EP1789515A1 - THERMISCHE BIOMASSENVERöLUNG - Google Patents

THERMISCHE BIOMASSENVERöLUNG

Info

Publication number
EP1789515A1
EP1789515A1 EP05770008A EP05770008A EP1789515A1 EP 1789515 A1 EP1789515 A1 EP 1789515A1 EP 05770008 A EP05770008 A EP 05770008A EP 05770008 A EP05770008 A EP 05770008A EP 1789515 A1 EP1789515 A1 EP 1789515A1
Authority
EP
European Patent Office
Prior art keywords
reaction
oil
boiling
educt
separation
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Withdrawn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
EP05770008A
Other languages
German (de)
English (en)
French (fr)
Inventor
Eckhardt Siekmann
Hermann Meyer
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.)
Proton Technology GmbH IG
Original Assignee
Proton Technology GmbH IG
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
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Application filed by Proton Technology GmbH IG filed Critical Proton Technology GmbH IG
Publication of EP1789515A1 publication Critical patent/EP1789515A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00Chemistry of inorganic compounds
    • Y10S423/18Treating trash or garbage

Definitions

  • the present invention relates generally to a process for producing hydrocarbon-containing oils, a modulus-of-oil modulus device for this process, a process for generating electrical, kinetic and / or potential energy, a process for producing a chemical product, a process obtainable from said process chemical product, goods at least partially based on or containing this chemical product, a process for the transport of goods or for the conveyance of persons and the use of one of the processes described above or the device described above in a sustainable environment Energy industry or to reduce the production of greenhouse gases.
  • BESTATIGUNGSKOPIE A number of documents are known from waste management, in which, for example, waste or waste raw materials are processed by pyrolytic processes, usually under very high temperatures and using suitable solid catalysts, to produce products which are compared to the waste or waste raw materials have lower molecular weights.
  • DE 102 15 679 A1 discloses a direct thermochemical conversion of high molecular weight organic substances into low-viscosity liquid fuels, whereby a combustible, low-viscosity liquid is obtained by shock heating of the biomass used in combination with a circulation of a product phase which is difficult to evaporate.
  • a disadvantage of this method is that obvious and technical usual measures for Verweilzeit Kunststoffung for this procedural Ren are not sufficient.
  • the process described in DE 102 15 679 A1 is carried out at a pressure of 80 bar, so that the reactor must be designed specifically for such high pressures. A use of such a reactor in, for example, mobile plants for the production of fuels from renewable raw materials is therefore not without problems.
  • DE 10049 277 A1 discloses a process for the catalytic production of diesel oil and gasolines from hydrocarbon-containing wastes and oils such as wood, a solid catalyst based on sodium aluminosilicate being used.
  • This method is disadvantageous on the one hand because solid particles, which also include solid catalyst components, are disadvantageous due to the risk of clogging caused by this solidification and the associated frequency of standstill times of a lubrication plant for a permanent, continuous and thus economical operation of a lubrication plant are.
  • DE 101 11 765 Al is It can be seen that predominantly residual catalyst residues remain in this process which can not be regenerated. Rather, such catalyst residues must be cleaned by incineration by expensive processes and, since such cleaning is generally possible only once, ultimately be disposed of.
  • the general object of the present invention is to contribute to the solution of the problems resulting from the prior art and to overcome the disadvantages resulting from the prior art.
  • the fuels obtainable by this process should be as less carcinogenic as possible and, when burned in an internal combustion engine, should ensure the highest possible cylinder pressure.
  • a further object of the invention is to provide a method and a device which can be operated in the smallest possible and decentralized units.
  • a contribution to achieving the above objects is made by a process for the preparation of hydrocarbons-containing oils, in which a starting material comprising a sugar and / or a sugar derivative is thermally split, comprising
  • a reaction step in which the starting material mass with a contact oil, wel ⁇ a boiling point of preferably determined according to DIN EN 60751 of at least 200 ° C, preferably of at least 250 ° C, even more preferably of at least 300 0 C, more preferably from at least 325 0 C and most preferably of at least 350 ° C at a pressure of 1013 mbar, to form a reaction phase at a reaction temperature in the range of 200 to 600 0 C, preferably in the range of 250 to 550 0 C, especially preferably in the range of 300 to 500 0 C and most preferably in a range of 350 to 450 0 C and an abso- Luten pressure in a range of 0.1 to 50 bar, preferably in a range from 0.5 bar Be ⁇ more preferably in a range from 0.75 bar to 10 bar, moreover preferably in a range from 0.9 bar to 1.5 bar, and most preferably at atmospheric pressure, into contact, and
  • reaction phase is separated into a light-boiling part and a heavy-silk part
  • thermochemical conversion of high molecular weight organic substances into low-viscosity liquid fuels also at pressures of not more than 50 bar down to 0.1 bar, but more preferably under atmospheric pressure (about 1013 mbar) can be performed.
