EP2134821A1 - Procédé de transformation chimique par voie humide de la biomasse par carbonisation thermohydraulique - Google Patents

Procédé de transformation chimique par voie humide de la biomasse par carbonisation thermohydraulique

Info

Publication number
EP2134821A1
EP2134821A1 EP07856078A EP07856078A EP2134821A1 EP 2134821 A1 EP2134821 A1 EP 2134821A1 EP 07856078 A EP07856078 A EP 07856078A EP 07856078 A EP07856078 A EP 07856078A EP 2134821 A1 EP2134821 A1 EP 2134821A1
Authority
EP
European Patent Office
Prior art keywords
suspension
reaction
reactor
reaction volume
water
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.)
Withdrawn
Application number
EP07856078A
Other languages
German (de)
English (en)
Inventor
Peter Eisner
Andreas Malberg
Andreas STÄBLER
Michael Menner
Markus Antonietti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP2134821A1 publication Critical patent/EP2134821A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • 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
    • 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
    • C10L9/02—Treating solid fuels to improve their combustion by chemical means
    • 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

  • the present invention relates to a process for the conversion of biomass into higher energy density solids, in particular coal, humus or peat, in which organic matter from the biomass is slurried to form a suspension in water and at least one part of the suspension to be converted heated to a reaction temperature and converted at elevated pressure by hydrothermal carbonation in the solids of higher energy density.
  • the organic substances may, for example, be plant parts, other biomass or organic waste.
  • the ingredients especially the carbohydrates (eg sugar, starch, celluloses, hemi-celluloses or others), in various raw materials, different plants and parts of plants, residues from food production, sewage sludge or other biogenic materials and waste, the Reaction faster or slower.
  • the concentration and structure of the ingredients especially the carbohydrates (eg sugar, starch, celluloses, hemi-celluloses or others), in various raw materials, different plants and parts of plants, residues from food production, sewage sludge or other biogenic materials and waste, the Reaction faster or slower.
  • the concentration of the ingredients especially the carbohydrates (eg sugar, starch, celluloses, hemi-celluloses or others), in various raw materials, different plants and parts of plants, residues from food production, sewage sludge or other biogenic materials and waste, the Reaction faster or slower.
  • more or less heat is released per unit of time
  • the object of the present invention is to provide a process for the conversion of biomass into higher energy density solids by hydrothermal carbonation, with which a more uniform quality of the products is achieved and the efficiency of the process is increased.
  • organic matter from the biomass is slurried to form a suspension in water.
  • a suspension in water.
  • a preferred embodiment is in the water a
  • the material that supports the conversion may be for example, an acid and / or an organic or inorganic substance which accelerates the reaction.
  • the biomass may be, for example, organic waste, plant parts, wood, algae or other organic carbonaceous products.
  • At least one part of the suspension to be converted is heated to a reaction temperature and converted at elevated pressure by means of hydrothermal carbonization into the solids of higher energy density.
  • the method is characterized in that the conversion is carried out in a reaction volume which is located below the surface of the earth.
  • reaction volume to a first reaction volume Preferably, the reaction volume to a first reaction volume
  • Earth's surface is understood to be the boundary layer between the solid earth crust or the waters on the one side and the atmosphere on the other side.
  • this material can be a large part of the reaction in the
  • the pressure also does not vary so much. As a result, the reaction does not start so quickly and more evenly at the beginning.
  • the concentration of convertible biomass constituents decreases over time, the temperature falls within
  • Reaction volume does not decrease as quickly as in the case of the previous known process control. Rather, the surrounding material then slowly releases the stored heat back to the reaction volume.
  • the reaction volume thus remains much longer warm and the reaction can be continued without additional heating of the suspension over many hours or even days, until even different raw materials are converted to comparable products with higher energy density.
  • a further advantage of the proposed method is that new biomass can be supplied by the return of heat from the surrounding material into the reaction volume even after removal of the products and can be reacted without external heating or at least without strong additional heating. This allows in many cases the carbonization of several batches in a row without external supply of heat. Basically, the method thus allows both a continuous supply of biomass and a batch operation. As a result, the throughput in the process of the invention can be varied very greatly due to the heat buffering of the surrounding soil or water, without sacrificing the uniformity of the product quality.
