[go: up one dir, main page]

WO2018015610A1 - Procédé simple de conversion de matières lignocellulosiques - Google Patents

Procédé simple de conversion de matières lignocellulosiques Download PDF

Info

Publication number
WO2018015610A1
WO2018015610A1 PCT/FI2016/050530 FI2016050530W WO2018015610A1 WO 2018015610 A1 WO2018015610 A1 WO 2018015610A1 FI 2016050530 W FI2016050530 W FI 2016050530W WO 2018015610 A1 WO2018015610 A1 WO 2018015610A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
zirconia
hydrotreating
phase
alkali
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/FI2016/050530
Other languages
English (en)
Inventor
Marcelo DOMINE
Marvin CHÁVEZ-SIFONTES
Andrea Gutierrez
Kati VILONEN
Timo STRENGELL
Pekka Jokela
Isto Eilos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UPM Kymmene Oy
Original Assignee
UPM Kymmene Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UPM Kymmene Oy filed Critical UPM Kymmene Oy
Priority to PCT/FI2016/050530 priority Critical patent/WO2018015610A1/fr
Publication of WO2018015610A1 publication Critical patent/WO2018015610A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • 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
    • 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
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • 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
    • 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 invention relates to converting of lignocellulosic materials and more particularly to a simple process for converting lignocellulosic materials to aromatic compounds, hydrocarbons and other chemicals.
  • Lignin is one of the most abundant biopolymers in the nature and it is produced in large amounts in the paper industry. Global commercial yearly production of lignin is around 1.1 million metric tons and lignin is used in a wide range of low volume niche applications where typically the form but not the quality of lignin is important. Lignin functions as a support through strengthening of wood (xylem cells). Lignin is an unusual biopolymer because of its heterogeneity and lack of defined primary structure. The building blocks of lignin are aromatic compounds and thus it is a valuable renewable source of aromatic compounds, useful for chemical and fuel production. The chemical structures of lignin and lignin precursors (coumaryl alcohol, coniferyl alcohol and sinapyl alcohol) are shown below.
  • lignin In the conversion of lignin it may be subjected to depolymerization carried out in homogeneous or heterogeneous phases where the depolymerization may be performed in the presence of catalysts. After the depolymerization the obtained depolymerized product may be hydrotreated, followed by separation of the product obtained from hydrotreating into different fractions which may further be processed into hydrocarbons or other chemicals. Conversion of lignin may also be realized by hydrotreating without depolymerization. It is necessary to depolymerize lignin to smaller oligomers and monomers, which are suitable for further processing by hydrotreating etc.
  • a process for converting feedstock comprising lignocellulosic material comprises the steps of hydrotreating the feedstock catalytically with hydrogen in the presence of an alkali and a catalyst composition comprising ruthenium (Ru) supported on zirconia (ZrC ), where said zirconia comprises 60-100 wt% of monoclinic phase of zirconia, whereby an effluent is obtained, and separating from the effluent at least one of the following : an aqueous phase, light gaseous phase, liquid organic phase and residual lignin phase.
  • Ru ruthenium
  • catalytic conversion of lignocellulosic material refers here to treating lignocellulosic material in the presence of at least one catalytic material to effect change in the structure of the lignocellulosic material, at least to reduce the molecular size and change the functionality.
  • Mgnocellulosic material refers here to lignin or derivatives thereof and combinations thereof.
  • the lignin or derivatives thereof may be derived from any wood or plant based material, such as wood based raw material, woody biomass, lignin containing biomass such as agricultural residues, bagasse and corn stover, woody perennials, vascular plants, recycled brown board, deinking pulp and their combinations.
  • the term also refers to lignin or derivatives thereof obtained from Kraft black liquor (Kraft lignin), alkaline pulping process, soda process, organosolv pulping and any combination thereof, such as lignosulfonates.
  • the degree of polymerization of this kind of lignin is 10- 25. Lignin separated from pure biomass is sulphur-free and thus valuable in further processing.
  • lignin refers here to a class of complex organic polymers that form important structural materials in the support tissues of vascular plants and some algae. Chemically, lignin is a very irregular, randomly cross-linked polymer with a weight average molecular weight of 500 Daltons or higher. Said polymer is the result of an enzyme-mediated dehydrogenative polymerization of three phenyl propanoid monomer precursors, i.e. coniferyl, synapyl and coumaryl alcohols. Coniferyl alcohol is the dominant monomer in conifers (softwoods). Deciduous (hardwood) species contain up to 40% syringyl alcohol units while grasses and agricultural crops may also contain coumaryl alcohol units.
