WO2011159154A1 - Pyrolyse de lignine - Google Patents

Pyrolyse de lignine Download PDF

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Publication number
WO2011159154A1
WO2011159154A1 PCT/NL2011/050429 NL2011050429W WO2011159154A1 WO 2011159154 A1 WO2011159154 A1 WO 2011159154A1 NL 2011050429 W NL2011050429 W NL 2011050429W WO 2011159154 A1 WO2011159154 A1 WO 2011159154A1
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WIPO (PCT)
Prior art keywords
lignin
clay
pelletised
pyrolysis
biomass
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PCT/NL2011/050429
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English (en)
Inventor
Ruud Wilberink
Ron Van Der Laan
Paulus Johannes De Wild
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Stichting Energieonderzoek Centrum Nederland
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Publication of WO2011159154A1 publication Critical patent/WO2011159154A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • 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
    • B01J21/16—Clays or other mineral silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
    • C10B49/04—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated
    • C10B49/08—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form
    • C10B49/10—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form according to the "fluidised bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/34—Other details of the shaped fuels, e.g. briquettes
    • C10L5/36—Shape
    • C10L5/363—Pellets or granulates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • C10L5/447—Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives
    • 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
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • 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 the thermolysis of bio mass, such as lignin.
  • the invention further relates to the product obtained thereby, as well as to the use of such product.
  • the thermal treatment of biomass may be used to generate valuable materials such as char, activated charcoal, bio-oil, combustible gasses, etc.
  • WO2008/147711 describes a system and method for preparing a pelletised carbon black product.
  • the system includes a source of a carbon black product from a pyrolysis process.
  • a mixer is in communication with the source of the carbon black product.
  • a binder oil storage tank is in fluid communication with the mixer. The binder oil storage tank is configured to inject a desired amount of a binder oil into the mixer to form the pelletised carbon black product.
  • WO2009/138757 describes a biomass pyrolysis process in which biomass feed- stock is mixed with a heat carrier.
  • the heat carrier at least partly comprises char.
  • the ratio by weight of biomass to char is in the range 1 : 1 to 1 :20.
  • the process may be carried out by in a screw/auger pyrolysis reactor in which the solid feedstock components are conveyed along the reactor by a first screw.
  • a second screw conveys at least a portion of the solid products of the biomass pyrolysis back to a heat transfer medium input port.
  • the heat transfer medium includes char from the biomass pyrolysis.
  • WO2010/011675 describes a method for producing activated charcoal from lignocellulose-containing material residual solids, wherein the method comprises: i) pre-treating lignocellulose-containing material; ii) hydrolyzing pre-treated lignocellulose-containing material; iii) recovering residual solids; iv) producing activated charcoal from the residual solids.
  • the activated charcoal may be produced from charcoal made by carbonisation or pyrolysis.
  • WO 88/00935 describes a process for the pyrolysis of biomass to produce a high yield of a liquid bio-oil in a reactor that is capable of rapid heat exchange and short gas residence times.
  • the pyrolysis liquid typically contains 10 % - 30 % (wt%) water and can be further processed to divide it into a water-rich fraction and a water-poor fraction. These fractions can be used as feed stocks from which valuable chemicals can be extracted.
  • the pyrolysis process also can be used to produce a pyrolysis liquid that is suitable as a fuel oil.
  • the process can be used to produce a pyrolysis liquid that is suitable for use as liquid smoke which can be used to flavour food, particularly meat.
  • WO2000/06671 describes a method and device for forming synthesis gas from biomass.
  • the biomass is converted into a solid carbonisation product (char) and into gaseous pyrolysis products.
  • the gaseous pyrolysis products are burnt in a burner zone and supply the heat for the endothermic pyrolysis process and for an endothermic gasification process for forming synthesis gas.
  • the carbonisation products are fed to the gasification zone, in order to be converted, for example by means of steam, into H 2 and CO.