  • the process must be carried out in an area below the earth's surface in which a sufficient mass of surrounding material is available for the thermal buffering.
  • the material should in this case be constructed so compact that it has a total mass in the vicinity of four times the mean diameter of the reaction volume, which corresponds to at least eight times the mass contained in the reaction volume. Based on a cylindrical reaction volume of a diameter D and a height H, this means that a cylindrical volume with the same height and four times the diameter minus the cylindrical reaction volume should contain at least eight times the mass of the reaction volume filled with the suspension contains in order to achieve a particularly good heat buffering for the proposed method.
  • the surrounding material such as soil, loam, sand or water, is able to at least partially compensate for and absorb the pressure resulting from the reaction due to the pressure prevailing below the earth's surface.
  • a reactor used for the hydrothermal carbonization can therefore be made significantly thinner walled for use under the earth's surface than when used above the earth's surface. This saves additional costs.
  • this reactor may, for example, consist of steel, which in concrete or reinforced concrete in a cavity under the
  • the wall of this reactor can be made very thin-walled.
  • the wall of the cavity can be used as a reactor wall. If necessary, this cavity can be additionally lined with waterproof materials. Such a lining can also be achieved by synthetic additives in the water. An automatic seal by the reaction products of the process, such as. Carbon particles, may u.U. take place opposite the surrounding rock.
  • the product composition can also be made uniform as the pressure increases above the pressure corresponding to the reaction temperature becomes. Due to the additional application of a pressure in the reaction volume, the pressure also increases during the entire reaction and then decreases again, but the percentage relative pressure fluctuations are smaller. It is particularly advantageous if the pressure in the reaction volume is kept constant or at least largely constant by technical measures. These measures decouple temperature and pressure from each other. The operator of the hydrothermal carbonation is thus able to choose the pressure according to the composition of the input so that the homogenization of the product quality is improved. When applying an additional pressure not only the composition of the final product can be made uniform. Rather, depending on the input material, the yield of solid products with high energy density can be increased by the increased pressure, so that the process can be operated even more economically. The operator has with the additional pressure build-up a valuable
  • the additional pressure build-up, in addition to various other mechanical methods z. B. also be achieved in that the reaction volume is displaced sufficiently deep into the soil.
  • the location of the reaction volume is chosen so deep that a water column located above the reaction volume, which is needed for the supply and removal of the suspension, a hydrostatic pressure in the reaction volume which is higher than the equilibrium pressure which would be set at the reaction temperature in a gas-tight reactor filled with the suspension.
  • a hydrostatic pressure it is also very easy to maintain a constant pressure. It only has to be ensured that a liquid inlet or outlet is possible on the surface of the water column. This can, for example. Through openings or by using non-sealing pumps such as.
  • Centrifugal pumps are possible. With a temperature increase in the reaction volume, liquid can then escape at the surface and the pressure in the reaction volume remains largely constant.
  • the water column is used as a pressure buffer. The reaction conditions are thereby made uniform and the solids yield can be additionally increased.
  • reaction volume is formed with a greater width than height.
  • hydrostatic pressure generation an approximately equal pressure is generated at all points in the reaction volume, whereby the homogenization of the reaction conditions is additionally supported.
  • This formation of the reaction volume can be achieved by introducing into horizontally extending shafts, for example. Kohlemachiningchte.
  • a height difference of at least 100 m is selected between the upper fill level and the reaction volume.
  • the reactor is designed such that the inlet and outlet openings are arranged at the same height or at least, compared to the total reactor height, at a similar height, so that a hydrostatic pressure difference between the openings does not account for 10% of the pressure exceeds.
  • the pumps used then do not have to overcome high pressure differences and can thus be made very simple and inexpensive.
  • the outer wall of the reactor flexible, so that it conforms to the inner wall of the cavity or at least serves only as a barrier to the surrounding rock or water. It is also particularly advantageous to use thin sheets or metal foils which have a high temperature resistance in comparison to other materials.
