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WO2014090992A2 - Filtre et procédé de production de produits liquides à partir de produits de pyrolyse de biomasse - Google Patents

Filtre et procédé de production de produits liquides à partir de produits de pyrolyse de biomasse Download PDF

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Publication number
WO2014090992A2
WO2014090992A2 PCT/EP2013/076549 EP2013076549W WO2014090992A2 WO 2014090992 A2 WO2014090992 A2 WO 2014090992A2 EP 2013076549 W EP2013076549 W EP 2013076549W WO 2014090992 A2 WO2014090992 A2 WO 2014090992A2
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WO
WIPO (PCT)
Prior art keywords
pyrolysis
filter
filter unit
ppm
layer
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/EP2013/076549
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English (en)
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WO2014090992A3 (fr
Inventor
Zhiheng WU
Jose Antonio Medrano CATALAN
George Vernon Cordner Peacocke
Mark Coulson
Maria Eleni GYFTOPOULOU
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Future Blends Ltd
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Future Blends Ltd
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Publication date
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Publication of WO2014090992A2 publication Critical patent/WO2014090992A2/fr
Publication of WO2014090992A3 publication Critical patent/WO2014090992A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/10—Filter screens essentially made of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/10—Filter screens essentially made of metal
    • B01D39/12—Filter screens essentially made of metal of wire gauze; of knitted wire; of expanded metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/024—Dust removal by filtration
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2273/00—Operation of filters specially adapted for separating dispersed particles from gases or vapours
    • B01D2273/20—High temperature filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2275/00—Filter media structures for filters specially adapted for separating dispersed particles from gases or vapours
    • B01D2275/10—Multiple layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2275/00—Filter media structures for filters specially adapted for separating dispersed particles from gases or vapours
    • B01D2275/20—Shape of filtering material
    • B01D2275/201—Conical shape
    • 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
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/18—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge
    • C10B47/22—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge in dispersed form
    • C10B47/24—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge in dispersed form according to the "fluidised bed" technique
    • 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

Definitions

  • the present invention relates to a process of producing liquid products from carbonaceous feedstock, such as biomass through fast pyrolysis, further also comprising the catalytic processing of a pyrolysis oil in the gas/vapour/aerosol phase, and the use of the pyrolysis oil.
  • biomass derived from plants and municipal waste is increasingly considered valuable sources for liquid and gaseous hydrocarbon compounds.
  • One of the existing processes for the conversion of biomass includes the steps of pyrolysing biomass to obtain pyrolysis liquids. This is a known process for converting biomass to a gas/vapour/aerosol stream, and the biomass might for example be straw, bagasse, or other agricultural wastes, waste paper, wood, or the organic fraction of municipal solid waste, the resultant gas/vapour stream is then subsequently cooled and pyrolysis liquids recovered by a variety of methods.
  • the process may be applied to biomass grown specifically for the purpose, or to waste materials, such as waste wood and straw, however it is not limited to these materials.
  • the pyrolysis process typically involves heating the biomass to an elevated temperature, possibly in the presence of a restricted quantity of air, typically less than 0.2 of stoichiometric ratio, to break down organic materials and to generate permanent gases such as carbon dioxide, methane, carbon monoxide, hydrogen and small quantities of ethane, ethane, propene, propane and other higher hydrocarbons, pyrolysis oil, and byproducts such as char or charcoal, particulate carbon and pyrolytic water.
  • the obtained pyrolysis gaseous mixture may be combustible, subject to the amount of inert gas present in the mixture and other factors such as stoichiometric air/fuel ratio, temperature, degree of mixing and/or use of additional combustible fuels.
  • the condensable pyrolysis oil may be processed and/or upgraded to obtain specific chemicals, groups of chemicals, non-fuel and fuel products.
  • WO2008005476 disclosing a system comprised of dryer, pyrolysis reactor, char and thermal carriers separator, condenser and char burner for the production of energy, chemical products and other materials
  • US2010209965 disclosing a process for the thermal conversion of particle carbonaceous material as a source of energy into a particular fine particulate biomass is described
  • WO2008092557 disclosing a process and a plant for the conversion of rape seeds and/or their derivatives
  • WO2009138757 disclosing a process for the pyrolysis and gasification of biomass, using a mixing step involving a heat transmitter and transport by a system of screws.
  • Pyrolysis oils obtained typically comprise of a mixture of oxygenated compounds and water generated during the process and from the initial moisture content of the biomass.
  • the process typically includes the cooling and quenching of the gaseous phase directly obtained in the pyrolysis reactor to separate off the formed pyrolysis oxygenated compounds, hydrocarbons and water from non-condensable [at room temperature] gaseous compounds. Further liquids recovery may be performed using coalescing filters, electrostatic precipitators, demisters and/or a combination of these and other physical recovery methods.
  • Ceramic filters are comprised of, but not limited to: silica/alumina, calcium silicate with mineral fibres, e.g.