  • zirconia refers to zirconium oxide with the chemical formula Zr02.
  • the crystal structure of Zr02 exists in three polymorphic phases i.e. Zr02 has three different polymorphic forms: monoclinic, tetragonal and cubic.
  • the cubic phase is formed at very high temperatures (>2370°C), at intermediates temperatures (1150-2370°C) the oxide has a tetragonal structure, and from room temperature to 1150°C the material is stable as monoclinic structure.
  • Each of these polymorphic phases differ structurally significantly from each other and they exhibit different acid/base properties and surface hydroxyl group concentrations.
  • a phase diagram for Zr02 is shown in Figure 1. (www. materia Idesiqn.com/svstem/f iles/..JZr02 phase transitrion.pdf).
  • the structures cubic, tetragonal or monoclinic are different.
  • the chemical bond is the same Zr-0 but how they organized in the space is different.
  • the term "monoclinic phase of zirconia” or “monoclinic zirconia” or “monoclinic ZrCh” refers here to a specific crystal structure of zirconia having characteristic X-ray diffraction patterns, i.e.
  • tetragonal phase of zirconia or "tetragonal zirconia” or “tetragonal ZrCh” refers here to specific crystal structure of zirconia having characteristic X-ray diffraction patterns, i.e. 2 ⁇ reflections at 30.4 and 35.2 in the X-ray diffractogram (JCPDS card no. 17-0923).
  • the X-ray diffractogram of tetragonal phase zirconia is shown in Figure 2.
  • single stage method refers here to a method or process, which is carried out in one reaction stage and where several chemical reactions happen successively and/or in parallel.
  • the reactions may happen in one reaction vessel (reactor) or in several reaction vessels without any removal of products and/or byproducts in between the vessels.
  • reactor reaction vessel
  • reaction vessels without any removal of products and/or byproducts in between the vessels.
  • depolymerization/ hydrotreating or “depolymerization and hydrotreating” or “hydrotreatment” or “hydrotreating” refers to catalytic conversion of lignocellulosic materials in the presence of an alkali, where depolymerization and hydrotreating of the material is carried out in one reaction stage.
  • the depolymerization and hydrotreatong reactions comprising any combination/combinations of the reactions of depolymerization, hydrogenation and hydrodeoxygenation, hydroisomerization, hydrodenitrification, hydrodesulfurization, hydrocracking, and coke/carbon/char gasification, coke reforming, WGS (water-gas-shift) reactions and Bouduard reactions, take place simultaneously and/or in parallel, in any order. All weight percentages regarding the catalyst composition are calculated from the total weight of the catalyst composition.
  • Figure 1 shows a phase diagram of ZrCh.
  • Figure 2 illustrates X-ray diffraction patterns of monoclinic ZrCh and tetragonal ZrCh.
  • Figure 3 shows an embodiment of the process where lignocellulosic material is depolymerized and hydrotreated catalytically in the presence of an alkali and the catalyst composition comprising ruthenium (Ru) supported on zirconia (ZrCh).
  • Figure 4 shows another embodiment of the process where lignocellulosic materia l is pretreated and then depolymerized and hydrotreated catalytica lly in the presence of an alkali and the catalyst composition comprising ruthenium (Ru) supported on zirconia (Zr0 2 ) .
  • Figure 5 presents results of the single stage lignin depolymerization and hydrotreating using Ru supported materials as catalysts.
  • Figure 6 presents GPC analysis of organic phase vs residual lignin fractions obtained from Kraft lignin in a single stage depolymerization and hydrotreating catalyzed by catalyst composition comprising ruthenium (Ru) supported on zirconia (ZrCh) monoclinic material .
  • Ru ruthenium
  • ZrCh zirconia
  • Figure 7 presents GPC analysis of organic phase vs residual lignin fractions obtained from Kraft lignin in a single stage depolymerization and hydrotreating catalyzed by Ru/ZrCh tetragonal material .
  • compositions and methods can be implemented using any number of techniques.
  • ruthenium (Ru) supported on zirconia comprising 60- 100 wt% of monoclinic phase of zirconia is used in single stage catalytic conversion of lignocellulosic materials, where depolymerization and hydrotreaing are carried out simultaneously and/or in parallel, in any order.
  • Said catalyst composition is particula rly useful as a catalyst for conversion of lignocellulosic materials to aromatic compounds, linear and branched hydrocarbons and other chemicals.
  • It may be used in processing of lignocellulosic materials to effect one or more of the following depolymerization, hydrogenation, hydrodeoxygenation (HDO), hydroisomerization (HI), hydrodenitrification (HDN), hydrodesulfurization (HDS), hydrocracking (HC), coke reforming, coke/carbon/char gasification, WGS (water-gas-shift) reactions and Bouduard reactions, also under mild conditions.
  • HDO hydrodeoxygenation
  • HI hydroisomerization
  • HDN hydrodenitrification
  • HDS hydrodesulfurization
  • HC hydrocracking