  • the fact that the gaseous pyrolysis products and the off-gases from the combustion zone are separate from the gasification zone results in a product gas with a high calorific value which is virtually free of nitrogen.
  • a disadvantage of prior art solutions is that biomass containing high levels of lignin is not easily thermally treated, such as for instance by pyrolysis.
  • the invention provides a process for the thermolysis of lignin- containing biomass comprising:
  • the mixing is preferably performed in the presence of water and can be followed by drying and solidification to result in a particulate material for example by pelletisation.
  • the new and claimed concept for an efficient thermochemical conversion of lignin into value-added products up to 80 wt.% of the dry lignin can be transformed into useful products such as bio-char and phenolic bio-oil.
  • the phenolic oil is an interesting feedstock for e.g. bio-bitumen, phenol substitutes in wood-resins and for several high- value phenolic compounds like guaiacols, syringols and alkylated phenols for pharmaceutical, food, and/or transportation fuel applications.
  • continuous pyrolysis of lignin using conventional screw feeders is now possible.
  • the shape and composition of the solid (pelletised) end product may be tuneable, which allows a tuning to the desired later application of the pelletised end product.
  • the amount of carbon that originates from the pyrolysis of the lignin can be adjusted by the ratio lignin : clay in the pelletised feedstock material.
  • the solid end product ('biochar') will contain varying levels of carbon, depending on the soil characteristics. In case of a sandy soil, it may be preferable to have a relative high content of clay in the solid end product to enhance the water retention in the soil.
  • the application of the solid end product as gas and/or liquid filtration material for organic substances probably requires a higher amount of pyrolytic carbon because of its hydrophobic (apolar) character when compared to the clay constituent.
  • the clay may act as a porous support that gets coated with lignin-derived carbon during the pyrolysis process.
  • pelletised end product is used to distinguish from the pelletised starting material. The term does not exclude a later use or processing of the "pelletised end product”, but refers to the product obtained by the process of the invention. Hence, the invention also provides a pelletised end product obtainable by the process of the invention.
  • a pelletised carbonaceous product comprising pellets having mean dimensions in the range of 0.25-10 mm, such as 0.25-5 mm, like 0.5-5 mm, especially 1-3 mm, wherein the pellets comprise thermolysed biomass, and wherein the pellets preferably comprise carbon in an amount of 5-75 wt.%, preferably 5-60 wt.%, oxides of magnesium and silicon preferably in an amount of 20-95 wt.%, preferably 30-95 wt.%, and 0-25 wt.%, preferably 0-10 wt.% other materials, e.g. aluminium, alkali metals like sodium and potassium, alkaline earth metals like calcium and transition metals like iron, typically in their oxide form, relative to the total weight of the pellets and on dry weight basis.
  • the pellets comprise thermolysed biomass
  • the pellets preferably comprise carbon in an amount of 5-75 wt.%, preferably 5-60 wt.%, oxides of magnesium and silicon preferably in an amount of 20-95
  • thermolysed biomass especially comprises thermolysed cellulosic material, even more especially, the thermolysed biomass comprises thermolysed lignin, which preferably consists for at least 75%, especially more than 90% by weight of carbon, predominantly in elemental form. Preferably at least 50 wt.%), even more preferably at least 80 wt.%> of the pelletised end product particles has a particle size in the indicated ranges, respectively.
  • dimensions is used to refer to length, width and diameter. As will be clear to the person skilled in the art, diameter may especially be applicable for particles having a spherically or elliptically cross-section.
  • mean dimension refers to an average over a plurality of particles.
  • the pelletised carbonaceous material (pelletised end product) can be used as a soil improver, for instance to enable or enhance the growth of feed and food crops on barren soils.
  • the pelletised carbonaceous product may also be used as a precursor for activated carbon, for instance for the production of gas and liquid filtration media.