  • Cao, MgO and lesser oxides, glass fibre based media and other porous, woven and/or meshed and/or fibrous substrate Some of the compounds used in the filter can cause pyrolysis gases and vapours to decompose, leading to pore blockage, surface fouling and a reduction in filtration performance, usually seen as an irreversible increase in pressure drop across the filter media. Some of the larger molecules in the gas phase can also deposit on the surface or in the pores, leading to blockages and increased pressure drop across the candle.
  • a char layer on a filter medium may be overcome by using a cyclone separator.
  • centrifugal force created by the whirling action separates the denser solids from the lower-density gases.
  • the amount of centrifugal force generated is proportional to the square of the tangential entering velocity of the gas and solid mixture, as well as the inverse of the diameter of the cyclone.
  • the efficiency of separation of the solids from the gas is a function of the diameter of the solids, smaller particles are getting more difficult to separate and collect, hence reducing the ability of a cyclone to remove smaller particles and droplets from gases. This is more pronounced when a cyclone is scaled up in size, and/or where the particle size decreases, especially below 10 ⁇ .
  • the thus obtained pyrolysis liquids tend to comprise unacceptably high levels of metals and ash, making them unsuitable for use as a fuel and for direct upgrading treatment to hydrocarbons, though this does not necessarily preclude their use in other applications, e.g. product or chemical synthesis not related to energy applications.
  • To counter the loss in efficiency often higher gas velocities are employed.
  • the presence of solid particles in the liquids appears to cause the pyrolytic lignin present in the liquids to nucleate around the char particles, inhibiting filtration and causing excessive pressure build-up across the filter media.
  • a co- solvent such as an alcohol is typically required to improve filtration, by reducing the viscosity and solubilising the pyrolytic lignin, however this is generally not desirous as the alcohol cannot be easily recovered after filtration of the liquid.
  • Liquids derived from forestry residues which may have multiple phases, or globules present in or on the liquid, exhibit additional challenges with a low polarity, lower density phase which is only partially soluble in alcohols and is more soluble in hydrocarbons thereby requiring the application of two or more solvents to ensure effective filtration.
  • a low polarity, lower density phase which is only partially soluble in alcohols and is more soluble in hydrocarbons thereby requiring the application of two or more solvents to ensure effective filtration.
  • the present invention relates to a porous elongate filter unit for filtering particular matter from a gaseous and/or vapour mixture as obtainable during the pyrolysis of biomass, comprising: (i) a first layer of a porous, gas permeable filter medium having an average pore size in the range of 1 ⁇ to 250 ⁇ ; (ii) a second layer of a porous, gas permeable material having an average pore size in the range of from 1 ⁇ to 250 ⁇ , the layer being positioned in a downstream direction of the gas flow with respect to the first layer; and (iii) optionally, at least one support layer structurally supporting the first and/or the second layer.
  • the subject invention relates to a process for the preparation of filtered gaseous pyrolysis products comprising: (a) providing carbonaceous material to a pyrolysis reactor; (b) heating the carbonaceous material in the pyrolysis reactor under pyrolysis conditions to effect pyrolysis of the material into a gaseous and vapour/aerosol state in a substantially oxygen free and pressure controlled environment; (c) passing the gases through one or more filter units as set out herein above, to obtain separated-out particulate matter, and a purified gaseous pyrolysis mixture.
  • the separated-out particulate matter is herein referred to as char, and includes ash and carbon products such as carbon and tar formed in the process.
  • the process further comprises a step (d), of condensing normally liquid products from the purified gaseous mixture, to obtain normally liquid pyrolysis oil.
  • the subject invention relates to an apparatus for biomass pyrolysis, comprising at least one filter unit according to the invention.
  • the present invention further also relates to a process for pyrolysis of biomass, comprising the steps of (e) subjecting a feed comprising a pyrolysis oil to an esterification process, or a further reaction step, which may include, but is not limited to hydropyrolysis, hydrodeoxygenation and/or deoxygenation step in the presence of a catalyst comprising an active component on a catalyst carrier that is inert at the reaction conditions, to obtain a product stream comprising a partially deoxygenated pyrolysis oil to obtain a partially deoxygenated pyrolysis oil having an oxygen content of 10 to 30 mass fraction [dry liquid basis], and (f) separating at least one product fraction from the product stream obtained in (g), wherein the pyrolysis oil is obtained directly from pyrolysis of biomass under suitable conditions, and the filtration of the thus obtained gaseous and/or vapour product through a filter according
  • the present process further preferably comprises the step of (h) blending the pyrolyis oil obtained in (d) and/or at least one product fraction obtained in (g) with at least another fuel compound and/or an additive to obtain a biofuel suitable for use as is, or as intermediate following further processing to a hydrocarbon fuel or blendable component.
  • the present invention also relates to a process wherein the hydrogenation step is carried out in the presence of a hydrocarbon feed derived from a mineral crude oil or other suitable hydrogen carrier and/or donor material, directly resulting in an upgraded fuel product comprising biofuel components.
  • the hydrocarbon products include aliphatic, aromatic and cyclic hydrocarbon compounds which can directly be used, or when treated further can be converted into fuels.
