WO2009090072A1 - Carbonisation hydrothermique de biomasse - Google Patents

Carbonisation hydrothermique de biomasse Download PDF

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Publication number
WO2009090072A1
WO2009090072A1 PCT/EP2009/000228 EP2009000228W WO2009090072A1 WO 2009090072 A1 WO2009090072 A1 WO 2009090072A1 EP 2009000228 W EP2009000228 W EP 2009000228W WO 2009090072 A1 WO2009090072 A1 WO 2009090072A1
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WO
WIPO (PCT)
Prior art keywords
pressure vessel
biomass
controllable
pressure
catalyst
Prior art date
Application number
PCT/EP2009/000228
Other languages
German (de)
English (en)
Inventor
Lucia Viviane Sanders
Original Assignee
Lucia Viviane Sanders
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lucia Viviane Sanders filed Critical Lucia Viviane Sanders
Publication of WO2009090072A1 publication Critical patent/WO2009090072A1/fr

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Classifications

    • 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
    • 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
    • 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
    • C10G1/008—Controlling or regulating of liquefaction processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • 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
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • 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
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/086—Hydrothermal carbonization
    • 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

Definitions

  • biomass encompasses all living, dead and / or decomposed organisms.
  • these include, in particular, waste and / or residual wood, straw, grass, manure, leaves, sewage sludge, animal manure, residues from biogas plants and other conversion processes and / or organic household waste.
  • the biomass can be found in different compositions, qualities, sizes and / or the like use, depending on the needs and desired conversion product use.
  • a pressure vessel with biomass consisting essentially of plant products, water and a small amount of a catalyst, in particular citric acid, filled.
  • the pressure vessel is closed and performed under temperature and pressure increase the conversion or implementation of the biomass.
  • the resulting reaction is exothermic, which means that energy is released in the form of heat and / or light.
  • the duration of this conversion process depends on the desired state of the conversion product and has hitherto been, for example, for the conversion of biomass into coal in a time range of about twelve hours.
  • the pressure vessel is at a temperature of about 180 degrees Celsius to about 200 degrees Celsius held.
  • the pressure vessel is opened and the conversion product - in a conversion of biomass into coal small floating on the water coal particles - taken from the pressure vessel.
  • the object of the present invention in view of the state of the art, is to improve the hydrothermal carbonization of biomass, in particular with regard to the duration of the conversion process and with regard to the manner in which the process is conducted.
  • the technical solution to this problem is the present invention, a method and for the hydrothermal carbonization of biomass, biomass with water and at least one catalyst in a pressure vessel by increasing the temperature and / or pressure in substances such as coal, oil and / or the like related substances is proposed, which is characterized in that the biomass is disorganized before the conversion and / or during the conversion.
  • disorganization is understood to mean any damage to the structure of cells and / or complex molecules in the biomass with the aim of causing material damage in the mold such that defined fragments of the starting material are formed, as well as the end products defined particle size, respectively composition obtained.
  • the invention is based on the finding that the time duration of the biomass conversion process can be significantly reduced by a disorganization of the biomass according to the invention before and / or during the conversion process, in comparison to process guides without disorganization according to the invention.
  • the duration of the biomass conversion process according to the invention can be reduced, preferably to less than or equal to one hour, compared to the duration of a process without disorganization of the biomass according to the invention - depending on the desired or desired state of the final product.
  • An advantageous embodiment of the invention provides that the disorganization takes place by means of ultrasound.
  • the biomass is intended to be heated according to the invention.
  • the gradient of the heating in addition to the or the catalysts used for a defined disorganization is responsible. If the ultrasonic power does not reach a sufficient temperature gradient due to the type of biomass, for example, this can be supported by an additional heat source with sufficient gradient power.
  • This is advantageously done by the use of microwaves.
  • the disorganization of the structures of cells and / or complex molecules in the biomass is advantageously carried out in the flow by means of ultrasound in a tube.
  • the coupling of the microwave can be done directly in front of or behind this tube, advantageously in this tube.
  • a further advantageous embodiment of the invention provides that the disorganization takes place by means of microwave irradiation.
  • the biomass advantageously heats up.
  • the biomass is passed through a microwave flow reactor having at least one reaction space, which is advantageously the ultrasonic flow tube.
  • the biomass guided through the microwave flow reactor is advantageously heated, preferably within about 30 s and about 20 min, in particular in a range of about 1 min and about 5 min, to a temperature in a temperature range between about 150 degrees Celsius to about 250 degrees Celsius, in particular to a temperature between 160 degrees Celsius and 190 degrees Celsius.
  • Another embodiment of the invention is characterized by a pressure in the first reaction space (ultrasound and / or microwave) of the microwave flow reactor in a pressure range between about 15 bar to about 300 bar.
  • the ultrasonic power and the gradient of the temperature and its height can be advantageously a defined disorganization with regard to the achieved particles, as well as the separation of complex molecules at defined locations achieve.
  • Vegetable proteins in particular proteins of marine plants, here advantageously microalgae, can be brought into a chain form as defined by a multi-dimensional complex ball, which is then divided into specific amino acids. This type of division is essential for the synthesis of e.g. aliphatic hydrocarbon chains, as required in the petroleum synthesis of the invention mentioned here.