  • coke reforming coke/carbon/char gasification
  • WGS water-gas-shift
  • a process for converting feedstock comprising lignocellulosic material comprises the steps of hydrotreating the feedstock catalytically with hydrogen in the presence of an alkali and a catalyst composition comprising ruthenium supported on zirconia, where said zirconia comprises 60-100 wt% of monoclinic phase of zirconia, whereby an effluent is obtained, and separating from the effluent at least one of the following : an aqueous phase, light gaseous phase, a liquid organic phase and residual lignin phase.
  • the residual lignin phase refers here to a phase or fraction separated from the effluent and comprising unreacted lignin.
  • the hydrotreating is accomplished in a single stage.
  • Feedstock comprising lignocellulosic material is depolymerized and hydrotreated catalytically with hydrogen in the presence of an alkali and a catalyst composition comprising ruthenium supported on zirconia, where said zirconia comprises 60-100 wt% of monoclinic phase of zirconia.
  • Feedstock comprising lignocellulosic material 10 an aqueous solution formed of alkali 11 and a mixture 13 of water and ethanol, and hydrogen 12 are directed to hydrotreating 200 in the presence of a catalyst composition comprising ruthenium supported on zirconia, where said zirconia comprises 60-100 wt% of monoclinic phase of zirconia, whereby an effluent 21 is obtained.
  • the effluent 21 is directed to separation 300, where residual lignin phase 34 is separated and recycled to feedstock comprising lignocellulosic material 10, and an aqueous phase 31, light gaseous phase 32 and a liquid organic phase 33 are obtained.
  • the liquid organic phase 33 is directed to further processing 700, which may comprise hydrotreating, isomerization, cracking, fractionation etc. and combinations thereof, to obtain one or more product streams 71.
  • FIG 4 another embodiment is presented where feedstock comprising lignocellulosic material is first pretreated and then depolymerized and hydrotreated catalytically with hydrogen in the presence of an alkali and a catalyst composition comprising ruthenium supported on zirconia, where said zirconia comprises 60-100 wt% of monoclinic phase of zirconia.
  • Feedstock comprising lignocellulosic material 10, an aqueous solution formed of alkali 11 and a mixture 13 of water and ethanol are directed to pretreatment 100, whereby pretreated mixture 14 is obtained, the pretreated mixture 14 comprising pretreated feedstock, water, ethanol and alkali is directed to hydrotreating 200 in the presence of hydrogen 12 and a catalyst composition comprising ruthenium supported on zirconia, where said zirconia comprises 60-100 wt% of monoclinic phase of zirconia, whereby an effluent 21 is obtained.
  • alkali may be added to the hydrotreating 200 (not shown in the Figure).
  • the effluent 21 is directed to separation 300, where residual lignin phase 34 is separated and recycled to feedstock comprising lignocellulosic material 10, and an aqueous phase 31, light gaseous phase 32 and a liquid organic phase 33 are obtained.
  • the feedstock comprises lignocellulosic material selected from lignin, derivatives thereof and mixtures thereof.
  • lignocellulosic materials are Kraft lignin, native lignin, lignosulfonate, lignin obtained from biorefinery processes such as enzymatic, alkaline or acid hydrolysis or steam explosion, and any combinations thereof.
  • Lignin may be wood based, wood biomass based, corn based, bagasse based, agricultural waste based, woody perennials based, vascular plants based, recycled brown board based, deinking pulp based or nutshell based.
  • the weight average molecular weight of lignin used as feedstock is 500-10 000 Da, preferably 600-9000 Da and most preferably 700-8000 Da.
  • the lignocellulosic material such as lignin may be supplied from a feed source such as the pulp and/or paper industry or ethanol production facility or any other source.
  • the feedstock comprises 60-100 wt% of lignocellulosic material. In another embodiment the feedstock comprises 80-100 wt% of lignocellulosic material.
  • the feedstock may comprise co-feed selected from benzene ring containing polymers, such as PVC, polystyrene, PET, polyamide and the like, oil refinery vacuum distillation column bottoms, black liquor, pyrolysis oil, and combinations thereof.
  • the feedstock may comprise co-feed not more than 50 wt%, preferably not more than 20 wt%.
  • the alkali is selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, such as Na2C03, and alkaline earth metal carbonates.
  • alkali metal hydroxides such as Na2C03
  • alkali metal carbonates such as Na2C03
  • alkaline earth metal carbonates Preferably NaOH, KOH, CsOH, Ca(OH) 2 , Sr(OH) 2 or Ba(OH) 2 is used.
  • NaOH is used as alkali.
  • the alkali acts as a homogeneous depolymerization catalyst in the process.
  • the molar ratio of lignocellulosic material to the alkali in the process is from 0.2 : 1 to 20 : 1, respectively.
  • the feedstock comprising lignocellulosic material is mixed in an aqueous solution to obtain a mixture comprising the feedstock comprising lignocellulosic material and the aqueous solution comprising water and the alkali.
  • the aqueous solution comprises water and the alkali.