  • An advantage of the pressure build-up by the hydrostatic pressure in the reactor is that the pressure increases evenly with increasing depth.
  • the residence time can be set specifically and thus adapted to the respective raw material. It is useful to have cooling water connections at regular intervals over the height and volume of the reactor to introduce cold water and slow down the reaction when needed. This can be used to avoid overheating of the reaction and to use the heated water energetically. This process can also be done via to be installed in the reactor heat exchanger.
  • mixing elements can be incorporated into the reactor to limit the sedimentation of solids.
  • Particularly advantageous gases such as compressed air can be introduced into the reactor, which cause a mixing. It is also possible to achieve gas formation by partial evaporation of the water in the suspension. The turbulences that arise in this case lead to a good mixing and to avoid blockages. Targeted evaporation of some of the water can also be used to deflate the reactor after completion of the reaction. This can be done by pumping in the inlet or outlet befindlichem
  • the flow cross sections can be reduced so far that a critical flow velocity is exceeded. It is also possible to run a cascade in galleries underground
  • Rlickreaktoren to build and surrounded by soil, rock or water, which are flowed through in series. In this form, they are very inexpensive to manufacture and allow a quick flow.
  • Clogging of the reactor can also be avoided if the flow direction is reversed at regular intervals and thus a type of pulsation is achieved, which is superimposed on a constant flow velocity.
  • This pulsation leads to turbulence in the reactor and thus prevents deposits very efficiently.
  • impurities such as stones, metal, glass or similar inorganic materials
  • This may be gravitational separation, such as a clarifier in sewage treatment plants, or a hydrocyclone or other method known in the art for separating solids from suspensions.
  • particles that are prone to sedimentation can be selectively removed from the reactor.
  • devices may be introduced into the reactor which will batch or continuously convey sedimented solids from the reactor with prior art aggregates (e.g., conveyors, scrapers, chains, screws, pumps). These solids can be fractionated outside the reactor, so that coarse organic materials can be returned to the reaction space after a corresponding comminution.
  • the reactor consists only of a cavity present in deeper rock layers, wherein the feed of the reaction mixture is conveyed through a feed line to a depth sufficient for the reaction.
  • Particularly advantageous is e.g. the use of old production shafts from mining, shut down tunnels or other underground structures.
  • the existing lining of the shafts or tunnels can be used as a "reactor wall" and the entire volume of the shaft as a reactor.
  • Sealing of the system can be achieved by additives in the water or the system seals itself by the reaction products such as coal particles against the surrounding rock itself.
  • an inlet or outlet When using holes in the ground, an inlet or outlet must be provided in the lower part of the reactor. Through an inlet or outlet channel in the lower portion of the shaft or hole, the cross-sectional area and flow rate can be variably adjusted, an upward flow is set over the entire remaining shaft cross-section.
  • the area ratio of upflowed reactor space and upflowed reactor part can be up to 99.99% depending on the requirement of 0.01%.
  • Heat exchangers for cooling or heating which can be arranged in the shaft, are used for temperature and reaction control and thus the
  • horizontally extending coal shafts formerly used as underground mining areas and now shut down, can be used as reaction volumes.
  • the raw material suspension can be introduced into shafts via outlying areas, and all input streams from the production well can be conveyed centrally from deep within, or vice versa.
  • the water used for the suspension it is advantageous for the water used for the suspension to be completely or partially recirculated for the complete utilization of raw materials.
  • the desired reaction product such as coal particles from the suspension and remaining substrates, unreacted raw materials and reaction products such as phenols or other secondary products to promote together with new crushed biogenic raw material back into the reaction space.
  • the skilled person is aware that a concentration of minerals or unreactable Shares must be avoided. This can be done by a correspondingly dimensioned bleed current.
  • the described method brings additional advantages when operated in combination with geothermal energy.
  • energy is added to the reaction mixture in warmer areas in the soil, the reaction mixture is additionally heated and the reaction is thus accelerated.
  • the additional energy released can then be used in the prior art by dissipating the heat or by transformation into electricity or hydrogen.
  • the carbon-rich reaction products are in many cases present as finely dispersed nanospheres. This fact can be used to promote solid energy very beneficial.