  • inorganic bases or organic acids are used as catalysts.
  • an economically usable ammonia yield can be produced from the nitrogen-containing molecular parts thus separated, preferably from the biomass of marine origin.
  • the amounts of hydrogen required for this synthesis by adding hydrogen from a gas reservoir (eg gas cylinders), but preferably by composition of the biomass, preferably by Bacteria contained in the biomass, advantageously hydrogen-producing bacteria such as Chlamydomonas provided.
  • this is advantageously a tube piece filled with an acidic mineral (pH ⁇ 4), eg fractured quartz, the catalyst structure advantageously having a pore size of ⁇ 10 mm, in particular ⁇ 2 mm.
  • an acidic mineral pH ⁇ 4
  • the catalyst structure advantageously having a pore size of ⁇ 10 mm, in particular ⁇ 2 mm.
  • the supply of biomass, water and / or at least one catalyst for Filling of the first, ultrasonic and / or microwave for disorganization having pressure vessel can be carried out in parallel, so that biomass, water and / or catalyst are fed individually. Accordingly, a separate supply of biomass, a separate supply of water and / or a separate supply of catalyst are provided.
  • the mixing ratio of the components biomass, water and / or at least one catalyst is carried out via a corresponding control system.
  • an ultrasonic and / or microwave transmitter is arranged for disorganization in at least one region of the pipeline forming the pressure vessel. This is primarily the beginning of the pipeline system for achieving the specific biomass and molecular fragments necessary for the production of the coal or oil according to the invention.
  • the temperature and / or pressure conditions in the pressure vessel are controlled such that the product supplied to the pressure vessel from biomass, their Disorganisations located at the pipeline.
  • a mass layer passes through the pressure vessel designed as a pipeline during the conversion process.
  • the intermediate products corresponding to the respective time of the conversion process are present at different points along the pipeline at any time.
  • the supply of biomass, respectively their Disorganisations occur, water and / or at least one catalyst via at least one arranged before the at least one controllable inlet opening of the pressure vessel, at least one controllable inlet opening and at least one controllable outlet opening having lock chamber takes place the lock chamber is connectable on the part of the at least one controllable inlet opening with at least one storage reservoir of biomass, water and / or at least one catalyst and on the part of the at least one controllable outlet opening with the at least one controllable inlet opening of the pressure vessel.
  • the transport of biomass, water and / or takes place at least one catalyst from the lock chamber into the pressure vessel by pressurization.
  • a further advantageous embodiment of the invention provides that the supply of biomass, water and / or at least one catalyst takes place via a piston-pressing device arranged in front of the at least one controllable inlet opening of the pressure vessel, wherein the piston-pressing device has a chamber with at least one inlet opening, at least one controllable outlet opening and a movable piston in the chamber for pressing befindlichem in the chamber Good.
  • the transport of biomass, water and / or at least one catalyst from the chamber into the pressure vessel is carried out by means of the piston pressurization.
  • the supply of biomass, water and / or at least one catalyst advantageously takes place via an eccentric screw pump with pressure regulation arranged in front of the at least one controllable inlet opening of the pressure vessel.
  • the transport of contents located in the pressure vessel in particular in coal production consisting of land-bound biomass or macroalgae, supported by a preferably arranged in the pipeline of the pressure vessel controllable conveyor, particularly preferably in the form of a controllable screw conveyor.
  • the delivery volume of the conveyor can be controlled in advance, preferably via a control device.
  • the screw conveyor extends substantially over the entire length of the pipeline of the pressure vessel and is adapted substantially flush with the inner cross section of the pipeline of the pressure vessel.
  • a further advantageous embodiment of the invention provides that the temperature and / or pressure conditions in the pressure vessel are controlled via the at least one controllable inlet opening and / or the at least one controllable outlet opening, preferably via at least one control device.
  • the pressure vessel is heated.
  • the pipeline of the pressure vessel is at least partially disposed in a container which can be filled with at least one heat transfer medium, preferably oil, and the heating of the pressure vessel is controlled via the temperature of the at least one heat transfer medium in the vessel.
  • resulting heat energy (reactor heat) is dissipated directly and thus supplied to areas where the conversion process has already taken place or has progressed further.
  • an overheating of individual process sections is prevented.
  • a particularly advantageous embodiment of the invention for the production of coal products is characterized by using a thickener, preferably corn starch such as cereal and / or potato starch, for the contents of biomass, water and at least one catalyst.
  • a thickener preferably corn starch such as cereal and / or potato starch
  • parts or particles of the biomass can float in the water in the pressure vessel and / or deposit in the pressure vessel.
  • cereals and / or cereal-like products or their constituents used as biomass fall due to their specific weight in the pressure vessel, which sometimes increases Blockages in the pressure vessel leads.
  • biomass used foliage and / or foliage-like products or their components floats in the pressure vessel, which sometimes also leads to blockages in the pressure vessel.
  • the thickener is added in amounts effective to provide a substantially viscous consistency.