  • the aqueous solution comprises 1- 10 wt%, suitably 2-5 wt% of the alkali.
  • the aqueous solution may comprise a co-solvent selected from lower (C1-C5) alkyl alcohols, lower (C1-C6) alkyl ethers and lower (C1-C6) alkyl esters.
  • a co-solvent selected from lower (C1-C5) alkyl alcohols, lower (C1-C6) alkyl ethers and lower (C1-C6) alkyl esters.
  • the lower (C1-C5) alkyl alcohol is selected from methanol, ethanol, 1-propanol, iso-propanol, 1-butanol and sec-butanol.
  • the aqueous solution may comprise a co-solvent selected from ethyl acetate, methyl tert-butyl ether, furan, methyl furan, dimethyl furan, tetrahydrofuran, methyl-tetrahydrofuran, dimethyl-tetrahydrofuran and furfuryl alcohol.
  • a co-solvent selected from ethyl acetate, methyl tert-butyl ether, furan, methyl furan, dimethyl furan, tetrahydrofuran, methyl-tetrahydrofuran, dimethyl-tetrahydrofuran and furfuryl alcohol.
  • the co-solvent is ethanol.
  • the volumetric ratio of water to the co-solvent may be from 0.5 : 1 to 10 : 1, respectively, preferably from 1 : 1 to 5 : 1, particularly preferably from 2 : 1 to 3 : 1.
  • the volumetric ratio of water to ethanol is from 1 : 1 to 5 : 1, preferably from 1 : 1 to 3 : 1, respectively.
  • the ratio of the lignocellulosic material to Ru is from 0.25 : 1 to 30 : 1, respectively.
  • the catalyst composition comprises ruthenium supported on zirconia, where said zirconia comprises 80-100 wt% of monoclinic phase of zirconia. In an embodiment the zirconia comprises 85-100 wt% of monoclinic phase of zirconia.
  • the zirconia comprises 90-100 wt% of monoclinic phase of zirconia.
  • the zirconia comprises 95-100 wt% of monoclinic phase of zirconia.
  • the zirconia comprises 98-100 wt% of monoclinic phase of zirconia.
  • the remaining part of zirconia may exist as tetragonal phase or another crystal form.
  • the catalyst composition comprises 0.2 - 5 wt% of Ru. In another embodiment the catalyst composition comprises 0.3 - 3 wt% of Ru. In still another embodiment the catalyst composition comprises 0.5 - 2.5 wt% of Ru.
  • the catalyst composition comprises metallic Ru particles having small average particle size, in the range from 0.1 to 30 nm. In another embodiment the catalyst composition comprises metallic Ru particles having average particle size in the range from 0.5 to 20 nm. In still another embodiment the catalyst composition comprises metallic particles having average particle size in the range from 1 to 15 nm.
  • the particle size determination may suitably be carried out by methods based on SEM (Scanning Electron Microscope) or HR-TEM (High Resolution Transmission Electron Microscope).
  • the Ru metallic particles are highly dispersed onto the support.
  • the metal dispersion of Ru measured by CO chemisorption method, is in the range from 15 to 45%, where the specific surface area (BET) of zirconia is not more than 100m 2 /g and the Ru loading is not more than 2 wt% in the catalyst composition.
  • the catalyst composition may additionally comprise at least one dopant selected from Pd, Pt, Vn, Ni, Sn, La, Ga, Co and combinations thereof.
  • the amount of the dopant in the catalyst composition is not more than 2 wt%.
  • the total amount of Ru and the dopant is not more than 5 wt%.
  • Zr02 comprising 60-100 wt% of monoclinic phase of zirconia interacts strongly with the active phase (Ru), it inhibits sintering of supported oxides in the presence of water and high temperatures, it possesses high thermal stability and good chemical stability, and it is more inert than the classical supported oxides. Further, Zr02 comprising 60-100 wt% of monoclinic phase of zirconia possesses acidity, basicity as well as reducing and oxidizing ability.
  • Ru active phase
  • the catalyst composition comprises Zr02 comprising 60-100 wt% of monoclinic phase of zirconia as the only support.
  • the catalyst composition may comprise as an additional support an oxide selected from Ce02, T1O2, MgO, ZnO, S1O2 AI2O3 and combinations thereof.
  • suitable mixtures are ZrCh-SiCh, ZrC -AkOs, ZrCh-TiCh, ZrC -ZnO, Zr02- Ce02 and ZrC -MgO, where Zr02 refers to Zr02 comprising 60-100 wt% of monoclinic phase of zirconia.
  • the support may comprise the Zr02 comprising 60-100 wt% of monoclinic phase of zirconia and less than 50 wt% of an additional support.
  • the support may comprise Zr02 comprising 60-100 wt% of monoclinic phase of zirconia and less than 40 wt% of the additional support, suitably less than 30 wt% of the additional support, and even more suitably less than 20 wt% of the additional support.
  • the support may comprise Zr02 comprising 60-100 wt% of monoclinic phase of zirconia and less than 10 wt% of the additional support, suitably less than 5 wt% of the additional support, and even more suitably less than 2 wt% of the additional support.
  • the hydrotreating is carried out at the temperature from 180 to 420°C.
  • the hydrotreating is carried out at the temperature from 200 to 350°C.
  • the hydrotreating is carried out at the temperature from 220 to 280°C.
  • the hydrotreating is carried out under the pressure from 5 to 140 bar. In another embodiment the hydrotreating is carried out under the pressure from 5 to 110 bar. In another embodiment the hydrotreating is carried out under a pressure from 10 to 70 bar.