  • the pelletised carbonaceous material may also be used as a (low-cost) lignin-based cracking catalyst, for instance in pyrolysis processes like the one that is described in this patent.
  • the pelletised carbonaceous product may also be used as a C0 2 -neutral fuel, for instance in waste incinerators or as internal fuel for lignin-pyrolysis processes, whereby the combustion of the carbonaceous fuel pellets ensures that the endothermic pyrolysis process is self-sufficient with respect to its heat demand.
  • the bio-oil contains lignin monomers, oligomers and decomposition products such as high-value phenolic compounds like guaiacols, syringols and alkylated phenols, and may also be used in all kinds of applications.
  • lignin monomers, oligomers and decomposition products such as high-value phenolic compounds like guaiacols, syringols and alkylated phenols, and may also be used in all kinds of applications.
  • feedstock for e.g. bio-bitumen, phenol substitutes in wood resins or phenol resins for use in adhesives and the like, for pharmaceutical, food, and/or transportation fuel applications, as well as for producing carbon fibres.
  • References A1-A4 indicate the components of the mixture for the pre-treatment, comprising lignin (Al), clay (A2), water (A3) and optional one or more other components (A4), like catalysts for cracking, demethoxylation, decarbonylation, decarboxylation, hydrolysis, and/or dehydration, etc.
  • lignin Al
  • clay A2
  • water A3
  • optional one or more other components A4
  • catalysts for cracking demethoxylation, decarbonylation, decarboxylation, hydrolysis, and/or dehydration, etc.
  • Examples are commercial FCC catalysts, ZSM-5 catalysts, supported transition metals (e.g. Ni), and natural tar cracking catalysts like dolomite, olivine and iron ore.
  • the mixture is then subjected to a pre-treatment (B), which at least involves a pelletisation to provide a pelletised starting material. Thereafter, the pelletised starting material is subject to thermolysis (C) to provide the pelletised end product.
  • the pelletised end product may be used in all kinds of applications (D).
  • Figure 2 schematically depicts an arrangement 1 of apparatus that may be used for the process of the invention.
  • Reference numbers 2, 3 and 4 schematically depict the feeds for water (A3), lignin (Al), and clay (A2), respectively.
  • Reference 10 indicates a mixer, wherein the starting materials are mixed into a paste.
  • the paste may be extruded in an extruder, reference 20. This may for instance be followed by strand cutting and rotary drying, indicated with reference 30.
  • the pelletised starting material thus obtained is fed to a reactor. In an embodiment, this is done via a two stage process, via a metered pellet feeding screw 40 and a (water) cooled reactor feeding screw 50.
  • the feeder is cooled so as to prevent the lignin feed from melting prior to entering the reactor.
  • a feed downer pipe 31 may be arranged, but other constructions may also be possible.
  • a feed bunker 41 may be arranged, but other constructions are also possible.
  • the pelletised starting material is provided to a lower part of the reactor.
  • the reactor is indicated with reference 60.
  • a pyro lysis reactor fluid-bed based
  • Reference 61 indicates the fluid bed
  • reference 62 indicates a char overflow pipe, leading to a char bin 63.
  • Fluidisation gas 64 may amongst others be introduced at the bottom 65 of the reactor 60.
  • Particulate product may for instance be recovered via a cyclone 70.
  • An ash bin 71 may be used to collect solid material that is entrained in the fluidisation gas, e.g. fine sand, clay and char particles.
  • a hot gas particle filter 80 the particulate product, here indicate with reference 90, may be obtained.
  • Reference 100 indicates a compressor.
  • Figure 3 shows the Phenolic yields from the pyrolysis of promoted Alcell lignin (A) at 400°C;
  • AMI and AM2 magnesium oxide,
  • AS silica (sand).
  • the y-axis in this figure indicates the product yield in wt.% dry basis (d.b.); MP indicates monomeric phenols, OP, indicates oligomeric phenols and TP indicates total phenolic fraction.