  • Fig. 1 discloses a schematic diagram of an exemplary filter according to the invention.
  • Fig. 2 discloses a cross-cut of the filter unit.
  • Fig. 3 discloses a top view of the filter unit.
  • Fig. 4 discloses a schematic view of a preferred filter unit according to the invention in a filter chamber/housing.
  • Fig. 5 discloses the schematic view of a further preferred filter unit according to the invention in a filter chamber/housing.
  • PI porosity index
  • the filter medium preferably has a porosity index of 45% to 95%, such as for example 50% to 90%, 65 to 85%.
  • the filter medium preferably is inert under reaction/filtration conditions, i.e. it does not react or physically deform under the temperature and in the presence of pyrolysis mixture and other gases.
  • Suitable materials include ceramic materials, silica, and metals or metal alloys. Metals and/or metal alloys are particularly advantageous due to the inherent lower acidity as compared to ceramics, their resistance to water and corrosion resistance.
  • Preferred materials include silica, copper, platinum, palladium; stainless steel alloys, nickel, Inconel, or a combination of these and similar materials that can withstand temperatures of up to 1000°C, and gas velocities and compositions as typically present in pyrolysis gas.
  • Combinations of metals and ceramics, e.g. metal coated ceramics, and/or ceramic coated metals compositions may also suitably be employed.
  • the filter medium comprises one or more mesh structures formed from fibres or wires, but may also include sintered materials giving similar performance and robustness.
  • the filter medium may comprise wires, fibres or expanded plates, in particular for the filter medium with the larger pore size. These may be prepared from metals or alloys, from silica or ceramics, or any other suitable material that is essentially inert at the reaction conditions. Alternatively or
  • the filter medium may comprise metal powder sheets, perforated sheets such as perforated metal, silicon or ceramic sheets or expanded metal, silicon or ceramic sheets.
  • perforated sheets such as perforated metal, silicon or ceramic sheets or expanded metal, silicon or ceramic sheets.
  • metal fibre and/or "metal wire” is to be understood as a fibre made of any suitable metal or metal alloy.
  • Metal fibres or wires may be prepared by different suitable production processes such as (bundle) drawing processes, coil shaving processes, electro-deposition, and/or or melt extraction.
  • Metal fibres are typically characterised by an equivalent diameter, for the invention preferably in the range of 1 ⁇ to 1 mm.
  • the fibres may be long filaments, or may be provided as fibres having an average length in the range of 1 mm to 1000 m.
  • Metal fibres or wires may advantageously be present as metal wire mesh or grid.
  • any support structure may advantageously be formed such material to reinforce the filter medium.
  • Metal wires may be present as metal wire mesh or grid.
  • the filter medium may comprise metal powder sheets, perforated sheets such as perforated synthetic sheets or expanded synthetic sheets. Less commonly employed, yet also suitable may be porous layer of particles with the required pore size as obtained through sintering of metal powders.
  • filter medium is to be understood any medium, which is able to separate solid particles from a fluid, more specifically from a gaseous feed stream.
  • the filter medium comprises a woven or knitted filter medium.
  • the filter medium comprises a sintered material.
  • the filter medium comprises of a sheet-like material with elongate or otherwise dimensioned and formed perforations, e.g. meshes, grids, expanded sheets or the like. Combinations of woven or knitted filter mesh, sintered and/or sheet like materials such as grids or expanded sheets may also be preferably employed.
  • ring shape is to be understood as having a shape with an outer edge and an inner edge which inner edge encompasses the centre of the outer edge and which inner edge is usually concentric with the outer edge, although the inner and/or outer edge is not necessarily circular. Circular edges are however preferred.
  • the term “elongate” refers to a filter having a shape wherein the length of the filter is higher than its width.
  • the terms “substantially rectangular”, “substantially conical” and “substantially cylindrical” are to be understood as allowing deviation from a perfect rectangular, conical or cylindrical shape due, for example, to normal production tolerances, or as required by the purpose or shape of the filter location, with angular deviations or deviation on length dimensions as appropriate.
  • the term "lumen” relates to space enclosed by the gas permeable filter medium.
  • the lumen is fluidly connected to a further downstream part of the apparatus.
  • layer (i) preferably envelops layer (ii).
  • the gas permeable and porous filter medium preferably comprises a woven or non-woven sheet like material, more preferably at least one mesh or grid-like material.
  • the filter unit may have any suitable shape or dimension, preferably a pyramidal, cylindrical, frustro-conical or conical shape.
  • the filter unit according to the invention is a so-called filter candle. It thus preferably further comprises an axial opening, and an end fitting fixed to the filter medium, the end fitting providing a first end of the filter unit, the end fitting having an end inner surface defining an end fitting opening through the end fitting, the end fitting opening being co-axial with the axial opening of the filter unit; wherein layer (ii) forms a first hollow lumen positioned within the axial opening of the filter unit.
  • the heat source required for the filter housing may involve a furnace or electrical heating means having an independent heating source not associated with another part of the process.