  • the hydrotreating is carried out under the initial pressure from 5 to 80 bar H2 in batch wise operation, where the reactor is packed at room temperature, with the reaction mixture comprising feedstock, alkali in an aqueous solution and the catalyst. Then the reactor is heated until the reaction temperature and reaction pressure are reached. Reaction time in batch wise operation may be from 20 min to 24 hours. In an embodiment the hydrotreating is carried out under the pressure from 10 to 110 bar in continuous operation.
  • WHSV in the hydrotreating may be 0.1- 10 h 1 . In another embodiment WHSV in the hydrotreating may be 0.5-5 h _1 .
  • the catalytic hydrotreating is carried out in the presence of water, originating from the aqueous solution.
  • the catalyst composition comprising Ru supported zirconia comprising monoclinic phase of zirconia tolerates water. Thus it is capable of carrying out hydrotreating reactions in an environment where water (or aqueous solution) forms a part of the material to be treated.
  • the hydrotreating is carried out in a single stage in one reaction vessel.
  • the hydrotreating is carried out in the presence of hydrogen.
  • the hydrotreating comprises depolymerization reactions and any combination of the reactions of hydrogenation, hydrodeoxygenation, hydroisomerization, hydrodenitrification, hydrodesulfurization, hydrocracking, coke/carbon/char gasification and coke reforming reactions, water-gas- shift reactions and Bouduard reactions, the reactions taking place simultaneously, and/or in parallel, in any order.
  • the feedstock comprising lignocellulosic material is pretreated prior to subjecting to the hydrotreating to obtain a pretreated mixture.
  • the pretreatment softens the lignocellulosic material and effects at least partly depolymerization of lignin.
  • the mixture comprising the feedstock comprising lignocellulosic material and the aqueous solution comprising the alkali is mixed at a temperature from 30 to 110°C under a pressure from 0.5 to 1.5 bar, whereby a pretreated mixture is obtained.
  • the mixing is carried out at a temperature from 50 to 80°C.
  • the mixing is carried out for 15 min to 12 hours, preferably for 0.5 to 6 hours.
  • the mixing is carried out at a temperature from 40 to 80°C.
  • the mixing is carried out under a pressure from 0.5 to 1.5 bar.
  • atmospheric pressure is used.
  • the pretreated mixture comprises pretreated feedstock and an aqueous solution comprising the alkali. It may also comprise unreacted feedstock.
  • the pretreated mixture may be directed as such to the hydrotreating.
  • the alkali used in the pretreatment acts as homogeneous catalyst in the hydrotreating and depolymerization, whereby it may not be necessary to add alkali to the hydrotreating. Same alkali may be used in the hydrotreating and in the pretreatment.
  • the effluent obtained from the process comprising aromatic compounds, alcohols, ethers, esters, gases and some residual lignin may be subjected separation, whereby light gaseous components, residual lignin and an aqueous phase are separated from a liquid organic phase.
  • the liquid organic phase may be further fractionated and/or subjected to further processing, such as hydrotreating, isomerizing, cracking etc. for obtaining components suitable as biofuels, biofuel components and other chemicals.
  • the residual lignin may be recycled to the feedstock.
  • the light gaseous phase comprises light gaseous components, which are mainly gases, such as unreacted (excess) hydrogen (H2), CO and CO2, methane, ethane, ethene, propane, propene, butanes and butenes that can be used in the production of H2 after optional separation of excess hydrogen (H2).
  • This H2 produced or separated excess H2 can be recycled to the hydrotreating step.
  • the optional separation of excess H2 may be carried out by membrane or pressure swing absorption technique.
  • the aqueous phase typically comprises sugars, acids, some aromatic compounds (phenols) and inorganic impurities. The aromatic compounds may be separated and used as chemicals. Low molecular weight acids in the water phase may be condensed for example via ketonization and consecutive aldol condensation reactions to produce hydrocarbon mixtures for further applications.
  • the aqueous water phase may also be used in H2 production, particularly in steam reforming.
  • the liquid organic phase comprises aromatic compounds, alcohols, ethers, esters and hydrocarbons.
  • the liquid organic phase may be fractionated and/or subjected to further processing, such as further hydrotreating to provide chemical compounds and hydrocarbon boiling in the liquid fuel range, particularly the gasoline and diesel range.
  • the process may be carried out in any reactor or reactor system comprising one or more reactors suitable for the purpose, such as a slurry reactor CSRT (Continuous Stirred Tank) reactor, a continuous flow fixed-bed reactor, fixed bed (trickle or gas phase), loop reactor, tubular reactor (plug-flow reactor PFR and packed-bed reactor) or ebullated bed reactor.
  • CSRT Continuous Stirred Tank
  • a continuous flow fixed-bed reactor fixed bed (trickle or gas phase)