  • "high boilers” are understood to mean compounds which have a boiling point at atmospheric pressure (ie 1013 mbar) or, for a boiling range, a boiling point of at least 200 ° C., preferably at least 25O 0 C, particularly preferably at least 300 C., moreover preferably at least 325 ° C. and most preferably at least 350 ° C.
  • low boilers are preferably compounds which have a boiling point or a boiling range of at most 200 ° C., preferably at most, at atmospheric pressure 250 ° C, more preferably not more than 300 0 C, further preferably at most 325 ° C and most preferably at most 350 0 C.
  • hydrocarbons-containing oils obtainable by the process according to the invention are preferably fuels which are liquid at room temperature and more preferably have a cetane index according to EN 590 of at least 46, preferably at least 48, more preferably at least 50 and most preferably 54 exhibit.
  • Petroleum, diesel, fuel oil, benzine or mixtures of at least two of these, particularly preferred hydrocarbons which are preferred according to the invention, are petroleum, with diesel being the most preferred.
  • oils containing hydrocarbons obtainable by the process according to the invention have a content of aromatic hydrocarbons determined by OENORM 12916 of at most 50% by weight, more preferably at most 25% by weight, even more preferably at most 10 wt .-%, more preferably at most 5 wt .-%, more preferably still more preferably at most 100 ppm and most preferably at most 1 ppm of aromatic hydrocarbons.
  • the proportion of starting material in the reaction phase is preferably in the range from 5 to 80% by weight, more preferably in a range from 10 to 70% by weight, even more preferably in one range from 20 to 60% by weight and most preferably in a range from 25 to 40% by weight, based in each case on the total mass of the reaction phase.
  • Suitable sugar or sugar derivatives are all synthetically known or naturally occurring sugar compounds known to the person skilled in the art.
  • sugar and / or sugar derivative according to the invention includes both mono-, di-, tri-, tetra-, penta-, oligo- or poly-sugar. This applies regardless of whether these sugars are cyclic, linear, branched or crosslinked.
  • Suitable sugar derivatives are all chemical reaction products formed from sugars. These include, for example, sugar esters, sugar alcohols, sugar ethers, sugar phosphates, sugar salts, sugar whitening compounds and the like.
  • the abovementioned sugars or sugar derivatives may be composed of sucrose, manose, lactose, chitter, dextrose or combinations of at least two thereof.
  • Examples of cyclic sugars are cyclodextrins.
  • linear sugars are starch and starch derivatives.
  • Examples of branched sugars are celluloses.
  • crosslinked sugars are, for example, networks obtained from linear sugars or branched sugars by crosslinking reactions, as obtained, inter alia, in papermaking, paperboard or cardboard production.
  • the educt composition is at least 5% by weight, preferably at least 10% by weight, particularly preferably at least 15% by weight and moreover preferably at least 20% by weight, based in each case on the educt composition, sugar and / or a sugar derivative.
  • the starting material mass may include impurities. These are, in addition to other organic compounds such as proteins and der ⁇ same often water.
  • the starting material it is preferred in the process according to the invention for the starting material to have a water content in the range from 0.001 to 30% by weight, preferably in the range from 0.01 to 25% by weight, more preferably in the range from 1 to 20% by weight .-% and moreover preferably in the range of 5 to 10 wt .-%, each based on the educt mass having.
  • Certain quantities of water are advantageous in the process according to the invention, since these improve the stirrability of the educt mass on the one hand and less oil-soluble on the other hand, but so on more water-soluble constituents, in particular solids, during the reaction step and the subsequent workup can carry out the oil containing hydrocarbons and thus lead to an improvement in the product quality of this oil.
  • the educt composition used in the reaction step is at least 5% by weight, preferably at least 20% by weight and moreover preferably at least 70% by weight, based in each case on the educt composition , Particles having a particle size in the range of 0.001 to 50 mm, preferably in the range of 0.01 to 40 mm, particularly preferably in the range of 0.1 to 20 mm and moreover preferably in the range of 1 to 10 mm.
  • the above particle sizes can be determined by sieve analysis. The above selection of particle sizes makes it possible, on the one hand, to provide a homogeneous educt mass which leads to a reaction phase which can be stirred in a suitable manner. Such a reaction phase contributes to the most uniform possible course of the reaction step, in which in particular no undesirable bumping occurs.
  • the educt composition comprises at least one vegetable agricultural product comprising the sugar and / or the sugar derivative.
  • This product preferably forms the main part of the educt composition.
  • a vegetable agricultural product all plants which are familiar to the person skilled in the art and are used in agriculture are considered.
  • straw, hay and crops are preferred. Straw, hay and crops are in each case preferred embodiments.