  • heat energy from other parts of the process may be reclaimed and/or recycled and used for heating of the filter and/or filter housing.
  • the heat energy from heating means of one or more of the pyrolysis chambers is directed to the filter housing. If for instance the pyrolysis reactor is heated by a furnace, the heat from the furnace exhaust gases may be reclaimed to e.g. preheat the feed material, using suitable heat exchangers, and then employed for maintaining the filter housing at a desired temperature range.
  • the present invention further advantageously relates to a process for the preparation of filtered gaseous pyrolysis products comprising: (a) providing carbonaceous material to a pyrolysis reactor; (b) heating the carbonaceous material in the pyrolysis reactor under pyrolysis conditions to effect pyrolysis of the material into a gaseous, vapour and/or aerosol state in a substantially oxygen free and pressure controlled environment; and (c) passing the gases through one or more filter units according to the invention, to obtain separated-out particulate matter, and a purified gaseous pyrolysis mixture.
  • step (a) the carbonaceous feedstock is provided to the pyrolysis reactor.
  • ablative systems such as screw-pyrolysers, fluidised beds, stirred or moving beds and vacuum pyrolysis systems.
  • a fluidised bed reactor due to the possibility of a comparatively fast pyrolysis, and the fast removal of the formed products.
  • a fluidised bed reactor typically a pre-weighed mass of inert material, such as round sand is also present.
  • the inert material and the feedstock are the typically fluidised by a gas, which may advantageously be an inert gas, recycled non-condensable pyrolysis gases, partially combusted non-condensable pyrolysis gases, fully combusted non-condensable gases, combustion gases from another material or a combination of these.
  • a gas which may advantageously be an inert gas, recycled non-condensable pyrolysis gases, partially combusted non-condensable pyrolysis gases, fully combusted non-condensable gases, combustion gases from another material or a combination of these.
  • the pyrolysis reactor is typically externally heated, while the heat provided to the fluidised bed leads to the pyrolysis of the introduced biomass.
  • the reactor pressure preferably is in the range of from 0 to 50 bar g, but preferably in the range of from 0 to 12, more preferably in the range of from 0.1 to 1 , yet more preferably less than 0.2 bar g.
  • the filtered vapours are then cooled and condensed, preferably comprising a quenching step.
  • a quenching step involves cooled recirculated isopar V, for instance in a co-current weir-tray column.
  • the co-current flow advantageously reduces fouling and the majority of the pyrolysis vapours and condensable organics can be recovered in such a column.
  • the cooled non-condensed gases will disengage from the condensing liquids, and are preferably passed into a further separator unit to remove aerosols.
  • This may be any suitable separation unit, but preferably involves electrostatic precipitation, e.g. with a wet-walled electrostatic precipitator where the charged central electrode imparts a charge on the generally upflowing aerosols, which essentially deposit on the earthed wetted wall, to obtain deposited aerosols, and a residual cleaned syngas feed.
  • the residual cleaned gases may then preferably subjected to a further condensing step to remove residual water and traces of low boiling compounds such as e.g. acetic acid, prior to atmospheric discharge or recycling to any suitable stage of the process.
  • Char collected on the filter was found to periodically drop off and is preferably collected in the bottom of the filter vessel or housing, which may be advantageously be fitted with a char collection vessel that permits to remove char during the operation.
  • step (a) generally includes preparation of a suitable feedstock composition, e.g. suitable particle size and particle size distribution, appropriate moisture levels and dust load for any chosen reactor design and configuration.
  • step (b) the biomass feedstock particles are typically pyrolysed at a temperature in the range 350°C to 650°C, i.e. lower than temperatures typically used for gasification.
  • the pyrolysis step (b) lasts for at least 1 second, more preferably at least 5 seconds, more preferably at least 10 seconds, and at most 30 seconds.
  • the preferred time for the pyrolysis step depends on the properties of the biomass particles, and in particular on the dimensions of the biomass particles, the ash and water contents.
  • the time for the pyrolysis step may be at least one minute.
  • the time for the pyrolysis step may be relatively shorter than the time for larger particles.
  • the conditions for pyrolysis as described in WO 2010/130988, and the citations therein may be applied; preferably, however vapour temperature is such that neither water formed or present, nor the formed vapours condense prior to step (d).
  • the reactor is preferably operated at a temperature in the range of 400 to 700°C, more preferably from 450 to 570°C, yet more preferably from 500 to 520°C to maximise the yield of organic, condensable products.
  • the feedstock particles are heated by contact with the fluidised sand bed and to a lesser degree by the hot gas used to fluidise the sand bed.
  • Char removal from the bed can be by entrainment in the pyrolysis products and gases, or by other means, e.g., solids overflow via a weir or via an internal cyclone to remove large particles from the exiting products.
  • the pyrolysis reactor internal geometry is preferably chosen such that only fully reacted carbonaceous feed particles exit from the reactor, leaving new carbonaceous feed and partially reacted carbonaceous feed in the reactor.
