US20100101142A1 - Method for the wet-chemical transformation of biomass by hydrothermal carbonization - Google Patents

Method for the wet-chemical transformation of biomass by hydrothermal carbonization Download PDF

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Publication number
US20100101142A1
US20100101142A1 US12/450,323 US45032307A US2010101142A1 US 20100101142 A1 US20100101142 A1 US 20100101142A1 US 45032307 A US45032307 A US 45032307A US 2010101142 A1 US2010101142 A1 US 2010101142A1
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Prior art keywords
suspension
reactor
reaction
reaction volume
water
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US12/450,323
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English (en)
Inventor
Peter Eisner
Andreas Malberg
Andreas Stäbler
Michael Menner
Markus Antonietti
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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    • 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 method for converting biomass into higher-energy-density solids, in particular carbon, humus or peat, wherein organic substances from the biomass are suspended in water to form a suspension and wherein at least a part of the suspension to be converted is heated to a reaction temperature and is converted into higher-energy-density solids by hydrothermal carbonisation at elevated pressure.
  • the organic substances can be plant parts, other biomass or organic waste.
  • the reaction proceeds faster or slower depending on the concentration and structure of the contents, primarily the carbohydrates (e.g. sugar, starch, cellulose, hemicellulose or others) in various raw materials, various plants and plant parts, residue from food production, sewage sludge or other biogenic materials and waste.
  • carbohydrates e.g. sugar, starch, cellulose, hemicellulose or others
  • the temperature and the pressure in the reactor increase more rapidly or more slowly and different absolute values are achieved for pressure and temperature.
  • the reaction is slowed considerably.
  • the temperature drops again until the reaction is terminated after a certain time because the temperature is too low. This possibly leads to incomplete conversion of the material used, for which a reaction time of several hours up to several days or longer may be necessary.
  • external after-heating of the reactor to lengthen reaction times requires an additional energy input which can make the carbonisation uneconomical.
  • the coupling of temperature and pressure in this reaction and the different reaction rates of different raw materials used have the result that the temperature and pressure profiles during the reaction are very different depending on the composition and concentration of the biomass in the input stream of the hydrothermal carbonisation.
  • the products obtained can thus differ very substantially in their composition. This can have the result that the products have no constant quality and do not give high yields which can make the hydrothermal carbonisation uneconomical.
  • the object of the present invention is to provide a method for converting biomass into higher-energy-density solids by hydrothermal carbonisation whereby a more uniform product quality is achieved and the economic efficiency of the process is increased.
  • organic substances from the biomass are suspended in water to form a suspension.
  • a conversion-promoting substance is present in the water or is added to the water or the suspension.
  • the conversion-promoting substance can, for example, be an acid and/or an organic or inorganic substance which accelerates the reaction.
  • the biomass can comprise, for example, organic waste, plant parts, wood, algae or other carbon-containing organic products.
  • At least a part of the suspension to be converted is heated to a reaction temperature and is converted into higher-energy-density solids by means of hydrothermal carbonisation at elevated pressure.
  • the method is characterised in that the conversion is carried out in a reaction volume that is located underneath the Earth's surface.
  • the reaction volume for buffering released reaction heat in a surrounding area corresponding to at least four times the mean diameter of the reaction volume is preferably surrounded by a mass of compact liquid and/or solid material which is greater than eight times the mass contained in the reaction volume. Good homogenisation of the product properties is already observed above this mass.
  • the reaction therefore takes place underneath the Earth's surface.
  • the Earth's surface is understood in this context as the boundary layer between the solid Earth's crust or the oceans on the one side and the atmosphere on the other side.
  • this material By moving the reaction chamber below the Earth's surface with the surrounding material such as, for example, rock, sand, water or soil, this material can absorb a large part of the energy released in the form of heat at the initial stage of the reaction.
  • the temperature in the reaction volume or reaction mixture increases more slowly and not so far as in a reactor above the Earth's surface, and the pressure likewise does not fluctuate so strongly. In consequence at the beginning, the reaction does not proceed so rapidly and is more uniform.
  • the concentration of convertible biomass contents decreases with time, the temperature in the reaction does not fall so rapidly as in the hitherto known process. Rather, the surrounding material then slowly delivers the stored heat back to the reaction volume.
  • reaction volume thus remains warm for much longer and the reaction can be continued without additional heating of the suspension for many hours or even days until different raw materials have been converted to comparable products having a higher energy density.