  • Suitable straws are, in particular, stalks, rice straw or corn sharks that are produced during the grain harvest. Furthermore, straw can be obtained from reed, rapeseed, soybean, sugar cane stems or bamboo. As hay come all in agriculture resulting grassland cuts into consideration. Thus, for example, cuts obtained on meadows, decommissioning areas, dikes, football fields, street embankments and gardens can be used as today's.
  • Field crops include fodder beet, sugar beets, swede, stubble, comfrey, carrots, mustard, fodder beet, potatoes, maize, cereals such as barley, wheat, oats, rape, peas, beans, soy, rice or sugar cane, with fodder beet being particularly preferred are preferred.
  • Each of the examples mentioned above for straw, hay or field crops constitutes a preferred embodiment and can thus form a main component of the educt composition.
  • wood or foliage can also be used as educt mass or as constituent of the educt mass.
  • the educt composition is harvested less than two, preferably less than five, more preferably less than ten or even less than 15 hours before the reaction step.
  • This can be carried out, for example, by the reaction step following directly on the harvesting step, where appropriate between the harvesting step and the reaction step, a confectioning step in which the harvested agricultural product is prepared for the reaction step, in which, for example, it the right size and suitable th water content is brought.
  • the harvest step may also be combined with one or more order operations. In particular, a freight sequence adapted to the ground conditions is preferred as the order process.
  • crop rotation is particularly preferred in which cereals, preferably barley or soybeans, are first cultivated and harvested in a harvesting step, preferably in summer, and then oiled in the reaction step.
  • the cereals are then followed by beets as crops, with beets or stubble turnips being particularly preferred.
  • the beets are preferably harvested and oiled in the autumn of the same year.
  • the following spring, fodder beets can be grown in the same field on which cereals and then beets were first cultivated, which can be harvested and oiled in the autumn.
  • Another crop rotation preferred according to the invention provides that sugar cane is first cultivated and feed beets are cultivated directly following the crop of the sugar cane.
  • sugar cane or sugar beet When sugar cane or sugar beet is harvested, it is preferred that in the preparation step upstream of the reaction, the sugar cane or sugar beets can first be passed on to sugar juice, which if appropriate concentrated, to the sugar processing and pomace are digested.
  • sugar juice which if appropriate concentrated, to the sugar processing and pomace are digested.
  • the pomace thus obtained can be added to the liquid in the reaction step following the preparation step.
  • the contact oil used in the reaction step it is preferred for this to be at least 1% by weight, preferably at least 10% by weight, more preferably at least 40% by weight and moreover preferably at least 70% by weight, based in each case on the contact oil, a C 30 to C so, preferably a C 4 o to C 7 o and particularly preferably a C 50 to C 6S hydrocarbon includes.
  • These hydrocarbons preferably have at least 10% by weight, more preferably at least 50% by weight and more preferably at least 70% by weight, in each case based on the hydrocarbon, of unbranched hydrocarbon molecules.
  • the contact oil is brought to a temperature of more than 100 0 C, preferably more than 200 0 C and be ⁇ especially preferably more than 300 0 C prior to bringing into contact with the educt composition , It is particularly preferred that the contact oil is preheated to at least 70%, preferably at least 85% and particularly preferably at least 95% of the reaction temperature expressed in C 0 . In this way, as rapid as possible and uniform reaction is achieved by the contacting of vorgemérm ⁇ tem contact oil with the advantageously also preheated Eduktmasse.
  • the contact oil is based to at least 50% by weight, more preferably at least 75% by weight, even more preferably at least 99% by weight and most preferably at least 99.9 Wt .-% on the high boiler part, which, preferably after the separation of solids (see below) is recycled to the reaction step.
  • the reaction phase is less than 0.05% by weight, preferably less than 0.1% by weight and more preferably less than 1% by weight, in each case based on the educt composition having a solid catalyst.
  • This solid catalyst is preferably a sodium silicate catalyst molecular sieve.
  • the separation of the reaction phase obtained in the reaction step into a low-boiling part and a high-boiling part is preferably carried out by first separating the liquid phase formed in the reaction phase under the pressure and temperature conditions of the reaction phase, which comprises mainly high-boiling components, in the case of a continuous mode of operation Separation is preferably carried out by overflow valves.
  • the condensed high boilers are then separated from the still present after cooling gaseous phase comprising the low boilers.
  • the condensed high boilers are then preferably combined with the phase separated from the reaction phase and liquid under the pressure and temperature conditions of the reaction phase, which likewise comprises high boilers.
  • the high boilers are then fed in a further process step to a solids removal device and, after they have been freed of solids, then optionally stored in a high boiler as "high boiler.” From the high boiler, a portion of the high boilers can be recycled as contact oil into the reaction space ,
  • the retained in the first separating gaseous phase is then preferably conducted in a second cooling zone in which these gaseous phase, more preferably to a temperature in a range of 10 to 100 0 C, preferably from about 20 to 80 0 C of about 30 to 70 0 C and most preferably cooled to a temperature of about 50 0 C, wherein also in this case the cooling is preferably carried out by heat exchangers.