  • lignin is growing due to an increasing interest in renewable raw materials. Large amounts of lignin and lignin containing residues originate from the pulp- and paper industry. The expected growth of the production capacity of second generation bio-fuels from ligno-cellulosic biomass will lead to another source of lignin and lignin containing residues.
  • lignin may be problematic due to the physico-chemical characteristics of lignin as a heterogeneous powder-like material that is sticky, thermoplastic but simultaneously thermally stable.
  • the valorisation of lignin by pyrolysis processes may especially be hampered by feeding difficulties and by the recalcitrant nature of the lignin polymer towards thermal degradation.
  • the products of thermal treatment of state of the art processes may be used in for example agricultural applications of construction applications (for instance solidification of dykes, etc.).
  • the composition of such products of thermal treatment of state of the art process may not easily be varied.
  • thermochemical conversion of lignin into value-added products up to 80 wt.% (weight percentage) of the dry lignin can be transformed into useful products such as bio-char (30-50 wt.%) and phenolic bio-oil (30-50 wt.%).
  • the phenolic oil is an interesting feedstock for e.g. bio-bitumen, phenol substitutes in wood-resins and for several high-value phenolic compounds like guaiacols, syringols and alkylated phenols for pharmaceutical, food, and/or transportation fuel applications.
  • the pyrolysis concept of the invention may include a combination of pre- treatment, feeding and pyrolysis conditions to convert lignin into valuable products.
  • the pre-treatment is the main technical innovation and involves mixing of the lignin with a low-cost clay additive that - in intimate contact with the lignin - improves its feeding and pyrolysis behaviour, preferably in the presence of water.
  • the mixing of the lignin with the additive can be achieved by state of the art pelletising methods such as extrusion and subsequent drying of an aqueous slurry of the lignin.
  • Feeding of the (lignin-additive) pellets into the reactor may be accomplished by using an adapted continuous screw feeder.
  • a combination of feed-rate, reactor temperature and fluidisation gas velocity may ensure an efficient pyrolysis of the pelletised starting material in such a way that a maximum yield of valuable products is obtained.
  • the application of the additive, in the form of lignin clay, may surprisingly prevent defluidisation of the reactor sand bed and enables an efficient separation of char, sand and condensable pyrolysis products.
  • the invention provides a process for the thermolysis of bio mass containing lignin comprising:
  • the composition of the pelletised end product may be tuneable, which allows a tuning to the desired later application of the pelletised end product.
  • the amount of carbon that originates from the pyrolysis of the lignin can be adjusted by the ratio ligninxlay in the pelletised feedstock material.
  • the pelletised end product ('biochar') should contain more or less carbon, depending on the soil characteristics. In case of a sandy soil, it might be preferable to have a relatively high content of clay in the pelletised end product to enhance the water retention in the soil.
  • the application of the pelletised end product as gas and/or liquid filtration material for organic substances probably requires a higher amount of pyrolytic carbon because of its hydrophobic (apolar) character when compared to the clay constituent.
  • the clay acts as a porous support that gets coated with lignin-derived carbon during the pyrolysis process.
  • the thermolysis of the pelletised starting material in the reactor comprises pyrolysing the pelletised starting material.
  • Pyrolysis is the chemical decomposition of condensed substances by heating that occurs spontaneously at high enough temperatures without combustion. Pyrolysis is a special case of thermolysis, and is most commonly used for organic materials, being then one of the processes involved in charring. This chemical process is widely used in the chemical industry, for example, to produce charcoal, activated carbon, methanol and other chemicals from wood, to convert ethylene dichloride into vinyl chloride to make PVC, to produce coke from coal, to convert biomass into syn-gas, to turn waste into safely disposable substances, and for transforming medium-weight hydrocarbons from oil into lighter ones like gasoline.
  • pyrolysis especially refers to the process of heating materials without introduction of oxygen or air at a temperature in the range of about 300-700 °C, like 300-600 °C, such as 350-550 °C or even 400-600°C.