  • the fluidised bed preferably operates at 1 .1 to 4U mf , more preferably at from
  • step (c) the gases formed are passed through one or more filter units according to the invention, to obtain separated-out particulate matter, and a purified gaseous pyrolysis mixture. Also in this step, a vapour temperature should be maintained such that neither water formed or present, nor the formed vapours condense prior to step (d).
  • the temperature of the gas/vapour phase product obtained in step (b) is preferably in the range of 350 to 650°C. Preferably, it is in the range of 425 to
  • the process is preferably conducted such that the gas/vapour phase product residence time at the filter unit is in the range of from 1 second to 10 seconds, preferably of from 0.5 to 5 seconds.
  • the filtration or superficial gas velocity through the filter unit preferably is in excess of 0.5 cm/s, with a preferred upper limit of 10 cm/s. Preferred is the range of from 2 to 5 cm/s.
  • the absolute gas pressure in the filter unit may for example be in the range of 1 to 10 bar absolute gas pressure, such as for example of from 1 to 5 bar absolute gas pressure, or of from 1 .2 to 3 bar absolute gas pressure, although it is not necessarily limited to those ranges.
  • the filtered pyrolysis gases are preferably condensed into normally liquid products.
  • Normally gaseous products that are not condensed may advantageously be employed as fuel gas for the pyrolysis stage or other processes within and external to the pyrolysis process.
  • the condenser means may include a selective condensation, or staged condensation to remove light fractions from the gaseous pyrolysis material as required.
  • the condenser means may differentially condense different fractions of the gaseous product to select one or more fractions suitable for use as a fuel, directly, or after subsequent catalytic treatment.
  • the condenser means may include one or more condensers capable of condensing fractions at different temperatures or ranges thereof.
  • the condenser means includes a condenser for obtaining fractions suitable for treatment into lighter and heavier fractions.
  • Typical condensing means include direct liquid quenching, staged differential temperature quenching and cooling, indirect cooling in heat exchangers, spray towers, distillation columns and/or direct contact with liquids in towers of various configurations.
  • the invention provides for a process for the thermal conversion of carbonaceous materials into fuels, wherein char and particulate matter is removed from pyrolysis gases by use of one or more of the filters according to the invention.
  • the invention provides for a process for the pyrolysis conversion of carbonaceous materials into fuel products, preferably in a continuous manner.
  • the continuous process system may operate, in principle, similar to a batch system. It may have, however, several distinct refinements that differ from the batch system. Principally, the continuous process may include a continuous feed system to the pyrolysis chambers and/or distillation columns in lieu of one or a series of condensers.
  • the invention further preferably relates to a pyrolysis apparatus comprising: (a) a pyrolysis reactor chamber that heats and thermally decomposes a carbonaceous, preferably biomass material to generate a solid, called char and a particular matter containing pyrolysis gas and/or vapour and/or aerosol from the carbonaceous biomass material, and (b) a filter comprising at least one filter unit as set out herein above, to essentially remove char and particular matter from a filtered gas and/or vapour stream, and (c) a condenser means for cooling and condensing at least one normally fluid pyrolysis oil fraction from the filtered gas and/or vapour stream, and optionally, (d) a hydropyrolysis, hydrodeoxygenation and/or deoxygenation unit for treatment of the normally fluid pyrolysis oil fraction.
  • the pyrolysis apparatus or process plant may be employed to convert carbonaceous matter, i.e. biomass materials and/or other suitable feeds, such as the organic fraction of municipal solid waste, into useable clean fuel, in particular boiling in the middle distillate range.
  • Suitable carbonaceous materials include biomass materials such as vegetable oils, algal biomass; animal debree such as chicken litter; lignocellulosic materials, such as wood chips, saw dust, waste paper, bagasse, grass, straw or corn husks, and/or any other suitable biomass materials that can be subjected to a pyrolysis process, and that generate normally liquid pyrolysis oils.
  • biomass materials such as vegetable oils, algal biomass
  • animal debree such as chicken litter
  • lignocellulosic materials such as wood chips, saw dust, waste paper, bagasse, grass, straw or corn husks, and/or any other suitable biomass materials that can be subjected to a pyrolysis process, and that generate normally liquid pyrolysis oils.
  • normal liquid refers to materials that are liquid under normal conditions, i.e. a temperature of 25°C and an absolute pressure of 1013 mbar.
  • Plant derived biomass is generally composed of three main groups of natural polymeric materials: cellulose, hemicellulose and lignin. Other typical components include smaller organic molecules or lower molecular weight polymers, and inorganic compounds such as metal salts and/or silica.
  • alkali metal salts are known to catalytically promote pyrolysis reactions leading to increased cracking and hence gas make in some circumstances, in addition to ash yield.
  • the process thermally degrades carbonaceous, preferably biomass materials in an essentially oxygen-free environment inside a pyrolysis chamber, thereby pyrolysing it into a gaseous state under the reaction conditions.
  • the components referred to in the gaseous state comprise gaseous components, vapours and/or aerosols.