  • the heat released in the two heat exchangers can serve, for example, for preheating the contact oil or the educt mass.
  • the low boilers which are liquid after the second cooling, then condense, which are then separated off in a further separation device, preferably another cyclone, from gaseous constituents still present after cooling.
  • a further separation device preferably another cyclone
  • gaseous constituents still present after cooling.
  • still gaseous components which include, inter alia, methane, can be burned and the heat released can likewise be used to preheat the contact oil and / or the educt mass or to heat the reaction space.
  • the oil separated in this way, condensed, hydrocarbons and also water-containing oil can already be used directly as biodiesel fuel in Verbrennungsma ⁇ machines.
  • the separation into a high boiler fraction and a low boiler fraction is not effected by passing a carrier gas stream through the reaction phase which selectively absorbs volatile components from the reaction phase.
  • the heavy-boiling part obtained in the work-up step is at least partially recycled to the reaction step in the process according to the invention.
  • the process according to the invention can be operated continuously and discontinuously, continuous operation being preferred.
  • the educt composition and the contact oil which may be a commercially available oil or else the high-boiling component obtained in the working up step or a mixture of both, may be in contact under the abovementioned pressure and temperature conditions brought. This is preferably done until no further thermal cleavage of the educt composition used is more.
  • the process according to the invention is prolonged, preferably at least one hour, more preferably at least five hours and above In addition, preferably at least ten hours, most preferably at least 24 hours are used.
  • the method is continuously by permanently supplying starting material mass and continuous supply of the high boiler obtained during the process as a contact oil after reaching a stable state in the temperature and concentration less than 20%, preferably less than 15% and more preferably less than 10% , carried out.
  • the contact oil more than 20 wt .-%, preferably at most 10 wt .-%, still more preferably at most 5 wt .-%, and 'most preferably at most 1 wt .-% of Feststofrpumblen having a particle size less than 50 microns, preferably less than 25 microns, even more preferably less than 10 microns, more preferably less than 1 micron, and most preferably less than 100 microns.
  • the contact oil originally used in the starting step successively is replaced in a particular embodiment of the process according to the invention, the contact oil to at least 50 wt .-%, preferably at least 75 wt .-%, even more preferably at least 90 wt .-% and am Most preferably at least 99.9 wt .-% on the high boiler part.
  • the solids which are separated off from the heavy-boiling part recycled into the reaction step before being returned to the reaction step as the contact oil may on the one hand be the carbon radicals which are formed in the reaction temperature range.
  • insoluble, in particular mineral constituents may be obtained as solids in the course of the process according to the invention.
  • the high-boiling part is passed through a sieve or a membrane.
  • Preferred sieves or membranes have a mesh or pore size in the range from 1 to 200 .mu.m, more preferably in the range from 10 to 100 .mu.m, moreover preferably in the range from 20 to 50 .mu.m and most preferably in the range from about 30 .mu.m
  • Particularly preferred in this context are porous filter masses. These include ceramic surface filters of high chemical and pressure resistance in stone, hollow candle or plate form and glass frits. In order to reduce the risk of pore clogging, such surface filters are preferably provided with an upper, fine-pored filter layer, while the remaining part is coarse-pored (multilayer filter).
  • Coke, plastics, hard rubber, animal skins and sintered metal powders can also be basic materials of porous filter masses. It is likewise possible to use metal filters produced by powder metallurgy as porous filter masses. As sedimentation especially two subspecies are considered. On the one hand, the solid particles, if they have a higher density than the high boiler, can be separated by settling. If the solid particles have a lower density than the high-boiling part, they float on the high-boiling part in a quiescent bath and can be removed from the surface of the high-boiling part. The other method of sedimentation is based on the separation of the at least one solid by centrifugal forces.
  • the high-boiling components contaminated with at least one solid can be agitated against the filter by the centrifugal force, the solids remaining on the filter and the heavy-boiling components passing through Filter penetrate and these freed from the solids leaving sen.
  • the high-boiling part is freed from the at least one solid by the use of so-called separators (also called plate centrifugal joints).
  • Contact oil is recycled to the reaction step, preferably characterized in that initially in a first separation step solids by filtration, particularly preferably by means of edge gap filter, as described for example by EDAK
  • the heavy-boiling part which is already partially freed from solids, is then separated in a second separation step by means of separators, in particular by means of Westfalia Separators, freed from further solids.
  • this third separation step may be followed by a third separation step, in which the high-boiling part is also separated, for example, by electrostatic filtration using filtration equipment, such as those available from FRIESS GmbH, Monheim, Germany, designated Model D2, Model D4, Model D4-1E, model D8, model D8-1E, model D16 and model D16-1E are commercially available, freed from further solids.