  • biomass means any solid, liquid or intermediate material containing organic matter at least partly derived from biological processes, in particular plant-derived material.
  • the biomass comprises cellulosic material, even more preferably, the biomass comprises lignin.
  • the content of lignin in the (dry) biomass is preferably more than 50 wt.%, more preferably more than 65 wt.%, most preferably more than 80 wt.%.
  • the biomass comprises technical lignin (i.e. especially a material that contains typically > 90 wt% pure lignin).
  • the biomass comprises a lignin from the pulp and paper industry, e.g.
  • black liquor derived lignin e.g. from organosolv, soda, sulfite or Kraft pulping
  • a lignin from the production of second generation bio fuels like bio-ethanol
  • the processes and the products of the invention are especially suitable for relatively pure lignins (> 80 wt.% lignin (dry base)) that are prepared from biomass such as wood, straw, hulls and grass by techniques such as organosolv (a mixture of water and an appropriate organic solvent such as methanol, ethanol, organic acids, etc.), delignification and soda pulping.
  • Alcell organosolv lignin prepared from organosolv fractionation of a mixture of hardwoods
  • Granit soda pulping lignin prepared from a mixture of wheat straw and Sarkanda grass
  • organosolv wheat straw lignin OWSL
  • the physical appearance of these lignins is a light (Granit) to dark brown (Alcell) powder (particle size ⁇ 0.1 mm) that easily melts at low temperatures ( ⁇ 200°C).
  • the lignins are virtually immiscible with water.
  • technical lignins from e.g. organosolv fractionation or from soda pulping are not easily miscible with water due to their hydrophobic character.
  • lignin may refer to a natural lignin, but may also refer to chemical derivatives thereof. In one embodiment, the term “lignin” may also refer to "lignin sulfonate". In another embodiment, ammonium lignosulfonate is used as lignin compound.
  • Lignin compounds are found in cell walls as a cement layer between cellulose strands. They are copolymers, i.e. macromolecules of which the monomers are of a different nature. Three phenyl-propane (C6-C3) derivates are considered as being monomers of lignin: e.g. coniferyl alcohol, sinapyl alcohol and coumaryl or p- hydroxy cinnamyl alcohol.
  • the lignin compound used in the invention comprises one or more of lignin and lignosulfonate.
  • Lignins can be obtained from wood, like e.g. softwood (conifers) or hardwood. The molecular weight varies between about 5,000 and 10,000.
  • clay as additive provides a mixture that is relatively easily pelletisable and later thermolysable in a reactor, without substantial clogging of equipment.
  • mixing the lignin powder with some specific powdered (particle size ⁇ 0.1 mm) clays such as sepiolite, attapulgite and/or bentonite greatly enhances the miscibility with water and enables the preparation of an homogeneous aqueous lignin-clay slurry, e.g. using conventional homogenising equipment.
  • the thickness of the slurry can be adjusted by the amount of water, preferably using a total amount of water of 30-70 wt.% of the total of lignin biomass, clay, water and other components.
  • the lignin-clay slurry can easily be pelletised by well-known techniques such as extrusion.
  • the homogeneity of the lignin-clay slurry may ensure an even distribution of clay and lignin in the resulting pellets or extrudates.
  • a mild temperature treatment preferably ⁇ 150°C in air or vacuum
  • the clay acts as a sort of binder for the lignin.
  • Other clays that possess a high level of porosity and water uptake capacity might be suitable as well.
  • the clay may have a catalytic effect in the pyro lysis of lignin.
  • the clay is preferably a porous clay, especially a phyllo silicate clay, such as magnesium and/or aluminium phyllosilicates.
  • Suitable clays include a hormite clay (such as a sepiolite or attapulgite clay), and a smectite clay (such as a montmorrilonite clay or another bentonite clay). Especially preferred are bentonite and/or sepiolite.