  • the thickening agent is first added to the water and / or the catalyst. Subsequently, this viscous water-catalyst mixture is added to the biomass.
  • the removal of the at least one reaction product of the filling material takes place via a separating device arranged downstream of the at least one controllable outlet opening of the pressure vessel, preferably by filtering.
  • a further advantageous embodiment of the invention is characterized in that the reaction product is pressed before and / or after removal.
  • Another particularly advantageous embodiment of the invention provides that the supply of biomass, water and / or at least one catalyst, the temperature and / or pressure conditions in the pressure vessel, the transport of the contents through the pressure vessel and / or the removal of the at least one Reaction product of the filling material from the pressure vessel via a control.
  • a control According to the invention, in particular the operating and personnel expenses in the course of the process control can be further reduced.
  • a further embodiment of the invention advantageously provides for fully automatic process control.
  • a device for the hydrothermal carbonization of biomass wherein biomass is converted with water and at least one catalyst in a pressure vessel by increasing the temperature and / or pressure in substances such as coal, oil and / or the like related substances proposed , which is characterized by at least one device for disorganization of biomass, which is arranged in fluid communication before and / or in the pressure vessel.
  • the disorganizing device has at least one ultrasonic transmitter, at least one microwave transmitter and / or at least one microwave flow reactor.
  • the pressure vessel is formed from at least one pipeline with at least one controllable inlet opening and at least one controllable outlet opening.
  • a particularly advantageous embodiment of the invention is characterized in that the pipeline between the at least one inlet opening and the at least one outlet opening has at least one bend, preferably at least one substantially U-shaped bend.
  • the at least one pipeline of the pressure vessel is arranged at least partially in a container which can be filled with at least one heat transfer medium, preferably oil.
  • a further advantageous embodiment of the invention is characterized by at least one controllable heating device for controlling the temperature in the pressure vessel.
  • the temperature of the heat transfer medium in the container via the heater is controllable.
  • a further embodiment of the invention is advantageously characterized by at least one lock chamber arranged in front of the at least one controllable inlet opening of the pressure vessel for supplying biomass, Water and / or at least one catalyst through the at least one controllable inlet opening of the pressure vessel, comprising at least one controllable inlet opening and at least one controllable outlet opening.
  • the lock chamber is advantageously connectable on the part of the at least one controllable inlet opening with at least one storage reservoir of biomass, water and / or at least one catalyst and on the part of the at least one controllable outlet opening with the at least one controllable inlet opening of the pressure vessel.
  • a concrete embodiment of the invention provides that the controllable inlet opening of the pressure vessel forms the controllable outlet opening of the lock chamber.
  • a further embodiment of the invention is characterized by at least one pump for controllable and / or controllable pressurization of the lock chamber.
  • a further advantageous embodiment of the invention is characterized by a prior to the at least one controllable inlet opening of the pressure vessel arranged piston-pressing device for supplying biomass, water and / or at least one catalyst through the at least one controllable inlet opening of the pressure vessel, comprising a chamber with at least one inlet opening , at least one controllable outlet opening and a piston movable in the chamber for pressing material located in the chamber.
  • a further advantageous embodiment of the invention is characterized by an eccentric screw pump with pressure regulation arranged in front of the at least one controllable inlet opening of the pressure vessel for supplying biomass, water and / or at least one catalyst through the at least one controllable inlet opening of the pressure vessel.
  • a further advantageous embodiment of the invention is characterized by at least one control device for at least partially automatic control of the temperature and / or pressure conditions in the pressure vessel via the at least one controllable inlet opening and / or the at least one controllable outlet opening.
  • a further advantageous embodiment of the invention is characterized by at least one control device for at least partially automatic control of the supply of biomass, water and / or at least one catalyst, the temperature and / or pressure conditions in the pressure vessel, the transport of the contents through the pressure vessel and / or the removal of the at least one reaction product of the filling material from the pressure vessel.
  • FIG. 1 is a schematic diagram of an embodiment of a device for the hydrothermal carbonization of biomass in a discontinuous operation according to the prior art
  • FIG. 2 a shows a schematic illustration of an embodiment of an apparatus according to the invention for the hydrothermal carbonization of biomass in a continuous operation
  • FIG. 1 is a schematic diagram of an embodiment of a device for the hydrothermal carbonization of biomass in a discontinuous operation according to the prior art
  • FIG. 2 a shows a schematic illustration of an embodiment of an apparatus according to the invention for the hydrothermal carbonization of biomass in a continuous operation
  • FIG. 1 is a schematic diagram of an embodiment of a device for the hydrothermal carbonization of biomass in a discontinuous operation according to the prior art
  • FIG. 2 a shows a schematic illustration of an embodiment of an apparatus according to the invention for the hydrothermal carbonization of biomass in a continuous operation
  • FIG. 1 is a schematic diagram of an embodiment of a device for the hydrothermal carbonization of biomass in a discontinuous operation according to the prior art
  • FIG. 2b in a schematic diagram of another
  • Embodiment of a device according to the invention for the hydrothermal carbonization of biomass in a continuous operation Embodiment of a device according to the invention for the hydrothermal carbonization of biomass in a continuous operation
  • FIG. 3 shows a sectional side view of an exemplary embodiment of a pressure vessel according to the invention for the hydrothermal carbonization of biomass in a continuous operation according to FIG. 2a;
  • FIG. 4 shows a schematic side view of an exemplary embodiment of a pressure vessel according to the invention for the hydrothermal carbonization of biomass in a continuous operation according to FIG. 2b;
  • 5a-5c show a schematic illustration of an embodiment of an inventive filling of the pressure vessel of a device according to the invention for the hydrothermal carbonization of biomass in a continuous operation via a lock chamber.