  • the separation of solids from the high boiler part takes place in that the high boiler, after which they have been condensed by the first cooling of the gaseous reaction phase and combined with the liquid constituents taken from the reaction space, in a corresponding separating device are passed.
  • the high-boiling component which has been substantially freed from solids after passing through the separation control can then be stored, for example, in a high-boiling tank as "high-boiling buffer.” It is further preferred in this connection for the high-boiling components to be fed to the separating apparatus a temperature of at least 150 0 C, preferably cooled by at least 100 ° C.
  • the high boilers freed from solids can be partly recycled directly into the Reaktiqnsraum as contact oil both directly after they have passed the separation device for separating solids, it is also conceivable, from the high boiler tank, in which the high boilers freed of solids "puffed" be returned to the high-boiling part as a contact oil in the reaction chamber.
  • the embodiment of the process according to the invention according to which at least one reaction step takes place continuously and the embodiment of the process according to the invention, in which part of the high boiler is continuously fed to the reaction step, further contribute to ensuring that the Onsön prevailing reaction conditions were ⁇ kept as constant as possible. It is advantageous here that the part of the high boiler is fed to the reaction space through nozzles. In this way, if necessary assisted by an agitator, a very rapid and uniform mixing of the educt composition and the contact oil or the supplied part of the high boiler is achieved.
  • this can also be carried out with at least two series-connected reaction and workup systems.
  • the heavy-boiling fraction which has been separated off in the first work-up unit after work-up of the reaction phase obtained in the first reaction unit and optionally freed from solids is fed as contact oil to the reaction step in the second reaction unit.
  • the heavy-boiling fraction which has been separated off after work-up of the reaction phase obtained in the second reaction unit is, as described above, freed of solids and can be recycled as contact oil to the reaction step of the first reaction unit.
  • the gas phase obtained in the two processing plants can be condensed individually or together to form the low-boiling phase and worked up further.
  • a production device located in a vehicle.
  • One possibility here is to carry out at least the harvest step and the reaction step on one and the same vehicle.
  • Another possibility is to carry out the harvesting step on a separate vehicle and to transfer the educt mass collected in the harvest step to another vehicle which has a production device in which at least the reaction step can take place.
  • Forestry products are especially wood or Wood waste, as may occur for example during harvesting by branches and derglei ⁇ chen or even in the further processing of the wood in the form of wood chips, shavings, chips or abrasive dustsj ⁇ .
  • the method according to the invention directly during harvesting of the wood, in order to supply, for example, bark, branches or other wood residues which are no longer usable, which are obtained during the harvesting of the wood, to the oiling.
  • a production device located in a vehicle, which has at least one reaction step, on site in the wood harvest in the forest.
  • the further processing of wood can be carried out in wood processing plants, such as sawmills, press chip or laminate board manufacturing companies, Schrei ⁇ nereien or paper or pulp mills.
  • wood processing plants such as sawmills, press chip or laminate board manufacturing companies, Schrei ⁇ nereien or paper or pulp mills.
  • the use of the method according to the invention in each of the abovementioned woodworking operations for the recycling of wood waste constitutes a preferred embodiment of the method according to the invention.
  • the method according to the invention can also be used for the utilization of large quantities of leaves accumulating in the fall, in particular for its oiling ,
  • the public especially when caring parks incurred needles' Von'Nadelbäumen as firs, Fich ⁇ th, pine or larks can be oil ver ⁇ by the inventive process.
  • the present invention also relates to a device comprising a vaporizing module at least comprising, as transporting substance with one another in
  • a starting material feed - a reaction chamber connected to the starting material feed, optionally druckbe ⁇ loadable reaction space, this reaction space is particularly in the case of difficult to crack molecules such as lignin preferably equipped with a microwave, a to the Reaction space adjoining separator with a low-boiling outlet and a high-boiling outlet, wherein the light-boiling outlet is followed by a fractionation unit, wherein the high-boiling outlet is followed by a solids separation, wherein the solids separation has a liquid outlet and a solids outlet, wherein the liquid outlet is connected via an oil return directly or optionally via a high boiler tank to the reaction space.
  • lignin preferably equipped with a microwave
  • a to the Reaction space adjoining separator with a low-boiling outlet and a high-boiling outlet, wherein the light-boiling outlet is followed by a fractionation unit, wherein the high-boiling outlet is followed by a solids separation
  • the Eduktmasse- feed has a pressure valve.
  • this pressure valve which adjoins the reaction space or is located in the reaction chamber, educt matter can be conveyed by one or more conveying agents likewise located in the feedstock feed.
  • conveying means may be a conveyor belt, a conveyor screw or a delivery piston, wherein a screw conveyor is not least preferred in view of the continuous operation of the oiling module.
  • the pressure valve has an at least partially spherical component, that preferably spring pressure is applied. Furthermore, it is preferred that this component is formed at least partially of ceramic.