  • the reaction volume is preferably in direct contact with the surrounding compact material, at least in some places.
  • Another advantage of the proposed method is that by returning heat from the surrounding material into the reaction volume even after removal of the products, new biomass can be supplied again and brought to reaction without external heating or at least without strong additional heating. In many cases, this allows several batches to be carbonised successively without any external supply of heat. In principle, the method therefore allows both a continuous supply of biomass and also batch operation. As a result, the throughput in the method according to the invention can be varied very substantially as a result of the thermal buffering of the surrounding soil or water without any losses of uniformity in the product quality.
  • the method must be carried out in a region underneath the Earth's surface in which a sufficient mass of surrounding material is available for thermal buffering.
  • the material should preferably have such a compact structure that in the surrounding area of four times the mean diameter of the reaction volume, it should have a total mass which corresponds to eight times the mass contained in the reaction volume. Relative to a cylindrical reaction volume of diameter D and height H, this means that a cylindrical volume having the same height and four times the diameter minus the cylindrical reaction volume should contain at least eight times the mass contained by the reaction volume filled with the suspension in order to achieve particularly good buffering for the proposed method.
  • the surrounding material such as, for example, soil, loam, sand or water is capable of at least partly compensating for and absorbing the pressure coming from the reaction.
  • a reactor used for hydrothermal carbonisation underneath the Earth's surface can therefore be designed as considerably thinner-walled compared with that for use above the Earth's surface. This additionally saves costs.
  • this reactor can, for example, consist of steel which is embedded in concrete or -reinforced concrete in a cavity under the Earth's surface. Very good heat transfer to the surrounding material takes place through the concrete cladding. The wall of this reactor can be very thin-walled.
  • the wall of the cavity can be used as the reactor wall. If necessary, this wall can be additionally lined with watertight materials. Such a lining can also be achieved by synthetic additives in the water. Automatic sealing by the reaction products of the process such as, for example, coal particles can possibly take place with respect to the surrounding rock.
  • the product composition can additionally be homogenised if the pressure is increased above the pressure corresponding to the reaction temperature.
  • the pressure certainly increases during the entire reaction and then falls again but the percentage relative pressure fluctuations are smaller.
  • the pressure in the reaction volume is kept constant or at least largely constant by means of technical measures. By means of these measures temperature and pressure are decoupled from one another. The operator of the hydrothermal carbonisation is therefore in a position to select the pressure according to the composition of the input so that the homogenisation of the product quality is improved. Application of an additional pressure can not only homogenise the composition of the end product.
  • the yield of solid products having high energy density can be increased by the elevated pressure so that the process can be operated even more economically.
  • the operator has a valuable instrument at his disposal that can specifically vary and thereby optimise the product quality or the yield depending on the requirement and composition.
  • the pressure build-up can be achieved by moving the reaction volume sufficiently deep into the ground.
  • the location of the reaction volume is selected to be sufficiently deep that a water column located above the reaction volume which is required to supply and remove the suspension, produces a hydrostatic pressure in the reaction volume which is higher than the equilibrium pressure which would be established at the reaction temperature in a gastight reactor filled with the suspension.
  • a hydrostatic pressure it is additionally very simple to maintain a constant pressure.
  • liquid can enter or exit at the surface of the water column. This can be made possible, for example, by openings or by using non-sealing pumps such as, for example, rotary pumps.
  • the water column is thereby used as a pressure buffer.
  • the reaction conditions are thereby homogenised and the solid material yield can be additionally increased.
  • reaction volume is configured to have a greater width than height.
  • hydrostatic pressure an approximately equal pressure is thus generated at all points in the reaction volume, thereby additionally promoting homogenisation of the reaction conditions.
  • the reaction volume can be formed by insertion into horizontal shafts, for example coal shafts.
  • a height difference of at least 100 m is selected between the upper filling level and the reaction volume.
  • a pressure higher than 10*10 5 Pa (10 bar) is thus formed in the reaction volume as a result of the water column located thereabove. Larger height differences of 200 m or more allow higher pressures to be established which can be very advantageous depending on the requirement.
  • the reactor is designed so that an inlet and outlet opening are located at the same height or at least at a similar height compared to the total reactor height so that the hydrostatic pressure difference between the openings does not exceed 10% of the pressure.