  • FIG. 7 is a schematic diagram of an exemplary embodiment of a part of a regulation according to the invention of a device according to the invention for the hydrothermal carbonization of biomass in a continuous operation
  • FIG. 8 is a schematic diagram of an embodiment of a device according to the invention for the hydrothermal carbonization of biomass in a continuous operation with a filling via a piston-pressing device
  • FIG. 8 is a schematic diagram of an embodiment of a device according to the invention for the hydrothermal carbonization of biomass in a continuous operation with a filling via a piston-pressing device
  • FIG. 11 in a schematic schematic diagram of another
  • FIG. 14a shows a schematic side view of a further exemplary embodiment of a pressure vessel according to the invention of a device according to the invention for the hydrothermal carbonization of biomass
  • Fig. 14b is a view of the end face of the bottom of the pressure vessel of Fig. 14a;
  • 16a shows a schematic side view of an exemplary embodiment of a special flange of a pressure vessel according to the invention of a device according to the invention for the hydrothermal carbonization of biomass;
  • Fig. 16b is a view of the end face of the special flange pressure vessel of Fig. 16a;
  • FIG. 17 in a schematic schematic diagram of another
  • FIG. 18a shows a schematic side view of an exemplary embodiment of a conveying device according to the invention in a pressure vessel according to the invention of a device according to the invention for the hydrothermal carbonization of biomass;
  • FIG. 18b shows a view of an end face of the conveyor device according to FIG. 18a;
  • FIG. 19a shows a schematic illustration of another embodiment of a device according to the invention for the hydrothermal carbonization of biomass
  • FIG. 19b shows a schematic side view of the outer container of the device according to FIG. 19a;
  • FIG. 1 shows a device for the hydrothermal carbonization of biomass in a discontinuous operation according to the prior art.
  • an existing from biomass with water and at least one catalyst product 1 is filled in a first pressure vessel 2 (start container) and the pressure vessel 2 then sealed pressure-tight.
  • start container the pressure vessel 2
  • the pressure vessel is maintained at a temperature of about 180 degrees Celsius to about 200 degrees Celsius.
  • the duration of this exothermic conversion process in the present case is about twelve hours.
  • the pressure vessel 2 is opened and the conversion product taken from the pressure vessel 2. The removal takes place in the present case via a shut-off device 3 in a pressure vessel 4 (follow container 1).
  • shut-off elements 5 and 7, respectively Connected to the pressure vessel 4 in a correspondingly cascaded manner via shut-off elements 5 and 7, respectively, are further pressure vessels 6 or 8 (follow-up containers 2 to follow-up containers n).
  • the reaction product 10 in this case in particular in the form of coal sludge, finally taken over a shut-9.
  • the withdrawn reaction product is fed to the first pressure vessel 2 (start tank) via a heating pipe system having a pump 11 to utilize the heat of reaction.
  • the pressure vessel 13 forming the raw pipe is formed straight.
  • the pressure vessel 13 or 13 'forming pipeline via the controllable obturator 14 of the inlet opening of the pressure vessel 13, the existing biomass, water and / or at least one catalyst 12 is supplied and then the pressure vessel 13 or 13' sealed pressure-tight. Then, the temperature and the pressure in the pressure vessel 13 and 13 'are increased. The temperature and / or pressure conditions in the pressure vessel 13 or 13 'are controlled such that the pressure vessel 13 or 13' supplied product 12 is transported independently and preferably defined through the pipeline. The biomass, water and catalyst of the product in the pipeline react with each other. According to the invention, a mass layer passes through the pressure vessel designed as a pipeline during the conversion process.
  • the length of the pipeline in conjunction with the filling quantity - and thus with the size or the diameter of the pipeline - determines the duration of the process.
  • the reaction product 16 Via the controllable obturator 15 of the outlet opening of the pressure vessel 13 or 13 ', the reaction product 16, in this case in particular in the form of coal sludge and / or oil-like products, finally for further processing and / or use by opening the obturator 15 is removed.
  • the embodiment according to the invention advantageously allows a continuous operation, wherein via the controllable inlet opening the pressure vessel 13 or 13 'continuously, that is present sometimes at intervals, contents 12 is supplied and via the controllable outlet opening of the pressure vessel 13 or 13' continuously, the In the present case, sometimes also at intervals, the reaction product 16 is taken.
  • the illustrated in Fig. 3 in a sectional side view of the invention illustrated pressure vessel 17 for hydrothermal carbonization of biomass in a continuous operation of Fig. 2a is formed of two straight, different diameter and substantially coaxially arranged extending pipes 18 and 19, an inner tube 18th and an outer tube 19. At the free ends of the inner tube (inner tube 18) forming the pipe 18, flanges 20 and 21 are welded.