  • the educt mass supply reaction chamber side distribution elements which serve as uniform as possible distribution of the educt composition in the reaction space and are advantageously designed as a distributor wing.
  • the educt mass is thus introduced into the educt mass feed, which has a continuously operating conveying means, which is preferably configured at least partially like a screw.
  • the educt mass feed is heatable by a feed heating element.
  • This feed heating element is preferably provided at least partially in the region of the continuously operating conveying means on the outside of the reaction space.
  • the reaction space it is preferred for the reaction space to have a reactor heating element for heating the reaction space.
  • the feed heating element and also the reactor heating element can simultaneously or independently of one another be used as electrical heating elements, hot air heating be formed dement, oil heater or gas heater.
  • a microwave-emitting device is preferably used as the heating element.
  • the reaction space it is preferable for the reaction space to have a mixing device.
  • a mixing device As Mischeinrich ⁇ tion all known to those skilled stirring equipment into consideration.
  • Another form of mixing device form nozzles with which, for example, the contact oil or the high-boiling part used as contact oil can be atomized in order to ensure a corresponding thorough mixing of the reaction phase.
  • the reaction space is designed in the form of a trough in whose bottom the contact oil is located.
  • suitable sliding devices such as a rotating screw, the educt composition can be pulled or pushed within the reaction space from the place of entry of the educt composition through the contact oil.
  • the separator are formed as a thermo or mechano separator or a combination thereof, wherein each separator variant constitutes a preferred embodiment of the erfindungs ⁇ proper device per se.
  • Thermoäbscheider separators are to be drawn, which exploit the Siedetemperaturunter Kunststoffe the various onsphase in the reaction phase resulting hydrocarbons containing oils. Typical Thermoäbscheider are distillation or rectification columns.
  • a cooling module is provided as part of the separator before this. This cooling module is designed so that the gas mixture emerging from the reaction space can be cooled in the separator by a temperature of about 50.degree.
  • Particularly preferred cooling modules are tube heat exchangers, preferably tube bundle heat exchangers.
  • mechano separators according to the invention devices are understood that not by different temperatures but make it possible to separate mixtures of substances by utilizing different molecular weights. Mechanoabscheider are particularly preferred because of their compactness in Verkölungsmodulen that show a high Verkölungs even with a small space andconcentrszweürfis.
  • Typical mechano separators are separators, centrifuges or cyclones which function according to the centrifugal principle, with cyclones which accomplish the separation using gas streams being particularly preferred. Such cyclones or separators can be obtained, for example, from Westfalia Separator GmbH, Germany.
  • the device according to the invention can furthermore have devices as separators which operate according to the line or osmosis principle.
  • the device has a heavy-boiling tank, which is arranged such that the high-boiling boiler, after having passed the solids separation, can be introduced into it.
  • This high-boiling tank can also be provided with an oil return, can be attributed zu ⁇ with the high boiler from the high boiler tank as contact oil in the reaction space.
  • the liquid outlet of the Feststoff ⁇ separation is not directly connected to the reaction space, but on the high boiler tank.
  • the fractionation unit is likewise preferably a separator comprising a cooling module, which is preferably a distillation or rectification device or else a separator, the cooling module preferably being designed in such a way as to leave the exit from the first separator , gaseous low boilers to a temperature of about 5O 0 C are cooled.
  • a cooling module which is preferably a distillation or rectification device or else a separator, the cooling module preferably being designed in such a way as to leave the exit from the first separator , gaseous low boilers to a temperature of about 5O 0 C are cooled.
  • the solids separation takes place in at least two separation regions.
  • the mechano separators discussed above can likewise be used.
  • the first separating region comprises a mechanical separating device, preferably an edge-gap filter. has.
  • the further separation region has a separator, preferably a Westfalia separator.
  • the solids removal it is preferred according to the invention for the solids removal to have a cooling module which is arranged such that the heavy-boiling part introduced into the solids separation can be cooled to a temperature of at most 100 ° C. before separation.
  • the solids separation is followed by a solid-state energy conversion unit.
  • a solid-state energy conversion unit is particularly preferably a combustion unit which provides heat energy for heating the various heating elements of the oiling module.
  • the oil return has a return heating element.
  • the part of the high boiler part serving as contact oil introduced via the oil return into the reaction space can be preheated to the reaction temperature so that no significant temperature inhomogeneities occur within the reaction phase, which could adversely affect the process and the product quality.
  • At least one further reaction space adjoins the high boiler outlet.
  • the oiling module can follow a harvesting module.
  • the oiling module can directly follow the harvesting module.
  • another module preferably a confectioning module, in which the crop of the harvesting module can be further comminuted or pre-dried, for example, can be located between the harvesting module and the oiling module.
  • the inventive device tion is arranged on a vehicle. The measures described in this paragraph permit the harvesting of vegetable agricultural products suitable for Eduktmassen and their disposal as soon as possible. Consequently, it is preferred that the device according to the invention is used in the process according to the invention for the production of oils containing hydrocarbons.