  • loop reactor plug-flow reactor PFR and packed-bed reactor
  • ebullated bed reactor ebullated bed reactor.
  • the catalyst composition comprising Ru supported on Zr02 comprising 60-100 w% of monoclinic phase of zirconia may be obtained by a method comprising the steps, where in the first step an aqueous solution of Ru precursor is mixed with Zr02 comprising 60- 100 wt% of monoclinic phase of zirconia, at a temperature from 5 to 85°C to obtain a mixture,
  • the pH of the mixture is adjusted to 7.5 - 10 with an alkali and mixing is continued for 30 min to 30 hours,
  • solid material is recovered from the mixture obtained in the second step, in the fourth step the solid material is dried at a temperature from 50 to 200°C and a catalyst composition comprising Ru supported on Zr02 comprising 60-100 w% of monoclinic phase of zirconia is obtained.
  • ⁇ 2 comprising 60-100 w% of monoclinic phase of zirconia may be obtained using hydrothermal synthesis methods or other methods known in the art.
  • the Ru precursor may be selected from salts a nd organometallic complexes of Ru .
  • the Ru precursor may be selected from [Rus(CO)i2], Ru(NH 3 )4Cl2, [((Cy)RuCl2)2], [(Cp)Ru(PPh 3 ) 2 CI)], [((pMeCp)RuCI2)2], RuCl3-3H 2 0 and Ru(N0 3 ) 2 .
  • the Ru precursor is selected from [Ru3(CO)i2], Ru(NH3)4Cl2, RuCl3-3H20 and
  • RuCl3-3H20 is used as Ru precursor and 0.0065 - 0.1424 grams of this precursor are diluted in an aqueous solution (20 - 30 ml) to attain 0.2 - 5.0 wt% of Ru in the final solid .
  • the aqueous solution of the Ru precursor is mixed with 1 gram of the Zr02 comprising 60-100 w% of monoclinic phase of zirconia .
  • the concentration of the Ru precursor in the aqueous solution is 0.01 -1 wt%.
  • the mixing in the first step is carried at a temperature from 5°C to 85°C, preferably from 15°C to 70°C, and most preferably from 20°C to 50°C.
  • the Zr02 comprising 60-100 w% of monoclinic phase is pretreated at 150-300 °C, suitably in air, to eliminate humidity a nd other organic impurities from the solid .
  • the mixture is stirred in the first step for 10 min to 10 hours.
  • the alkali is selected from alkali metal hydroxides and alkaline earth metal hydroxides, preferably KOH or NaOH is used .
  • KOH or NaOH is used preferably an aqueous solution of NaOH, having concentration ranging from 0.1M to 2.0M is used .
  • the mixture in the second step, is stirred at the temperature from 5 to 35°C. In an embodiment the mixture is stirred for 0.5-30 hours, preferably form 1 to 24 hours.
  • the solid material in the third step, is recovered by filtration, centrifuging, spray drying or the like. The solid material is suitably washed with water until pH is in the range of 6.5 - 7.5.
  • the solid materia l is dried (under air, atmospheric pressure) at 50-200°C. Suitably the drying temperature is 60 - 140°C.
  • the Ru content in the thus obtained catalyst composition may be determined by ICP (inductively coupled plasma mass spectrometry) measurements.
  • the dried final solid material (the catalyst composition) is thermally activated (reduced) at 80-350°C, suitably under H2, in situ or separately, prior to its use in catalytic processing .
  • the dried solid material is thermally activated at 100-300°C, suitably at 200-300°C.
  • the liquid orga nic phase obtained by the process may be fractionated using methods well known in the art to one or several fractions comprising aromatics, hydrocarbons boiling in the liquid fuel range and other chemicals.
  • the aromatics, hyd rocarbons and chemicals may be used as fuels and fuel components and as starting materials in industrial processes.
  • the liquid organic phase may also be processed further by hydrotreating, cracking, isomerizing, etc. and combinations thereof.
  • the aromatics comprise benzene, toluene, ortho- and para- xylenes, ethyl-benzene, propyl-benzene, iso-propyl-benzene, di- and tri-alkyl substituted benzenes, where alkyl substituents are selected from methyl-, ethyl-, propyl- or iso- propyl .
  • the linear and branched hydroca rbons comprise C4-C12 linear and branched hydrocarbons selected from C4-C12 n-alkanes; and C4-C12 mono-alkyl-substituted alkanes, where alkyl substituents are selected from methyl-, ethyl, propyl-, and iso- propyl ; and also C4-C10 di- and tri- alkyl substituted alkane, where alkyl groups a re selected from methyl-, ethyl-, propyl-, and iso-propyl; a nd additionally C4-C9 alkyl substituted cycloalkanes, where alkyl groups a re selected from methyl-, ethyl-, propyl, and iso-propyl.
  • the process for converting lignocellulosic materials to aromatic compounds, linear and branched hydrocarbons and other chemicals has several advantageous effects. It was surprising that low temperatures and pressures can be used, whereby there is no need for equipment designed for high temperature/pressure processing. Further, less side- reactions and less cracking occur, whereby less light compounds and less char, coke and gases are formed. Thus high conversion and high organic yields, and products of high quality and with low oxygen content are achieved. The "single stage" approach is very easy to operate, efficient and cost effective. Varying lignocellulosic materials may be used as feedstock, such as lignin obtained from Kraft pulping and native lignin and mixture of these.