  • the flanges 20 and 21 are used for receiving or connecting controllable shut-off valves for the inlet opening or the outlet opening of the pressure vessel 17. In the region of the right in Fig. 3 end of the pipe 18, this is welded via a compensator 22 to the flange 21. In the space between the inner pipe 18 and the outer pipe 19 are present distributed over the length of the pipes 18 and 19 and spaced apart from each other ring-shaped stabilizing ribs 23 are arranged. The stabilizing ribs 23 in particular prevent damage and / or bending of the outer pipe 19, which due to the weight of the pressure vessel 17, in particular in the filled state and during operation, could be caused by the support relationship way 24 Aufstelllager of the pressure vessel 17.
  • the space between the inner pipe 18 and the outer pipe 19 is present preferably unpressurized, that is without pressurization with a heat transfer medium (not shown in Fig. 3), preferably a bio / thermal oil, filled, which for heating the pressure vessel 17, in particular the inner pipe 18, serves.
  • a heat transfer medium preferably a bio / thermal oil, filled, which for heating the pressure vessel 17, in particular the inner pipe 18, serves.
  • the heating of the pressure vessel 17 is controlled by the temperature of the oil.
  • the filling of the pressure vessel with the biomass, water and / or at least one catalyst via at least one lock chamber 32 with a controllable inlet opening and a controllable outlet opening, which in front of the at least one controllable inlet opening of Pressure vessel is arranged.
  • the controllability of the inlet opening of the lock chamber 32 is realized in the present case with a slide 33 which is controllable via an actuator or a drive 34.
  • the controllability of the outlet opening of the lock chamber 32 is realized in the present case with a slide 35 which is controllable via an actuator or a drive 36.
  • the lock chamber 32 can be sealed by means of the controllable slide 33 against a refill bearing 37 for biomass, water and / or catalyst and by means of the controllable slide 35 with respect to the pressure vessel.
  • the filling material 38 consisting of biomass, water and / or at least one catalyst is stored in front of the inlet opening of the lock chamber 32, in the present case in the refill bearing 37.
  • the inlet opening of the lock chamber 32 is opened by the controllable slide 33 - as shown in FIG. 5a shown - filling material 38 in the lock chamber 32, in this case by falling.
  • the lock chamber 32 which is substantially completely filled with contents 38 ', is then closed by adjusting the controllable slide 33 of the inlet opening of the lock chamber 32 (see Fig. 5b) and then the pressure in the lock chamber 32 is adjusted to the pressure in the pressure container.
  • Fig. 5b the controllable slide 33 of the inlet opening of the lock chamber 32
  • this pressure equalization is symbolically represented by a pressure equalization line 39 between the closed lock chamber 32 and the adjoining the slide 35 of the lock chamber 32 section which is connected to the at least one controllable inlet opening of the pressure vessel.
  • the pressure equalization takes place in the present case with a pump by means of compressed air or water.
  • the target pressure in this case the An Eisenbuchs, in the Lock chamber 32
  • the outlet opening of the lock chamber 32 by adjusting the controllable slide 35 is opened (see Fig. 5c).
  • the pressure in the lock chamber 32 is increased, represented symbolically in FIG. 5c by the arrow marked 40.
  • the filling material 38 'located in the lock chamber 32 is pressed into the pressure vessel-as shown in FIG. 5c-and the pressure vessel is filled. After emptying the lock chamber 32, this is closed again by adjusting the controllable slide 35 of the outlet opening of the lock chamber 32. Subsequently, the process repeats beginning with Fig. 5a.
  • the filling container 38 of a device 26 according to the invention for the hydrothermal carbonization of biomass in a continuous operation is continuously filled with biomass, water and / or at least one catalyst via at least one eccentric screw pump 41 with integrated pressure control 42 supplied, which is arranged in front of the at least one controllable inlet opening of the pressure vessel 29.
  • the finely divided, spherical carbon particles dissolved in the water are advantageously removed by filtration, preferably by means of filtration devices, decanters and / or centrifuges.
  • the wet coal mass is then in coal pellets with a diameter of about 6 mm to about 60 mm or pressed into briquettes.
  • the coal pellets are advantageously used in particular because of their high purity as a base product for the chemical industry, as a fertilizer or as directly usable or useful for combustion processes.
  • oil- or oil-like products advantageously form at certain pressure and / or temperature conditions, taking into account the concentration of the catalyst and / or the process or throughput time.
  • a device 47 according to the invention for the hydrothermal carbonization of biomass in a continuous operation shown in Fig. 8
  • the supply of biomass, water and / or at least one catalyst existing filling 48 takes place in the pressure vessel 49 of the device 47 via a piston-pressing device 50.
  • the piston-pressing device 50 has a chamber 51 with an inlet opening 52, a controllable outlet opening 53 and a piston movable in the chamber 51
  • controllable inlet opening of the pressure vessel 49 is formed by the controllable outlet opening 53 of the piston chamber 51.