  • the clay comprises hydrotalcite clay.
  • the term "clay" may in an embodiment refer to a combination of clays, such as a combination of bentonite and sepiolite.
  • the clay may especially be a clay from the hormite group.
  • the clay used is sepiolite.
  • the clays from the hormite group are known from the literature. Sepiolite and palygorskite are, for example, described by Galan (Clay Minerals (1996), 31, 443-453). Sepiolite is widely found in Spain.
  • the clay may also be from the smectite group.
  • Bentonite is an absorbent aluminium phyllosilicate, generally impure clay from the smectite group, consisting mostly of montmorillonite (Na,Ca) 2 (MgAl) 2 Si 4 0io.nH 2 0).
  • montmorillonite Na,Ca 2 (MgAl) 2 Si 4 0io.nH 2 0.
  • bentonites There are different types of bentonites and their names depend on the dominant elements, such as potassium (K), sodium (Na), calcium (Ca), and aluminium (Al).
  • Bentonite usually forms from weathering of volcanic ash, most often in the presence of water.
  • bentonite as well as a similar clay called tonstein, have been used for clay beds of uncertain origin.
  • bentonite For industrial purposes, two main classes of bentonite exist: sodium and calcium bentonite. Other smectites, such as saponite, beidellite, aliettite, hectorite, etc. (see www.mindata.org) can also be used.
  • the lignin and the clay are mixed, in general together with water, to provide a paste or slurry, preferably a paste.
  • the paste can be transformed to pellets following methods known in the art.
  • the pre-treatment may include a heating before and/or after the pelletisation.
  • the paste as such is subjected to thermolysis.
  • the biomass (typically containing 0 - 10 wt.% of moisture) and the clay (typically containing 0 - 10 wt.% of moisture) are preferably mixed in a weight ratio of 90: 10 to 10:90, preferably in a weight ratio of 80:20 to 20:80, based on the dry weight of the materials.
  • the amount of water of the mixture (before pelletisation and heating) is preferably in the range of about 30-70 wt.%, preferably in the range 40 - 60 wt% relative to the total weight of the mixture of lignin, clay and water (and optional other components).
  • the pre-treatment comprises (al) providing a paste of biomass, clay and water (and optional other components), (a2) extruding the paste, (a3) providing particulate material, and (a4) drying the particulate material to provide the pelletised starting material.
  • the paste may also be pressed through a sieve with appropriate meshes.
  • the pre-treatment advantageously provides a particulate material ("pelletised starting material"), that may be used for the thermolysis, especially pyrolysis.
  • the pelletised starting material preferably comprises pellets having mean dimensions in the range of 0.25-10 mm, preferably 1-3 mm.
  • At least 70 wt.%, more preferably at least 80 wt.%, even more preferably, at least 90 wt.% of the pelletised material consists of pellets having mean dimensions in the range of 0.25-10 mm or 1-3 mm, respectively.
  • too large and/or too small particles may be separated from the pelletised material, for instance by sieving or using a cyclone separator, or other methods known in the art.
  • the pelletised starting material may then be used in a thermal process, to provide bio-oil and a carbonaceous material, such as charcoal (herein also indicated as “bio char” since it originates from biological material).
  • a carbonaceous material such as charcoal (herein also indicated as “bio char” since it originates from biological material).
  • the thermal process is preferably applied in a fluidised bed reactor.
  • the invention also provides a process (for the thermolysis as described herein), wherein the reactor is a fluidised bed reactor.
  • the pelletised starting material is introduced in the fluidised bed reactor and fluidised.
  • the lignin is thermolysed (especially pyrolysed), by which a pelletised end product is obtained and by which bio oil is obtained.
  • the pelletised starting material is surprisingly stable, leading to a pelletised end product having substantially the same dimensions as the pelletised starting material, but now substantially consisting of thermolysed lignin (carbon) and clay.