  • the catalyst composition comprising Ru supported on Zr02 comprising 60- 100 w% of monoclinic phase is very efficient in conversion of lignocellulosic materials to aromatic monomers and other hydrocarbonaceous components, particularly to effect one or more of the following : depolymerization, hydrogenation, hydrodeoxygenation, hydroisomerization, hydrodenitrification, hydrodesulfurization, hydrocracking, coke/carbon/char gasification and coke reforming reractions, WGS (water-gas-shift) reactions and Bouduard reactions, simultaneously and/or in parallel, in any order.
  • depolymerization hydrogenation, hydrodeoxygenation, hydroisomerization, hydrodenitrification, hydrodesulfurization, hydrocracking, coke/carbon/char gasification and coke reforming reractions, WGS (water-gas-shift) reactions and Bouduard reactions, simultaneously and/or in parallel, in any order.
  • the catalyst composition comprising Ru supported on Zr02 is very stable and resistant at conversion reaction conditions and it is more tolerant than commercial sulfided hydrotreating catalysts under the harsh conditions. Further it is active and effective even at low temperatures and pressures.
  • the metal loading of the catalyst may be low, still maintaining the desired activity, whereby the need for expensive ruthenium is reduced.
  • Lignin was mixed in a reactor with an aqueous solution comprising NaOH (homogeneous depolymerisation catalyst) and water-ethanol mixture, and the heterogeneous hydrotreating catalyst, Ru/C (commercial as comparative catalyst) or Ru/monoclinic Zr02 comprising 90 W% of monoclinic phase of zirconia was added.
  • H2 was introduced in the reactor at room temperature and then the temperature was increased to 250°C. At this temperature the reaction pressure was 50 bar. The conditions were maintained for 6 h before the reactor was cooled down and the resulting effluent was analyzed.
  • the results obtained are presented in the Table 1 below.
  • the lignin feed was first pretreated for 3 h at 70°C in an aqueous solution comprising NaOH and a mixture of ethanol and water.
  • the pretreated mixture comprising pretreated lignin, NaOH, ethanol and water was depolymerized and hydrotreated in single stage.
  • compositions of the depolymerized and hydrotreated products are provided in table 2 below.
  • Table 2 Compositions of the depolymerized and hydrotreated effluents
  • composition of Pretreatment EtOH + water
  • EtOH + water 1 : 3 depolymerized and 1 : 3; NaOH (70°C, 3h) NaOH (70 °C, 3h)
  • Kraft lignin was pretreated in an aqueous solution comprising NaOH and a mixture of EtOH and water ( 1/3 mass ratio), at 70°C/atmospheric pressure to obtain pretreated lignin mixture comprising NaOH, ethanol and water, followed by depolymerization and hydrotreating of the pretreated mixture, where NaOH in the pretreated mixture acted as the homogeneous catalyst and Ru ( 1.9 wt%) supported on Zr02 comprising 90- 100 wt% of monoclinic phase of zirconia was used as a hydrotreating /depolymerization catalyst. This hydrotreating took place under H2 atmosphere (initial pressure ⁇ 22 bar) and at 250°C.
  • the yield of the organic phase i.e. the desired phase, was highest with the Ru catalyst supported on monoclinic Zr02. Even though the amount of ruthenium, the active metal, was highest for the commercial catalyst this did not improve the yield of organic phase. Having a low metal loading makes the catalyst more attractive because less of valuable Ru is needed.
  • the catalyst using tetragonal Zr02 as support is the least suitable due to the low yields of organic phase achieved and its activity towards gasification reactions (highest gas yield achieved with this catalyst).
  • Figure 5 shows the yields achieved for organic phase, residual lignin, gas phase and coke/char fraction obtained with Ru/Zr02 (monoclinic), Ru/Zr02 (tetragonal), and Ru/C catalysts.
  • Figure 6 presents GPC analysis of organic phase vs residual lignin fractions obtained from Kraft lignin depolymerization and hydrotreating in "single stage” catalyzed by Ru/Zr02 Monoclinic catalyst.
  • Figure 7 presents GPC analysis of organic phase vs residual lignin fractions obtained from Kraft lignin depolymerization and hydrotreating in "single stage" catalyzed by Ru/Zr02 tetragonal catalyst.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de conversion d'une matière première comprenant un matériau lignocellulosique, ledit procédé comprenant les étapes d'hydrotraitement catalytique de la matière première avec de l'hydrogène en présence d'un alcali et d'une composition de catalyseur comprenant du ruthénium supporté sur de la zircone, où ladite zircone comprend de 60 à 100 % en poids d'une phase monoclinique de zircone, ce qui permet d'obtenir un effluent, et la séparation de l'effluent, où une phase aqueuse, une phase gazeuse légère et une phase organique liquide sont obtenues.
PCT/FI2016/050530 2016-07-19 2016-07-19 Procédé simple de conversion de matières lignocellulosiques Ceased WO2018015610A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/FI2016/050530 WO2018015610A1 (fr) 2016-07-19 2016-07-19 Procédé simple de conversion de matières lignocellulosiques