  • filling material 48 is first introduced into the piston chamber 51 when the outlet opening 53 is closed and the piston 54 is withdrawn. Subsequently, the filling material 48 located in the piston chamber 51 is pre-pressed to a defined pressure by means of the piston 54. Upon reaching the defined pressure, the slider 55 opens from the piston chamber 51 to the pressure vessel 49 and the piston 51 presses the compressed filling material 48 into the pressure vessel 49. Subsequently, the slide 55 closes the inlet opening of the pressure vessel 49 of the device 47 and thus the outlet opening 53 the chamber 51 of the piston-pressing device 50.
  • this pressure increase is used to remove a chamber 57 for removal (Outlet chamber / lock chamber) to be filled by reaction products of the invention in the pressure vessel 49 converted contents with reaction products of the contents.
  • the chamber 57 has a controllable inlet opening 58 and a controllable outlet opening 59.
  • the controllable outlet opening of the pressure vessel 49 is formed by the controllable inlet opening 58 of the chamber 57.
  • the controllability of the inlet opening 58 of the lock chamber 57 is realized in the present case with a slide 60 which is controllable via an actuator or a drive 61.
  • the controllability of the outlet opening 59 of the chamber 57 is realized in the present case with a slide 62, which is controllable via an actuator 63 or a drive 63.
  • the slide 60 To fill the chamber 57 of the slider 60 opens the chamber 57. Before the slider 60 befindliches reaction product of the contents, in this case a water-carbon mixture, is then pressed from the pressure vessel 49 into the open chamber 57. With the completion of this press-fitting process, the slide 60 also closes off the inlet opening 58 of the lock chamber 57 in a pressure-tight manner relative to the pressure vessel 49. The reaction product located in the lock chamber 57 can then be removed via the slide 62 of the lock chamber 57, sometimes with the use of a controllable pressure compensation container 64 as needed. In FIG. 8, the removal is shown symbolically by the arrow marked with the reference numeral 65.
  • reaction product of the contents in this case a water-carbon mixture
  • the pressure vessel 49 is formed by straight pipe 49, which passes through another, in the present case also designed as a straight pipe line container 66.
  • the space between the pipe 49 of the pressure vessel 49 and the pipe 66 of the container is presently filled with a bio / thermal oil as a heat transfer medium, which is guided for heating the pressure vessel 49 advantageously under pressure in a circuit and heated or heated as needed.
  • the embodiment shown in FIG. 9 differs from the embodiment shown in FIG. 8 of a device 47 according to the invention hydrothermal carbonization of biomass in a continuous operation by the design of the pressure vessel 49 'and the container 66' through which the pressure vessel is performed.
  • the pressure vessel 49 'of the device 47 of FIG. 9 is formed by a curved pipe 49'.
  • the arrangement of the bends of the pipe 49 ' is advantageously designed so that the lighter biomass / coal is always transported against the buoyancy through the pipe 49'.
  • diaphragms 49 ' are disposed in the pipeline 49' as reflux and / or lift barriers 68 (shown symbolically in FIG. 9).
  • FIG. 10 of a device 47 according to the invention for the hydrothermal carbonization of biomass in a continuous operation substantially corresponds in structure and mode of operation to the embodiment illustrated in FIG. 8 and described above.
  • the transport of the biomass through the pressure vessel 49 depends on the consistency and / or the composition of the biomass to be filled into the pressure vessel 49.
  • biomass is in the pressure vessel forming pipe 49 a conveyor 69, in this case a screw helix 69 having screw conveyor with an external slow-speed motor Drive integrated.
  • the contents of biomass, water and catalyst is transported by rotation of the screw spiral in the pressure vessel to the outlet opening 58 of the pressure vessel 49.
  • the rotational speed of the screw conveyor is controllable and, in addition, the process of the conversion according to the invention.
  • the screw flight is essentially flush with the inner cross section of the pipeline 49 of the pressure vessel 49.
  • FIG. 11 The illustrated in Fig. 11 embodiment of a device according to the invention 47 for the hydrothermal carbonization of biomass in a continuous operation corresponds in construction and operation substantially the embodiment shown in Fig. 8 and described above and differs from the embodiment shown in Fig. 10 by the used conveyor 69 'to support the transport of biomass through the pressure vessel 49.
  • the conveyor 69' through a controllable pump is formed, which regulates the pressure gradient between the inlet opening and the outlet opening of the pressure vessel, in particular taking into account the pressure conditions to be observed for the conversion process.
  • the pressure vessel forming pipe is arranged as a arranged in a large pipe 70 pipe package from present total seven individual pipes 71 and admitted.
  • the large tube 70 serves at the same time as a container for the heat transfer medium. Due to this construction, the erfindungsgenzeße device can be advantageously carried out transportable.
  • FIG. 13 shows a schematic side view of a further pressure vessel
  • the pressure vessel 73 is essentially composed of a reactor tube which is closed at the left end in FIG. 13 with a dished bottom 77 and at the right-hand end with a connection flange
  • the reactor tube of the pressure vessel 73 is presently a spiral-welded tube DN600 with a length L of about 6.00 m and a diameter D of about 0.60 m.