  • a mechanical separation of the solids from the liquid takes place, for example by centrifugal separation processes.
  • the liquid fraction containing the amino acids and minerals from the organic raw material can be used as fertilizer directly or after concentration by partial separation of the water.
  • the nanoparticulate solids which consist predominantly of carbon, are again mixed with water and adjusted to a dry matter content of 40 to 60% by mass.
  • an energy density of up to 18 gigajoules per tonne can be set in the suspension, which corresponds to about half the energy density of crude oil.
  • the viscosity of the suspension in the feed of the reactor should be at least 20 mPas
  • the liquid phase should not exceed values of 5 mPas.
  • the promotion of biomass or reaction suspension takes place in depth in vessels or containers such as containers, barrels, baskets, sacks, cylindrical or cuboid vessels made of different materials or in similar spatially defined volumes in the interior of the under Earth attached reactor.
  • the containers or vessels are sufficiently heated in the reactor, so that the reaction can take place inside the container, without discharging the biomass from the containers.
  • valves in the containers that depending on the depth of the pressure in the reactor can be transferred to the interior of the container.
  • the promotion of the containers through the reaction space can be carried out in a displacement promotion, similar to the procedure in the case of tower heaters in the food industry, which are used for heating cans. Each container pushes the next container in the tubular reaction space on. It is also possible to use conveyors for containers of the prior art, such as e.g. Chain conveyors, screws, cables or other devices for transporting vessels through pipelines. The transport of the containers through the shaft or reaction cavities can also be carried out in a similar way to other transport
  • Reactor areas are separated by locks, sheets or other internals or that so-called. Pigging, which cause a substantial sealing of the reactor cross-section and are moved with the flow are used as partitions between individual reactor sections. Due to this multi-chamber design of the reaction space, different process conditions such as temperatures can be set in each segment, which facilitates process control.
  • Fig. 2 is a schematic representation of the process flow in the proposed
  • Figure 1 shows schematically an example of an embodiment of a reactor for carrying out the present method, which is introduced in this example in a shaft 1 below the earth's surface.
  • the shaft 1 is located at a depth of 200 m.
  • the reactor 2 has an inlet 3 to the reaction volume, which in this case occupies the entire volume of the horizontally arranged reactor.
  • the slurried biomass is pumped via this feed 3 in the reaction volume.
  • the reaction products are pumped back up via the outlet 4.
  • the wall of the reactor 2 can be made relatively thin, since the hydrostatically generated in this case pressure is absorbed by the surrounding soil 5.
  • the reactor 2 is surrounded in a radius of soil 5, which corresponds to at least four times the diameter D of the reaction volume.
  • the slurried biomass is first introduced into the reactor 2 at a temperature of about 80 ° C. Due to the very violent exothermic reaction in the reaction volume at the beginning of the process, the suspension heats up to over 200 0 C. The heat absorption and storage due to the large mass of the surrounding material means that there is no rapid overheating. In a later stage of the reaction, in which much less heat is generated, the reaction temperature is achieved by the heat given off by the surrounding material, so that the reaction can be maintained without external supply of energy over a longer period of time.
  • FIG. 2 shows schematically the process flow again in a flow chart.
  • the delivered from a farm biomass 6, which may be in a dry or wet state, is first crushed in a crushing and suspension step 7 and slurried in water.
  • acids, organic or inorganic catalysts can be used.
  • After heating the resulting suspension to about 80 0 C this is with a suitable pump in the deep shaft reactor 8, as shown schematically, for example, in Figure 1, promoted.
  • the reaction volume of this reactor the exothermic reaction takes place, whereby in the first period of the process, a hot suspension of about 200 0 C is discharged from the reactor containing water and carbon particles.
  • the heat of this suspension is used in a conversion step 9 to electrical To generate energy.
  • a separation step 10 the separation of water and coal, so that finally pure coal 11 is available for energy production.
  • the coal can be used, for example, as a raw material for liquid hydrocarbon-rich fuels.
  • Separation step 10 a fraction of water with dissolved minerals and amino acids is obtained.
  • the minerals and amino acids are separated in step 12 and transported as fertilizer 13 back to the field.
  • the water is reused in the crushing and suspension step 7.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Sludge (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