  • the present invention relates to a method for generating kinetic, electrical and / or potential energy, wherein an energy generator uses an oil obtainable by the process according to the invention for the production of hydrocarbons-containing oils.
  • energy producers Preferably mentioned are internal combustion engines, such as gasoline engines, diesel engines, Wankel engines, steam engines, turbines or jet engines. Another group of energy producers form fuel cells.
  • the resulting in the inventive process for the production of hydrocarbons oils at 20 ° C gaseous products, in particular methane, ethane, propane or butane, particularly preferably methane or ethane and more preferably methane can be used.
  • the invention also relates to a process for the preparation of chemical products, wherein an oil or gas obtainable by the process according to the invention for the preparation of hydrocarbons-containing oils is subjected to a chemical reaction.
  • Suitable chemical reactions are all chemical reactions known in the field of petrochemicals.
  • starting products can be obtained which can be converted into intermediates or polymers by further reactions, such as addition or polymerization reactions.
  • the invention also relates to chemical products containing or at least partly based on an oil or gas obtainable by the process according to the invention for the production of hydrocarbons containing oils.
  • chemical products especially call foils, molding compounds, foams, lacquers, films or liquids 2x1.
  • the invention further relates to goods containing or at least partially based on chemical products or on chemical products obtainable by the process according to the invention for the production of oils containing hydrocarbon substances. Furthermore, the present invention relates to a method for transporting goods or transportation of persons, wherein a transport means obtains the energy for the transport at least partly obtainable from an oil or gas obtainable by the process according to the invention for producing hydrocarbons-containing oils.
  • Suitable means of transport are all suitable for the expert appearing means of transport into consideration. Examples include land vehicles such as automobiles, trucks, construction vehicles, buses, motorcycles and the like, watercraft such as ferries, container ships, passenger ships, hydrofoils and the like, aircraft such as airliners, fighters, missiles, helicopters or airships.
  • the different persons are preferably persons who differ from each other on the basis of their legal status.
  • the person providing the educt composition can be, for example, a farmer or an employee of an agricultural society who is not at least in the direct possession of the device according to the invention.
  • the other person performing the reaction step preferably belongs to a company that owns the device.
  • Such a society preferably has either the business purpose of renting the device according to the invention together with personnel in order, for example, to ablate the field ordered with vegetable agricultural products and to carry out the oiling, or else the business purpose, educt mass or for educt mass suitable upstream products, which were produced by third parties, auf ⁇ buy up and approach the oiling.
  • the invention additionally relates to the use of one of the methods described here or one of the devices described here in a sustainable energy industry or to reduce the generation of greenhouse gases.
  • FIG. 1 shows a perspective view of a harvesting vehicle with a spoiling module
  • FIG. 2 shows a perspective view of a mobile oiling module
  • FIG. 3 shows a schematic cross section of a oiling module
  • FIG. 4 shows a cross section through a starting material feed
  • FIG. 5 shows a superstructure cross section of a feedstock material feed
  • FIG. 6 shows a heat transfer module with two reaction spaces
  • FIG. 7 shows a schematic cross section of a fractionation unit
  • FIG. 8 shows a schematic cross section of a pilot plant
  • Figure 9 is a graphical representation of cylinder pressure curves.
  • FIG. 1 shows a harvesting vehicle 1 that has a header 2 for plant-based agricultural products, also called energy crops.
  • the Erntevor ⁇ set 2 has a number of cutting devices 3, with which the plants Energy ⁇ plants are harvested.
  • the header 2 is supported by a chassis 5 and is located in the field of vision of a driver's cab 4.
  • the header 2 is followed by a packaging unit 6, in which the energy crop chips are optionally comminuted, freed of water or impurities or even compacted , If further usable vegetable juices are produced in the packaging unit 6, as is the case, for example, in the processing of sugar beets or cane sugar, then the confectioning unit 6 is followed by a vegetable juice tank 7, which can pick up these plant juices.
  • an Eduktmasse Appendix 8 downstream of the packaging unit 6, usually downstream of the vegetable juice tank 7, there can be an Eduktmasse Anything 8. In this it can come to a further drainage and compaction of the educt composition.
  • Either to the packaging unit 6 directly or to the Edukt- mass storage 8 is followed by a Verkölungsmodul 9, in which the educt composition is baked by the action of temperature in the presence of an organic contact oil and the resulting oil is optionally refined.
  • the chassis 5 further has a plurality of driven wheels 10, which allow a possible soil-gentle movement of the harvesting vehicle 1.
  • FIG. 2 illustrates a device which is comparable to the harvester but not self-propelled and configured as a trailer.
  • reference is made to the embodiments of FIG. 1 in connection with the meaning of reference numbers 5, 6, 7, 8 and 9 taken.
