 2006 (2006-07-01), pages 1744 - 1752, XP055017237, ISSN: 0887-0624, DOI: 10.1021/ef060113p *
P. ALVIRA; E. TOMAS-PEJO; M. BALLESTEROS; M.J. NEGRO, BIORES. TECHNOL., vol. 101, 2010, pages 4851 - 4861
P.F. BRITT; A.C. BUCHANAN; M.J. COONEY; D.R. MARTINEAU, J. ORG. CHEM., vol. 65, 2000, pages 1376 - 1389
R. D. PERLACK; L. L. WRIGHT; A. F. TURHOLLOW; R. L. GRAHAM; B. J. STOKES; D.C. ERBACH, U. S. DEPARTMENT OF ENERGY, BIOMASS AS FEEDSTOCK FOR A BIOENERGY AND BIOPRODUCTS INDUSTRY: THE TECHNICAL FEASIBILITY OF A BILLION-TON ANNUAL SUPPLY, 2005
R.D. CORTRIGHT; R.R. DAVDA; J.A. DUMESIC, NATURE, vol. 418, 2002, pages 964
R.J.A. GOSSELINK; E. DE JONG; B. GURAN; A. ABÄCHERLI, IND. CROPS PROD., vol. 20, 2004, pages 121 - 129
R.W. THRING; J. BREAU, FUEL, vol. 75, 1996, pages 795 - 800
S. BRETHAUER; C.E. WYMAN, BIORES. TECHNOL., vol. 101, 2010, pages 4862 - 4874
S. K. RITTER, CHEM. ENG. NEWS, vol. 86, 2008, pages 59 - 68
T. P. VISPUTE; H. Y. ZHANG; A. SANNA; R. XIAO; G. W. HUBER, SCIENCE, vol. 330, 2010, pages 1222 - 1227
TOKAREV ET AL., INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 35, no. 22, pages 12642 - 12649
Y. MATSUSHITA; S. YASUDA, BIORESOUR. TECHNOL., vol. 96, 2005, pages 465 - 470
Y.-H. P. ZHANG; S.-Y. DING; J. R. MIELENZ; J.-B. CUI; R. T. ELANDER; M. LASER; M. E. HIMMEL; J. R. MCMILLAN; L. R. LYND, BIOTECHNOL. BIOENG., vol. 97, 2007, pages 214 - 223

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