  • the pumps used then do not need to overcome any high pressure differences and can thus be designed very simply and cost effectively.
  • the outer wall of the reactor in addition to using a rigid reactor, it is also possible to configure the outer wall of the reactor as flexible so that this nestles against the inner wall of the cavity or at least serves as a barrier towards the surrounding rock or water. Thin metal sheets or metal films can be used particularly advantageously here, these having a high temperature resistance compared to other materials.
  • An advantage of the pressure build-up by the hydrostatic pressure in the reactor is that the pressure increases uniformly with increasing depth.
  • the reaction therefore does not begin abruptly and spontaneously but slowly and uniformly with increasing pressure and increasing temperature.
  • the dwell time can be specifically adjusted and thereby matched to the respective raw material. It is appropriate to attach cooling water connections at regular intervals over the height and volume of the reactor so that cold water can be introduced if required to slow the reaction. This can avoid overheating of the reaction and the heated water can thereby be used for energy.
  • This process can also take place via heat exchangers to be installed in the reactor.
  • mixing elements flow baffles, static mixers, agitators or other devices which influence the flow can be installed in the reactor to limit the sedimentation of solids.
  • Gases such as, for example, compressed air can be particularly advantageously introduced into the reactor to effect thorough mixing. It is also possible to achieve gas formation by making the water in the suspension partially evaporate. The turbulence thereby produced leads to thorough mixing and avoids blockages.
  • Specific evaporation of part of the water can also be used to empty the reactor after the end of the reaction.
  • a pressure reduction in the reaction volume can be achieved by pumping away water located in the inlet or outlet and spontaneous evaporation is achieved in the reaction volume.
  • the flow cross-sections can be reduced to such an extent that a critical flow rate is exceeded. It is also possible to erect a cascade of agitator reactors in tunnels underground and surround these with soil, rock or water, through which flow takes place in series. In this form, they can be manufactured very cost-effectively and allow rapid flow.
  • Blockage of the reactor can also be avoided if the flow direction is reversed at regular intervals and thus a type of pulsation is achieved on which a constant flow rate is superposed. This pulsation leads to turbulence in the reactor and thereby very efficiently prevents deposits.
  • particles which tend to sediment can be specifically removed from the reactor.
  • apparatus can be incorporated in the reactor which discontinuously or continuously conveys sedimented solids from the reactor using systems according to the prior art (e.g. conveyor belts, scrapers, chains, screws, pumps). These solids can be fractionated outside the reactor so that coarse organic materials can be returned to the reaction chamber following appropriate comminution.
  • the reactor merely consists of a cavity present in deeper layers of rock where the supply of reaction mixture is conveyed through a supply line to a sufficient depth for the reaction. It is particularly advantageous, for example, to use old conveyor shafts from mining, disused tunnels or other underground structures.
  • the existing lining of the shafts or tunnels can be used as the “reactor wall” and the entire volume of the shaft can be used as the reactor.
  • the system can be sealed by additives in waters or the system can seal itself with respect to the surrounding rock by reaction products such as coal particles.
  • an inlet or outlet When using bores in the ground, an inlet or outlet must be provided in the lower region of the reactor.
  • an inlet or outlet channel in the lower region of the shaft or the bore whose cross-sectional area and pump capacity can be variably adjusted, an upward flow is established over the remaining shaft cross section.
  • the area ratio of reactor space through which upward flow takes place and reactor space through which downward flow takes place can be 0.01% to 99.99%.
  • Heat exchangers for cooling or heating which can be arranged in the shaft, are used to control the temperature and the reaction and thereby ensure the product quality and the energy removal and consequently the energy utilisation outside the reactor.
  • Process-technology solution approaches such as secondary sedimentation basins, decanters, filter presses or briquetting installations can be used to separate coal particles.
  • the method described brings additional advantages when used in combination with geothermal energy.
  • energy is supplied to the reaction mixture in warmer regions of the Earth, the reaction mixture is additionally heated and the reaction thereby accelerated.
  • the additionally released energy can then be used according to the prior art by removing the heat or by converting into electrical current or hydrogen.
  • the carbon-rich reaction products are present in many cases as finely dispersed nanospheres. This circumstance can be used very advantageously for conveying the solid energy carriers.
  • mechanical separation of the solids from the liquid can initially be carried out, for example, by centrifugal separation methods.