  • the latter may not substantially be affected by the thermolysis, whereas the former may be transformed into char and bio-oils (and gasses).
  • the char particles can be retrieved from the reactor.
  • the carbonaceous product (char) will float on the fluidised bed and can conveniently be collected by providing a collecting means just above the bed surface in the form of an overflow pipe or the like, connect to a receiving bin.
  • This product mixture can be collected downstream the reactor by means of appropriate collecting equipment, including condensers for the condensable vapours and an electrostatic precipitator for the aerosols.
  • the invention especially provides a process for the thermolysis of bio mass as described above, to provide bio char and bio oil from a lignin.
  • the process of the invention may be a continuous process (for the production of the pelletised end product and/or bio oil).
  • thermolysis is performed at a temperature in the range of 300-700 °C, especially in the range of 400-600 °C.
  • the term “substantially” herein will be understood by the person skilled in the art.
  • the term “substantially” may also include embodiments with “entirely”, “completely”, “all”, etc. Hence, in embodiments the adjective substantially may also be removed.
  • the term “substantially” may also relate to 90% or higher, such as 95% or higher, especially 99% or higher, even more especially 99.5% or higher, including 100%.
  • the term “comprise” includes also embodiments wherein the term “comprises” means "consists of.
  • Pure lignin pellets can be prepared by (partially) dissolving the lignin in an organic solvent such as ethanol, methanol or acetone and subsequent evaporation of the solvent.
  • the resulting cake can be crushed and sieved into an appropriate size fraction.
  • Alcell lignin also can be pelletised by evaporation and subsequent crushing or extruding an aqueous slurry that is prepared by vigorously shaking the lignin powder with water. The resulting particles are weak and easily fall apart. The mechanical strength of these particles can be increased somewhat by a fusion treatment below 200°C and subsequent solidifying. This procedure also can be applied to the pure lignin powder.
  • Lignin - sand particles were prepared by crushing and sieving of a lignin-sand cake that was made by fusion at 170°C and subsequent solidifying of a 1 : 1 (wt/wt) mixture of Alcell lignin powder with silica sand (particle size -0.25 mm). (pettetising) experiments with natural MgO mineral
  • Natural magnesium oxide mineral was mixed 1 : 1 with Alcell lignin and water and converted into a slurry. It proved to be extremely difficult to extrude this slurry due to phase separation during the extrusion process. However, the slurry could be dried at 200°C under air without melting.
  • Powdered clay was mixed 1 : 1 with lignin and water and converted into an aqueous paste that was extruded into 3-5 mm (length) x 3 mm (diameter) extrudates.
  • the extrudates were dried at 50 - 100°C and subsequently sintered at 100 - 200°C, (pelletising) experiments with an organic binder material
  • Methyl cellulose wall paper glue powder was mixed 1 : 1 with lignin and water and converted into a sticky aqueous paste that could not be extruded. Instead, the paste was dried at 50-100°C and the resulting stone-hard cake was crushed with difficulty into particles of 2-3 mm in diameter.
  • the organosolv Alcell lignin is prepared from a mixture of hardwoods (deciduous wood) while the Granit lignin is a purified lignin from the pulp- and paper industry in India, where it is produced by soda pulping of a mixture of wheat straw and Sarkanda grass. It is a representative herbaceous-derived lignin (trade-name Protobind-1000) that is produced by ALM (Asean Lignin Manufacturing) and marketed by GreenValue SA, Switzerland.
  • Table 1 compares the yields of a set of GC-detected representative phenolic pyrolysis products that were obtained from the five experiments with lignin-sand 1 : 1 (m/m) and lignin-clay 1 : 1 (m/m). The yields are presented in weight percentages that are based on the dry input weight of the Alcell lignin. It should be noted that only a well characterised set of GC-detectable phenolics are presented for comparison. These compounds typically represent 40% of all GC- detected phenolics. The remaining 60% is of unknown origin. Based on their gas chromatographic behaviour (retention time in the chromatogram) it is assumed that they are of phenolic nature.