La présente invention concerne un procédé de transformation de la biomasse en matières solides à forte densité énergétique, notamment de la houille, l'humus ou la tourbe. Selon ce procédé, des matières organiques de la biomasse sont mises en suspension dans l'eau pour obtenir une suspension et une fraction de la suspension, fraction à transformer, est chauffée à une température de réaction et, à forte pression, elle est convertie par carbonisation thermohydraulique en matière solide de densité énergétique supérieure. Le procédé est caractérisé en ce que la transformation est conduite dans un volume réactionnel situé sous la surface de la terre. Ce procédé permet d'obtenir une uniformisation de la qualité des produits et une augmentation de la rentabilité du processus.
EP07856078A 2007-03-22 2007-12-11 Procédé de transformation chimique par voie humide de la biomasse par carbonisation thermohydraulique Withdrawn EP2134821A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007014429 2007-03-22
PCT/DE2007/002227 WO2008113309A1 (fr) 2007-03-22 2007-12-11 Procédé de transformation chimique par voie humide de la biomasse par carbonisation thermohydraulique

Publications (1)

Publication Number Publication Date
EP2134821A1 true EP2134821A1 (fr) 2009-12-23

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP07856078A Withdrawn EP2134821A1 (fr) 2007-03-22 2007-12-11 Procédé de transformation chimique par voie humide de la biomasse par carbonisation thermohydraulique

Country Status (14)

Country Link
US (1) US20100101142A1 (fr)
EP (1) EP2134821A1 (fr)
CN (1) CN101688139A (fr)
AR (1) AR071145A1 (fr)
AU (1) AU2007349712B2 (fr)
BR (1) BRPI0721461A2 (fr)
CA (1) CA2685420A1 (fr)
CL (1) CL2008000834A1 (fr)
DE (1) DE112007003523A5 (fr)
PE (1) PE20090169A1 (fr)
RU (1) RU2009138929A (fr)
UY (1) UY30965A1 (fr)
WO (1) WO2008113309A1 (fr)
ZA (1) ZA200906001B (fr)

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EP3470457A1 (fr) 2017-10-10 2019-04-17 Continental Reifen Deutschland GmbH Mélange de caoutchouc réticulable au soufre, vulcanisation de mélange de caoutchouc et pneumatique pour véhicule

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CN101688139A (zh) 2010-03-31
UY30965A1 (es) 2008-10-31
RU2009138929A (ru) 2011-04-27
CL2008000834A1 (es) 2008-07-04
US20100101142A1 (en) 2010-04-29
CA2685420A1 (fr) 2008-09-25
BRPI0721461A2 (pt) 2014-03-25
ZA200906001B (en) 2010-04-28
WO2008113309A1 (fr) 2008-09-25
AU2007349712A1 (en) 2008-09-25
DE112007003523A5 (de) 2010-03-11
AU2007349712B2 (en) 2011-11-17
PE20090169A1 (es) 2009-02-25
AR071145A1 (es) 2010-06-02

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