  • the liquid fraction containing the amino acids and minerals from the organic raw material can be used as manure directly or after concentrating by partial separation of the water.
  • the nanoparticle solids which predominantly consist of carbon are again mixed with water and adjusted to a dry substance content of 40 to 60 mass %.
  • An energy density of up to 18 gigajoules per tonne can thus be established in the suspension, which corresponds to approximately half the energy density of crude oil. Transporting nanoparticle energy carriers over large distances in this form is completely economical by pipelines known from the prior art.
  • the viscosity of the suspension in the reactor inlet should be at least 20 mPas (measured in a rotary viscosimeter at a shear rate of 10 m/s). In the reactor outlet, values of 5 mPas should not be exceeded for improved separation of particulate solids.
  • an elevated viscosity can be set by specifically using different biomasses, biomass having defined carbohydrates (cellulose, starch, oligo- or monosaccharides), their degree of comminution, concentration and via the swelling time of the carbohydrates.
  • biomass having defined carbohydrates cellulose, starch, oligo- or monosaccharides
  • the biomass or the reaction suspension is conveyed into the depths in vessels or drums such as containers, barrels, baskets, sacks, cylindrical or rectangular vessels made of different materials or in similar spatially defined volumes, into the interior of the reactor accommodated underground.
  • vessels or drums such as containers, barrels, baskets, sacks, cylindrical or rectangular vessels made of different materials or in similar spatially defined volumes
  • the containers or the vessels in the reactor are sufficiently heated so that the reaction can take place inside the container without removing the biomass from the containers.
  • the particle size can be variably adjusted or fine comminution can be dispensed with before carrying out the reaction.
  • larger particles such as, for example, pieces of wood can be conveyed into the reactor.
  • Coal particles having an edge length of several centimetres can thus be obtained, making it easier to separate the water from the coal after completion of the reaction.
  • the containers can be conveyed through the reaction space similar to the situation with tower heaters in the food industry which are used for heating tins in a displacement conveyance system, i.e. each container pushes the next container further in the tubular reaction space. It is also possible to use conveyor systems for containers according to the prior art such as, for example, chain conveyors, conveyor screws, cables and other devices for transporting vessels through conduits.
  • the containers can also be transported through the shaft or reaction space in like manner to other transport systems in mining by cables or on rails in a type of “underground railway”.
  • FIG. 1 is an example of the arrangement of the reaction volume underneath the Earth's surface
  • FIG. 2 is a schematic diagram of the process sequence in the proposed method.
  • FIG. 1 schematically shows an example of an embodiment of a reactor for carrying out the present method, which in this example is inserted in a shaft 1 underneath the Earth's surface.
  • the shaft 1 lies 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 suspended biomass is pumped via this inlet 3 into the reaction volume.
  • the reaction products are pumped upwards again via the outlet 4 .
  • the wall of the reactor 2 can be relative thin since the hydrostatically generated pressure in this case is absorbed by the surrounding soil 5 .
  • the reactor 2 is surrounded in an area of soil 5 which corresponds to at least four times the diameter D of the reaction volume.
  • No larger cavities can be present in this surrounding area so that the total mass in a volume occupied by the material in this surrounding area corresponds to at least eight times the mass of the reaction mixture in the reaction volume.
  • the suspended biomass is initially brought to a temperature of about 80° C. in the reactor 2 .
  • the suspension is heated above 200° C.
  • the heat absorption and storage has the result that no rapid overheating takes place.
  • the reaction temperature is achieved by the heat released by the surrounding material, so that the reaction can be maintained for a fairly long time without any external supply of energy.
  • FIG. 2 schematically shows the process sequence again in a flow diagram.
  • the biomass 6 supplied from a farm which can be in the dry or wet state, is initially comminuted in a comminution and suspension step 7 and suspended in water. Acids, organic and inorganic catalysts can be used as additives. After heating the suspension thus obtained to about 80° C., this is conveyed by means of a suitable pump into the deep shaft reactor 8 as shown schematically, for example, in FIG. 1 .
  • the exothermic reaction takes place in the reaction volume of this reactor whereby in the first time interval of the process, a hot suspension at about 200° C. containing water and coal particles is removed from the reactor.
  • the heat of this suspension is used in a conversion step 9 to produce electrical energy.
  • a separation step 10 the water and coal are separated so that finally pure coal 11 is available for energy production.