  • the hot pyrolysis gases are then directly passed through one or more filter units as described herein above, without the need for a removal of particulate matter and char by a cyclone.
  • this may also be done in conjunction with addition of reagents that may be added to the gas phase prior to, or after passing the filter, for instance in the filter of, but not limited to, alcohols having a low boiling point, e.g. methanol, ethanol or isopropanol, or other reactive gases such as hydrogen.
  • reagents that may be added to the gas phase prior to, or after passing the filter, for instance in the filter of, but not limited to, alcohols having a low boiling point, e.g. methanol, ethanol or isopropanol, or other reactive gases such as hydrogen.
  • suitable additives such as metal compounds
  • more preferably calcium compounds may advantageously be considered.
  • the filter according to the present invention is preferably not immersed in, or directly contacted by the fluidised bed for char removal, as for instance disclosed in E. Hoekstra at al, in “Fast Pyrolysis of Biomass in a Fluidized Bed Reactor: In Situ Filtering of the Vapours ", Ind. Eng. Chem. Res. 2009, 48, 4744-4756, but spaced such that it is not directly impinged by the fluidised bed particles, and more preferably placed in a filter housing separate from the pyrolysis reactor vessel.
  • the pyrolysis vapour feed is supplied directly and without an intermediate stage from the pyrolysis reactor to the filter.
  • the apparatus further advantageously comprises means for applying a reverse flow, preferably as a back pulse.
  • a reverse flow preferably as a back pulse.
  • Cleaning of the one or more filter elements is preferably performed individually, or serially during operation, by reversing the gas flow. This is preferably done with flue gas exhibiting the same, or even higher temperature than the vapours emanating from the pyrolysis process. This may be done through simple pulsing, jet pulsing, or under addition of suitable reagents, e.g. solvents, causing a backpulse due to evaporation and expansion.
  • suitable reagents e.g. solvents
  • the present invention also relates to a normally liquid pyrolysis oil comprising less than 25 ppm of Calcium, less than 20 ppm of Potassium, less than 27 ppm of Sodium, and/or less than 10 ppm of Aluminium.
  • the liquid pyrolysis oil comprises less than 23 ppm of Calcium, more preferably less than 20 ppm, yet more preferably less than 15 ppm, such as 14, 13, 12, 1 1 , 10, 9, or less than 8 ppm (as determined by ICP- OES).
  • the liquid pyrolysis oil comprises less than 10 ppm of potassium, more preferably less than 8 ppm, yet more preferably less than 9 ppm, such as 8, 7, 6, 5, 4, 3 or less than 2 ppm.
  • the liquid pyrolysis oil comprises less than 9 ppm of Magnesium, more preferably less than 8 ppm, yet more preferably less than 7 ppm, such as 6, 5, 4, 3, 2, 1 or less than 0.6 ppm.
  • the liquid pyrolysis oil comprises less than 23 ppm of Sodium, more preferably less than 20 ppm, yet more preferably less than 10 ppm, such as 9, 8, 7, 6, 5, 4, 3, 2, 1 , 0.5, 0.3, or less than 0.2 ppm.
  • the liquid pyrolysis oil comprises less than 9 ppm of Aluminium, more preferably less than 8 ppm, yet more preferably less than 7 ppm, such as 6, 5, 4, or less than 3.4 ppm.
  • the liquid pyrolysis oil comprises less than 5 ppm of Mn, more preferably less than 2 ppm, yet more preferably less than 1 ppm, such as 0.5, 0.4, or less than 0.3 ppm.
  • the liquid pyrolysis oil comprises less than 40 ppm of Fe, more preferably less than 22 ppm, yet more preferably less than 8 ppm, such as 6, 5, 4, or less than 3 ppm.
  • the liquid pyrolysis oil comprises less than 5 ppm of Ni, more preferably less than 4 ppm, such as 3, 2, 1 , or less than 0.8 ppm.
  • the liquid pyrolysis oil comprises less than 10 ppm of Cu, more preferably less than 3 ppm, such as 2, 1 , or less than 0.1 ppm, or even essentially free of copper.
  • the liquid pyrolysis oil comprises less than 21 ppm of Zn, more preferably less than 20 ppm, yet more preferably less than 1 1 ppm, such as 9, 8, 7, 6, 5, 4, 3, or less than 2 ppm.
  • the pyrolysis oils obtainable by the present process are furthermore highly storage stable without stabilisation or hydrotreatment, contrary to those typically obtained by processes that use cyclone separators, as also reported by e.g. Diebold, J. P. and Czernik, S, Energy and Fuels, 1 1 , pp. 1081 -1091 .
  • the high stability not only makes the pyrolysis oils according to the invention particularly suitable as intermediate for a further upgrading, but also as direct fuels or fuel components.
  • the present invention therefore preferably also relates to a pyrolysis oil fraction obtainable by the subject process, having a storage stability as expressed by the increase of viscosity of an oil sample provided in a closed vessel maintained at 25°C over time, of less than 50% over a period of 30 days, more preferably less than 30% over a period of 30 days, and yet more preferably less than 15% over a period of 30 days.