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/FI2016/050530 WO2018015610A1 (fr) 2016-07-19 2016-07-19 Procédé simple de conversion de matières lignocellulosiques

Publications (1)

Publication Number Publication Date
WO2018015610A1 true WO2018015610A1 (fr) 2018-01-25

Family

ID=60991927

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2016/050530 Ceased WO2018015610A1 (fr) 2016-07-19 2016-07-19 Procédé simple de conversion de matières lignocellulosiques

Country Status (1)

Country Link
WO (1) WO2018015610A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112759619A (zh) * 2021-02-25 2021-05-07 福建农林大学 将木质纤维素一锅法转化为酚类化合物、多元醇和有机酸的方法
CN114887622A (zh) * 2022-05-24 2022-08-12 中国科学院生态环境研究中心 一种选择性氢解木质素碳氧键的金属催化剂及其制备方法与应用
IT202100005024A1 (it) * 2021-03-04 2022-09-04 Hera S P A Catalizzatore magnetico per il frazionamento catalitico riduttivo di biomasse lignocellulosiche
JPWO2023074101A1 (fr) * 2021-10-28 2023-05-04

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100137663A1 (en) * 2009-02-27 2010-06-03 Chen John Q Combination of Hydrogenation and Base Catalyzed Depolymerization for Lignin Conversion
US20120318258A1 (en) * 2010-12-30 2012-12-20 Virent, Inc. Solvolysis of biomass to produce aqueous and organic products
US20140031546A1 (en) * 2012-07-25 2014-01-30 Wenqin Shen Hydrodeoxygenation catalyst
US20140275468A1 (en) * 2013-03-12 2014-09-18 The Procter & Gamble Company Catalysts And Processes For The Production Of Aromatic Compounds From Lignin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100137663A1 (en) * 2009-02-27 2010-06-03 Chen John Q Combination of Hydrogenation and Base Catalyzed Depolymerization for Lignin Conversion
US20120318258A1 (en) * 2010-12-30 2012-12-20 Virent, Inc. Solvolysis of biomass to produce aqueous and organic products
US20140031546A1 (en) * 2012-07-25 2014-01-30 Wenqin Shen Hydrodeoxygenation catalyst
US20140275468A1 (en) * 2013-03-12 2014-09-18 The Procter & Gamble Company Catalysts And Processes For The Production Of Aromatic Compounds From Lignin

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112759619A (zh) * 2021-02-25 2021-05-07 福建农林大学 将木质纤维素一锅法转化为酚类化合物、多元醇和有机酸的方法
CN112759619B (zh) * 2021-02-25 2023-10-20 山东百沃生物科技有限公司 将木质纤维素一锅法转化为酚类化合物、多元醇和有机酸的方法
IT202100005024A1 (it) * 2021-03-04 2022-09-04 Hera S P A Catalizzatore magnetico per il frazionamento catalitico riduttivo di biomasse lignocellulosiche
JPWO2023074101A1 (fr) * 2021-10-28 2023-05-04
CN114887622A (zh) * 2022-05-24 2022-08-12 中国科学院生态环境研究中心 一种选择性氢解木质素碳氧键的金属催化剂及其制备方法与应用

Similar Documents

Publication Publication Date Title
Biswas et al. Catalytic hydrothermal liquefaction of alkali lignin over activated bio-char supported bimetallic catalyst
Figueirêdo et al. Pyrolytic lignin: a promising biorefinery feedstock for the production of fuels and valuable chemicals
Dou et al. Catalytic waste Kraft lignin hydrodeoxygenation to liquid fuels over a hollow Ni-Fe catalyst
Shen et al. Product‐oriented direct cleavage of chemical linkages in lignin
Huang et al. Lignin-first biorefinery: a reusable catalyst for lignin depolymerization and application of lignin oil to jet fuel aromatics and polyurethane feedstock
Liu et al. One-pot catalytic conversion of raw lignocellulosic biomass into gasoline alkanes and chemicals over LiTaMoO6 and Ru/C in aqueous phosphoric acid
Huang et al. Role of Cu–Mg–Al mixed oxide catalysts in lignin depolymerization in supercritical ethanol
US8772557B2 (en) Aromatic hydrocarbons from depolymerization and deoxygenation of lignin
Pipitone et al. Aqueous phase reforming of sugar-based biorefinery streams: From the simplicity of model compounds to the complexity of real feeds
Gunawan et al. Upgrading of bio-oil into advanced biofuels and chemicals. Part I. Transformation of GC-detectable light species during the hydrotreatment of bio-oil using Pd/C catalyst
Cheng et al. Nonprecious metal/bimetallic catalytic hydrogenolysis of lignin in a mixed-solvent system
Guan et al. Highly Dispersed Rh/NbO x Invoking High Catalytic Performances for the Valorization of Lignin Monophenols and Lignin Oil into Aromatics
Suresh et al. Lignin waste processing into solid, liquid, and gaseous fuels: a comprehensive review
Dou et al. Catalytic hydrotreatment of Kraft lignin into liquid fuels over porous ZnCoOx nanoplates
Raikwar et al. Effects of solvents in the depolymerization of lignin into value-added products: a review
Rishikesh et al. A comprehensive review on lignin obtained from agro-residues: Potential source of useful chemicals
Wang et al. Lignin valorization: a novel in situ catalytic hydrogenolysis method in alkaline aqueous solution
Gong et al. Molybdenum-catalyzed hydrogenolysis of herbaceous biomass: A procedure integrated lignin fragmentation and components fractionation
Zhou et al. Microwave assisted depolymerization of alkaline lignin over hydrotalcite-based CuNiAl mixed oxides
WO2014163652A1 (fr) Appareil et procédé pour la préparation de lignine réactive à un rendement élevé à partir d'une biomasse végétale pour la production de carburants et de produits chimiques
WO2018015610A1 (fr) Procédé simple de conversion de matières lignocellulosiques
Yang et al. Catalytic ethanolysis and gasification of kraft lignin into aromatic alcohols and H2-rich gas over Rh supported on La2O3/CeO2–ZrO2
CN110511116A (zh) 一种在双相体系界面全组分解聚原生生物质制备平台化合物的方法
CN107849464B (zh) 使用无定形硅铝氧化物获取单氧化料流的生物质转化方法
Si et al. Enhanced catalytic cleavage of CO and CC bonds of raw biomass into lignin monomers and glucose

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16909448

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16909448

Country of ref document: EP

Kind code of ref document: A1