  • the coal can be used, for example, as raw material for liquid hydrocarbon-rich fuels.
  • a fraction comprising water with minerals and amino acids dissolved therein is obtained.
  • the minerals and amino acids are separated in step 12 and transported back to the fields again as manure.
  • the water is reused in the comminution 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)
US12/450,323 2007-03-22 2007-12-11 Method for the wet-chemical transformation of biomass by hydrothermal carbonization Abandoned US20100101142A1 (en)

Applications Claiming Priority (3)

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DE102007014429 2007-03-22
DE102007014429.8 2007-03-22
PCT/DE2007/002227 WO2008113309A1 (de) 2007-03-22 2007-12-11 Verfahren zur nasschemischen umwandlung von biomasse durch hydrothermale karbonisierung

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EP (1) EP2134821A1 (es)
CN (1) CN101688139A (es)
AR (1) AR071145A1 (es)
AU (1) AU2007349712B2 (es)
BR (1) BRPI0721461A2 (es)
CA (1) CA2685420A1 (es)
CL (1) CL2008000834A1 (es)
DE (1) DE112007003523A5 (es)
PE (1) PE20090169A1 (es)
RU (1) RU2009138929A (es)
UY (1) UY30965A1 (es)
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US20150117956A1 (en) * 2012-09-19 2015-04-30 Josh Seldner Geothermal pyrolysis process and system
US9109180B2 (en) 2009-04-01 2015-08-18 Suncoal Industries Gmbh Method for the hydrothermal carbonization of renewable raw materials and organic residues
US9662623B2 (en) 2012-02-09 2017-05-30 Tongji University System and method for hydrothermal reaction
KR20200055380A (ko) * 2018-11-13 2020-05-21 주식회사 휴비스워터 음식물 쓰레기를 이용한 고형연료의 제조방법
KR102357549B1 (ko) * 2021-04-22 2022-02-09 (주)키나바 유기성 또는 무기성 폐기물의 수열탄화 반응을 이용하여 악취가 저감되는 고형연료의 제조방법 및 그 방법으로 제조된 고형연료
US11724941B2 (en) 2018-02-15 2023-08-15 North Carolina State University Synthesis of micron and nanoscale carbon spheres and structures using hydrothemal carbonization
US11952494B2 (en) 2017-10-10 2024-04-09 Continental Reifen Deutschland Gmbh Sulfur-crosslinkable rubber mixture, vulcanizate of the rubber mixture, and vehicle tire

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DE102009015257B4 (de) 2009-04-01 2013-03-14 Suncoal Industries Gmbh Verfahren zur hydrothermalen Karbonisierung nachwachsender Rohstoffe und organischer Reststoffe
DE102009027007A1 (de) * 2009-06-17 2010-12-23 Technische Universität Berlin Verfahren zur Herstellung von mineralischem Biodünger
EP2284141A1 (de) 2009-08-12 2011-02-16 Leibniz-Institut für Agrartechnik Potsdam-Bornim e.V. (ATB) Verfahren und Vorrichtung zur Herstellung von mit Mineralstoffen angereicherten Kohlepartikeln
DE102010013050A1 (de) * 2010-03-27 2011-09-29 Terranova Energy Gmbh Additiv zur Verbesserung der Hydrothermalen Karbonisierung von Biomasse
DE202010018395U1 (de) 2010-03-24 2016-05-11 Antacor Ltd. Vorrichtung zur Behandlung von Fest-Flüssig-Gemischen
DE102010064715B3 (de) 2010-03-24 2022-04-28 Antacor Ltd. Verfahren und Verwendung eines Rohrreaktors zur Behandlung von Fest-Flüssig-Gemischen
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DE102010060656A1 (de) * 2010-11-18 2012-05-24 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur hydrothermalen Karbonisierung von biologischem Material und Verwendung des anfallenden Prozesswassers zur Fermentation
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AU2007349712B2 (en) 2011-11-17
CN101688139A (zh) 2010-03-31
CL2008000834A1 (es) 2008-07-04
DE112007003523A5 (de) 2010-03-11
UY30965A1 (es) 2008-10-31
AU2007349712A1 (en) 2008-09-25
PE20090169A1 (es) 2009-02-25
RU2009138929A (ru) 2011-04-27
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BRPI0721461A2 (pt) 2014-03-25
WO2008113309A1 (de) 2008-09-25

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