  • the viscosity increase preferably is less than 5 cSt (mm 2 /s)/ day, more preferably less than 3 cSt/day, yet more preferably less than 1 .5 cSt/day, again more preferably less than 1 cSt/day, and most preferably less than 0.5 cSt/day.
  • the viscosity referred to above is measured in a pyrolysis oil fraction containing 30 wt% of water as the kinematic viscosity at 40°C according to ASTM method D445A.
  • filtered pyrolysis gas and/or vapour mixture may then advantageously be fed into a hydropyrolysis, hydrodeoxygenation and/or deoxygenation unit, more advantageously, a catalytic hydrodeoxygenation unit, also referred to as a hydrogenation unit, typically by co-feeding a gaseous feed comprising hydrogen, to essentially to obtain water, a gaseous stream, and a normally liquid product stream of upgraded products.
  • a catalytic hydrodeoxygenation unit also referred to as a hydrogenation unit
  • the catalyst particles present in the treatment unit are not prone to catalyst poisoning or consumption.
  • the thus obtained hydrotreated hot gases of the desired carbon length range may be condensed in one or more condensers or, more preferably, in one or more distillation towers, to yield a hydrocarbon distillate and water, and a gaseous fraction. The latter may advantageously be recycled to the process as a heat source.
  • the pyrolysis oil is further subjected to a pyrolysis reaction in the presence of hydrogen.
  • a deoxygenation unit the pyrolysis oil is subjected to a deoxygenation reaction, e.g. reforming, leading to essentially aromatic and unsaturated compounds. All of these reactions are preferably performed in the presence of suitable catalysts.
  • the invention provides for a process wherein the catalyst particles comprise one or more active metal or metal oxide(s) on a carrier, more preferably selected from one or more of metals from Group VIII of the period system.
  • Preferred catalysts comprise iron, cobalt, nickel, manganese, chromium, copper; alumina, silica/titanium oxide and/or mixtures thereof.
  • the invention provides for a substantially carbon based fuel product obtainable by the process of the invention.
  • the fuel includes straight and branched chain aliphatic compounds, aliphatic compounds, branched and cyclic and aromatic hydrocarbons comprising of from 6 to 25 carbon atoms, more preferably from 12 to 18 carbon atoms.
  • the pyrolysis oil may be hydrodeoxygenated as co- feed with other hydrocarbon sources, such as crude mineral oil, tar sand- derived, or Fischer-Tropsch wax-derived hydrocarbon feeds.
  • hydrocarbon sources such as crude mineral oil, tar sand- derived, or Fischer-Tropsch wax-derived hydrocarbon feeds.
  • Example 1 Pyrolysis test using a hot vapour filter (HVF) according to the invention
  • HVF hot vapour filter
  • Commercially available Lignocel BK 8/15 - Spruce with a particle size of from 1 .4 to 1 .8 mm, an ash content of 0.65 wt%, and a water content of 13.3 wt% on a dry basis was fed into a fluidised bed pyrolysis reactor containing a pre-weighed mass of round sand, which was fluidised by nitrogen.
  • HVF hot vapour filter
  • the pyrolysis reactor was externally heated and the heat provided to the fluidised bed lead to the pyrolysis of the introduced biomass.
  • the reactor internal geometry allowed only fully reacted biomass particles to exit from the reactor, leaving new biomass and partially reacted biomass in the reactor.
  • the biomass particles were heated by contact with the fluidised sand bed and the hot gas used to fluidise the sand bed at a temperature in the range of 400 to 700°C, in particular at 500 to 520°C to maximise the yield of organic products.
  • the reactor pressure was maintained at below 0.2 bar g.
  • the sand bed was operated at 2-3.5 U m f, where U m f is the minimum fluidising velocity of the sand bed.
  • the overall gas/vapour product residence was up to 4.2 s, at an average temperature 460-485°C prior to quenching.
  • the filtered vapour were then cooled and quenched with cooled recirculated isopar V in a co-current weir-tray column.
  • the overall gas/vapour product residence was up to 4.2 s, at an average temperature 460-485°C prior to quenching.
  • the cooled gases comprising residual aerosols were passed upwards into a wet-walled electrostatic precipitator to deposit upflowing aerosols on the wetted wall.
  • the thus cleaned gases were passed through 2 dry ice/acetone condensers in series to remove residual water and traces of low boiling chemicals such as acetic acid, before being passed through a pre-dried and weighed cotton wool filter and a drying trap of dried molecular sieve of 3A pore size.
  • the dried non-condensable gases were then passed through a gas meter prior to atmospheric discharge.
  • Four different filters according to the invention were employed, having the following mesh sizes: 5, 25, 100 and 200 ⁇ for the second filter, followed by a second mesh of 100 ⁇ .
  • Table 1 depicts the results of the different runs, as well as a comparative test run using a cyclone particle separator instead of the HVF.