  • Distributed over the length of the pressure vessel 73 and spaced apart from each other are connecting pieces 75 with a diameter of approximately 1.25 inches, in particular for supplying substances or removing intermediate substances.
  • the hydrothermal carbonization process according to the invention advantageously takes place with disorganization of the biomass at an operating temperature of about 250 degrees Celsius to about 450 degrees Celsius, an operating pressure of about 25 bar to about 300 bar and coal production with a pH of 4.5 as well as in oil production with a pH between pH6 and pH9.
  • the pressure vessel 78 is essentially formed by a pipeline.
  • the pressure vessel 78 has a port 79 with a flange 80.
  • the pressure vessel 78 has spigot 81 with a diameter of about 1, 25 inches and further, the pressure vessel 78 in the region of the left in Fig. 14a end of its bottom connecting sleeves 82 having a diameter of about 0.75 Inch up.
  • the connection stubs 81 and connection sleeves 82 are used in particular for supplying substances or removing intermediate substances.
  • the container 80 has an inner bearing shell 83 for an agitator shaft which, in particular in conjunction with a corresponding disorganizing device, serves for disorganizing the biomass according to the invention.
  • connection sleeves 89 With a diameter of approximately 0.75 inches.
  • FIGS. 19a to 19d A further exemplary embodiment of a device 97 according to the invention for the hydrothermal carbonization of biomass is shown in FIGS. 19a to 19d.
  • the device 97 comprises a pressure vessel 98 formed of a bent multi-turn piping having a controllable inlet 99 and a controllable outlet 100.
  • the pressure vessel 98 is guided with its windings through an outer container 101 which is filled with a heat transfer medium, in this case a thermal oil.
  • the thermal oil is guided in a circuit through the container 101, for which purpose it has a controllable inlet opening 102 and a controllable outlet opening 103.
  • a disorganization of the plant structures takes place before and / or during the conversion process taking place in the pressure vessel.
  • the disorganization takes place by means of ultrasound in a tube.
  • the biomass is conveyed from a storage container by means of a screw or piston diaphragm pump in a vertical tube.
  • this tube is an ultrasonic transmitter, against which the biomass is promoted.
  • the degree of disorganization depends on the conveying speed, the power of the ultrasonic transmitter and the delivery pressure.
  • the disorganized material flows around the ultrasound exciter and is transported further by the delivery pressure of the subsequent material. In this step, a first heating of the biomass takes place.
  • the pressure within the reaction space can additionally be adjusted and / or controlled by pump pressure or gas pressure above the temperature corresponding to the vapor pressure curve values.
  • the material is heated to a temperature between about 180 degrees Celsius and about 250 degrees Celsius in a microwave reactor having a reaction space shaped as a helix (see Fig. 19d).
  • the reaction (conversion process) is carried out in the flow and over a period of about three minutes to about 20 minutes.
  • the reaction takes place at pressures of about 15 bar to about 300 bar.
  • the reaction mixture further reactants and catalysts can be supplied.
  • the supply of hydrogen H and carbon monoxide CO leads to the formation of complex organic structures, such as polymers.
  • the resulting in this way suspension and solution of monomers and / or polymers in water is forwarded to form new organizational structures / molecular structures in a likewise heated pipe.
  • the reaction time is up to four hours, depending on the desired end product.
  • the use of ultrasonic waves during the reaction under microwave irradiation in the first 20 minutes results in the production of pure carbon.
  • reaction product (coal dissolved in water in finely divided, spherical form)

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé et un dispositif de carbonisation hydrothermique de biomasse, de la biomasse étant transformée en substances telles que du charbon, du fioul et/ou similaires au moyen d'eau et d'au moins un catalyseur dans un contenant sous pression par augmentation de température et/ou de pression. Pour améliorer la carbonisation hydrothermique de biomasse, notamment en ce qui concerne la durée du processus de transformation et le type de commande de processus, la biomasse est désorganisée avant et/ou pendant la transformation, par exemple au moyen d'ultrasons, de micro-ondes ou par décompression.