  • the use of the clays ensured a smooth feeding procedure without clogging of the feed-tube by molten lignin.
  • the porous clays absorb the liquefied lignin and prevent it from sticking to the tube-wall.
  • severe agglomeration was observed in the feed-tube and in the reactor bed, causing fluidisation problems in the reactor bed.
  • Table 2 compares the results from the pyrolysis of Alcell-Sep (1 : 1 weight ratio) under optimised conditions with the results for Alcell-Sep from Table 1. The higher yields are probably due to a different sampling procedure, involving a significantly shorter residence time of the hot pyrolysis vapours in the reactor when compared to the residence time that was used for obtaining the results in Table 1.
  • Table 3 presents the results of the pyrolysis experiments in which the effects of reactor temperature, load and type of additive and type of lignin on the pyrolysis behaviour were investigated.
  • Table 3 Results of pyrolysis experiments at 400°C and 500°C with Alcell and Granit lignin, promoted with sepiolite clay, attapulgite clay, bentonite clay, natural magnesium oxide and silica sand.
  • X sepiolite
  • Y atapulgite
  • Z bentonite
  • M magnesium oxide
  • S silica sand.
  • Alkylphenols [wt%] 0.1 0.1 0.1 0.1 0.0 0.0 0.3 0.3 0.3 0.3
  • the Granit-oil contains more alkylphenols and catechols.
  • the pyrolysis oil from Granit contains more guaiacols than syringols, the oil from Alcell lignin is higher in syringiols than in guaiacols.
  • pyrolysis of clay-promoted Alcell lignin yields - on the average- 53 wt% char, 39 wt% oil and 8 wt% gas at 400°C and 43% char, 41 wt% oil and 16 wt% gas.
  • Pyrolysis of clay-promoted Granit lignin yields 47 wt% char, 43 wt% oil and 10 wt% gas at 400°C and 34 wt% char, 49 wt% oil and 16 wt% gas at 500°C.
  • the results for the magnesium oxide and sand promoted Alcell lignin indicate a less effective pyrolysis of the Alcell lignin.
  • the clay promoted lignins can be pyrolysed without operational problems due to melting and bed agglomeration.
  • the bio-oil product typically contains up to 10 wt% (d.b. of the original lignin feed) of monomeric phenols, predominantly methoxyphenols (syringols and guaiacols).
  • Total yield of phenolic substances varies from 23 to 38 wt%.
  • organosolv wheat straw lignin (OWSL1 : 250 g)
  • organosolv wheat straw lignin - organic methyl cellulose binder material OSL2: 60 g
  • organosolv wheat straw lignin - sepiolite clay material OSL3: 250 g
  • the lignin-containing feedstock was continuously fed into the pre-heated reactor using a cooled screw-feeder.
  • Pre-heated argon (20 ml/min) was used as fiuidisation gas and mixed with an additional 1 ml/min of nitrogen from the feedstock bunker and screw.
  • the reactor bed consisted of 600-1000 g silica sand (0.25 mm).
  • Table 4 shows the beneficial effect of the sepiolite clay additive.
  • both the pure lignin and the lignin treated with the organic binder do not pyrolyse very well.
  • the use of organic binders is not preferred because the organic constituents will be degraded as well, causing undesirable components that end up in the final liquid product. Also, from an economic perspective, the organic binders are expensive in comparison with both the lignin cost and the clay.

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Abstract

L'invention porte sur un procédé pour la pyrolyse de lignine. Le matériau contenant de la lignine est intimement mélangé avec une argile phyllosilicate et éventuellement réduit en granulés. La matière de départ en granulés est introduite dans un réacteur de pyrolyse et pyrolysée pour produire un produit carboné granulé et une bio-huile contenant des monomères de lignine.
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