  • Table 1 Overall run summary of Lignocel BK 8/15 pyrolysis
  • Table 3 lists the composition of the obtained pyrolysis oils: Table 3: Effects of HVF on pyrolysis oil property, such as organic elemental composition and metal contents of the oil
  • Example 2 Pyrolysis test using a hot vapour filter (HVF) according to the Invention
  • HVF hot vapour filter
  • Particles ranging from 335 ⁇ to 2 mm, an ash content of 6.24 wt% dry basis and a water content of 1 1 .7 wt% were fed into a fluidised bed pyrolysis reactor containing a pre-weighed mass of round olivine, which was fluidised by nitrogen.
  • the same pyrolysis reactor as Example 1 was used allowing only fully reacted biomass particles to exit from the reactor.
  • the biomass particles were heated by contact with the fluidised olivine bed and hot nitrogen was used to fluidise the olivine bed at a temperature in the range of 400 to 700°C, in particular at 500 to 520°C to maximise the yield of organic products.
  • the reactor pressure was maintained at below 0.2 bar g.
  • the olivine bed was operated at 1 .5-3.0 U m f, where Umf is the minimum fluidising velocity of the olivine bed.
  • the pyrolysis products exited the reactor and were passed into the hot vapour filter vessel where the gases, aerosols and vapours pass through the filter substrate and the char particles were stopped by the filter media.
  • the overall gas/vapour product residence was up to 4.2 s, at an average temperature 460-485°C prior to quenching. Char collected on the filter periodically dropped off and was collected in the bottom of the filter vessel into a fitted char pot.
  • the filtered vapour were then cooled and quenched with cooled recirculated isopar V in a co-current weir-tray column.
  • the cooled gases comprising residual aerosols were passed upwards into a wet-walled electrostatic precipitator to deposit upflowing aerosols on the wetted wall.
  • the thus cleaned gases were passed through 2 ethylene glycol-water mixture condensers in series to remove residual water and traces of low boiling chemicals such as acetic acid, before being passed through a pre-dried and weighed cotton wool filter and a drying trap of dried molecular sieve of 3A pore size.
  • the dried non-condensable gases were then passed through a gas meter prior to atmospheric discharge.
  • One filter according to the invention was employed, having a mesh size of 100 ⁇ for the first filtration medium and 100 ⁇ for the second filtration medium.
  • Table 6 depicts the summarised results for wheat straw particles (335 ⁇ -2 ⁇ ) pyrolysis under different char separation methods: cyclones and HVF.
  • Table 7 Effects on Properties of pyrolysis oil (PO) from wheat straw particles.
  • Table 8 shows the CI and Ca, K, Mg, Na, Al, Fe, P, Si contents in cyclone PO, filtered cyclone PO and HVF PO:
  • Table 8 CI, Ca, K, Mg, Na, Al, Fe, P an Si contents of pyrolysis oil (PO) from wheat straw particles.
  • Table 9 finally lists the properties of the wheat straw particles char:
  • Table 9 Properties of the wheat straw and its pyrolysis char

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Abstract

La présente invention concerne un élément filtrant allongé poreux permettant de filtrer une matière particulaire issue d'un mélange gazeux pouvant être obtenue pendant la pyrolyse d'une biomasse, comprenant : une première couche et une seconde couche de milieux filtrants poreux perméables aux gaz. L'invention concerne en outre un procédé et un appareil pour la pyrolyse d'une biomasse à l'aide de l'élément filtrant, et les produits ainsi obtenus.
PCT/EP2013/076549 2012-12-13 2013-12-13 Filtre et procédé de production de produits liquides à partir de produits de pyrolyse de biomasse Ceased WO2014090992A2 (fr)

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WO2018067814A1 (fr) * 2016-10-06 2018-04-12 Lyten, Inc. Système de réacteur à micro-ondes avec séparation gaz-solides
US9997334B1 (en) 2017-02-09 2018-06-12 Lyten, Inc. Seedless particles with carbon allotropes
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US11542448B2 (en) 2016-06-23 2023-01-03 Glock Ökoenergne Gmbh Method for gasifying carbon-containing material
US10781103B2 (en) 2016-10-06 2020-09-22 Lyten, Inc. Microwave reactor system with gas-solids separation
WO2018067814A1 (fr) * 2016-10-06 2018-04-12 Lyten, Inc. Système de réacteur à micro-ondes avec séparation gaz-solides
US12281013B2 (en) 2016-10-06 2025-04-22 Lyten, Inc. Microwave reactor system enclosing a self-igniting plasma
US10308512B2 (en) 2016-10-06 2019-06-04 Lyten, Inc. Microwave reactor system with gas-solids separation
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US10937632B2 (en) 2017-02-09 2021-03-02 Lyten, Inc. Microwave chemical processing reactor
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US10502705B2 (en) 2018-01-04 2019-12-10 Lyten, Inc. Resonant gas sensor
US10644368B2 (en) 2018-01-16 2020-05-05 Lyten, Inc. Pressure barrier comprising a transparent microwave window providing a pressure difference on opposite sides of the window
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