PCT/EP2009/000228 2008-01-16 2009-01-16 Carbonisation hydrothermique de biomasse WO2009090072A1 (fr)

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WO2012168502A1 (fr) * 2011-06-09 2012-12-13 Ingelia, S.L. Procédé d'extraction de produits biochimiques obtenus à partir d'un processus de carbonisation hydrothermique de la biomasse
US20130011327A1 (en) * 2010-03-24 2013-01-10 Dominik Peus Method and Device for Treating Solid-Fluid Mixtures
US8637718B2 (en) 2009-09-25 2014-01-28 Auburn University Biomass to biochar conversion in subcritical water
ES2441318A1 (es) * 2012-07-31 2014-02-03 Ingelia, S.L. Proceso de bombeo de biomasa en un proceso de carbonización hidrotermal
CN104560074A (zh) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 一种微波热解制生物油和活性炭的系统
AU2012341144B2 (en) * 2011-11-21 2015-07-23 Carbonscape Limited Apparatus and method for processing biomass
WO2016192403A1 (fr) * 2015-06-04 2016-12-08 浙江科技学院 Procédé de préparation d'engrais carboné à base de paille de riz afin de réduire les émissions de gaz à effet de serre des rizières
CN115520863A (zh) * 2022-11-04 2022-12-27 合肥工业大学 水热或溶剂热法制备的煤基活性炭及其制法和应用

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DE102010064715B3 (de) 2010-03-24 2022-04-28 Antacor Ltd. Verfahren und Verwendung eines Rohrreaktors zur Behandlung von Fest-Flüssig-Gemischen
DE202011001453U1 (de) 2011-01-13 2011-05-05 Ribegla S.A. Anlage zur Energierückgewinnung aus Biomasse und brennbaren Abfällen, insbesondere nachwachsenden Rohstoffen sowie zur Karbonisierung
DE102011004398A1 (de) * 2011-02-18 2012-08-23 Siemens Aktiengesellschaft Verfahren und Reaktor zur hydrothermalen Karbonisierung von Biomasse
DE102011051542B4 (de) * 2011-07-04 2013-04-25 Jenoptik Katasorb Gmbh Mikrowellenreaktor zur mikrowellenunterstützten Erwärmung eines Mediums
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DE102011055990A1 (de) * 2011-12-02 2013-06-06 Thomas Reichhart Verfahren sowie Vorrichtung zur hydrothermalen Karbonisierung von Biomasse
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CN108975305A (zh) * 2018-08-20 2018-12-11 宁夏和兴碳基材料有限公司 一种利用脱水污泥制备碳基材料的方法
CN111378464B (zh) * 2020-03-25 2022-02-25 重庆交通大学 一种水热碳化技术处理餐厨垃圾的家用小型原位处理设备及全封闭回收系统
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US20110226603A1 (en) * 2008-11-21 2011-09-22 Dominik Peus Method And Device For Producing Operating Materials Or Fuels
US8637718B2 (en) 2009-09-25 2014-01-28 Auburn University Biomass to biochar conversion in subcritical water
US11097249B2 (en) * 2010-03-24 2021-08-24 Antacor, Ltd. Method and device for treating solid-fluid mixtures
US20130011327A1 (en) * 2010-03-24 2013-01-10 Dominik Peus Method and Device for Treating Solid-Fluid Mixtures
EP2474591A1 (fr) 2011-01-10 2012-07-11 CSL Carbon Solutions Ltd Synthèse de matière humique synthétique par carbonisation hydrothermale
WO2012095408A1 (fr) 2011-01-10 2012-07-19 Csl Carbon Solutions Ltd. Synthèse d'une matière humique artificielle par carbonisation hydrothermale
EP2719748A1 (fr) * 2011-06-09 2014-04-16 Ingelia, S.L. Procédé d'extraction de produits biochimiques obtenus à partir d'un processus de carbonisation hydrothermique de la biomasse
EP2719748B1 (fr) 2011-06-09 2017-05-10 Ingelia, S.L. Procédé d'extraction de produits biochimiques obtenus à partir d'un processus de carbonisation hydrothermique de la biomasse
EP2719748A4 (fr) * 2011-06-09 2015-04-01 Ingelia S L Procédé d'extraction de produits biochimiques obtenus à partir d'un processus de carbonisation hydrothermique de la biomasse
ES2393464A1 (es) * 2011-06-09 2012-12-21 Ingelia, S.L. Procedimiento para la extracción de productos bioquímicos obtenidos a partir de un proceso de carbonización hidrotermal de biomasa.
WO2012168502A1 (fr) * 2011-06-09 2012-12-13 Ingelia, S.L. Procédé d'extraction de produits biochimiques obtenus à partir d'un processus de carbonisation hydrothermique de la biomasse
US9556384B2 (en) 2011-06-09 2017-01-31 Ingelia, S.L. Method for extracting biochemical products obtained from a process of hydrothermal carbonization of biomass
AU2012341144B2 (en) * 2011-11-21 2015-07-23 Carbonscape Limited Apparatus and method for processing biomass
US9505991B2 (en) 2011-11-21 2016-11-29 Carbonscape Limited Apparatus and method for processing biomass
AU2015246130B2 (en) * 2011-11-21 2017-08-24 Carbonscape Limited Apparatus and method for processing biomass
ES2441318A1 (es) * 2012-07-31 2014-02-03 Ingelia, S.L. Proceso de bombeo de biomasa en un proceso de carbonización hidrotermal
CN104560074A (zh) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 一种微波热解制生物油和活性炭的系统
CN104560074B (zh) * 2013-10-22 2017-03-01 中国石油化工股份有限公司 一种微波热解制生物油和活性炭的系统
WO2016192403A1 (fr) * 2015-06-04 2016-12-08 浙江科技学院 Procédé de préparation d'engrais carboné à base de paille de riz afin de réduire les émissions de gaz à effet de serre des rizières
CN115520863A (zh) * 2022-11-04 2022-12-27 合肥工业大学 水热或溶剂热法制备的煤基活性炭及其制法和应用
CN115520863B (zh) * 2022-11-04 2023-11-21 合肥工业大学 水热或溶剂热法制备的煤基活性炭及其制法和应用

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