  • FIG. 2 designates a tenter 11, which can optionally be connected to the vegetable juice tank 7, in which gas, preferably methane, can be obtained from the vegetable juice by suitable enzymes, which can be used for energy generation and for heating the oiling module.
  • gas preferably methane
  • suitable enzymes which can be used for energy generation and for heating the oiling module.
  • a device suitable for this purpose does not have a vegetable juice tank 7 and a fermenter 11.
  • wood waste originating, for example, from a sawmill or a wood processing plant, or animal waste, which may originate, for example, from a carcass utilization plant can be supplied directly to the oiling module 9 as educt mass.
  • FIG. 3 shows a oiling module 9 with a housing 12 such that a feedstock feed 13, an optionally pressurizable reaction space 14, which is preferably designed as a stainless steel reactor, has a separator 15 with a low boiler outlet 16 and adjoining it a high boiler outlet 17.
  • the high boiler outlet 17 is preferably tubular in the vertical direction and has a number of Society michsventi- len 18, with which a back-up ratio for liquid high boiler in or out of the reaction chamber 14 can be adjusted.
  • a nozzle 19 is arranged, with which it is possible to mix the reaction phase contained in the reaction space 14 by injecting oil.
  • reaction space 14 is at least partially surrounded on its walls externally by heating elements 20 which, together with the heating of the oil in the reaction chamber 14 heating elements 21 for the reaction temperature in ⁇ within the reaction chamber 14.
  • a high-boiling valve 22 which likewise controls, together with the fractionation valves 18, the fill level of the high boiler outlet 17 and thus the reflux ratio.
  • the high-boiling part discharged via the high-boiling valve 22 is fed to a solids separation 33, this solids separation 33 preferably operating in two stages and initially having a mechanical separating device 34, for example an edge gap filter and connected thereto a further mechanical separating device 35, preferably a separator (see FIG. 6).
  • the thus purified heavy-boiling part is stored in a high-boiling tank 36. From the high boiler tank 36 or immediately after leaving the solids separation 33, a part of the heavy boiler can be introduced via the heating element 21 into the first reaction space 14 by means of the nozzle 19
  • the starting material feed 13 is described in more detail.
  • This first has a collecting funnel 23 for receiving the starting material mass, which is continuously requested by a first conveying means 24, which is formed like a screw, from the collecting funnel 23 in the direction of the reaction space 14.
  • the first conveying means 24 is adjoined by a second conveying means 25 in that the educt mass requires a screw closure 26 by means of a screw-shaped conveyor.
  • the ball closure 26 has a ball 27 which is pressed by a spring bearing 28 on the VerInstitutöffhung 29.
  • FIG. 6 shows a further reaction space 30, which may follow the first reaction space 14, in which, starting from the high-boiling valve 22, a heating line 31 introduces high-boiling components into the lower region of the further reaction space 30.
  • a separator 15 with a low boiler outlet 16 and a high boiler outlet 17 also adjoin the further reaction chamber 30.
  • the low boiler outlet 16 of the further reaction space 30 is connected to the low boiler outlet 16 of the first reaction space 14 through a conduit.
  • a fractionation unit 32 can at thechtsiederauslass 16 connect (see Figure 7) in which the one worked deposited the water contained in the low-boiling and the low boiler in petrol, diesel or fuel oil fractions * voltage by distillation or by mechanical separation either or a combination thereof can be.
  • the heavy-boiling part taken off via high-boiling valve 22 is supplied to a solids outlet 33 preferably comprising a liquid outlet 35a and a solids outlet 35b, this solids separation 33 operating in two stages and a first mechanical separating device, preferably an edge-gap filter 34 and second second separating device mechanical separating device, preferably a separator 35 having.
  • the high-boiling part thus purified is also stored as a "heavy-liquid buffer" in a high-boiling tank 36. From this high-boiling tank 36, a part of the high boiler can be introduced via the heating element 21 into the first reaction space 14 by means of the nozzle 19.
  • FIG. 7 shows a fractionation unit 32 with a distillation zone having two or more distillations.
  • the fractionation unit 32 can be coupled to a heat recovery unit 38, preferably in the form of a heat exchanger or a heat pump, in order to reduce the fractionation unit operated by the cooling in the distillation unit 32 energy to be reintroduced into the example for preheating the screws.
  • the purified oil product obtained from the fractionation unit 32 is temporarily stored in a tank 39.
  • the components which are present in the fractionation unit 32 during workup are supplied to a generator 40 with which energy is generated by an internal combustion engine which generates at least partially, preferably completely, the energy supply of the oiling module 9 or the harvesting vehicle 1 can be used.
  • FIG. 8 shows a test setup in which a reactor 41 forms a reaction space 14, which receives a stirrer 42 and can be fed in a controllable manner via an educt inlet 43 with an educt valve via a feed valve 48. Furthermore, the reactor 41 has a controllable via the control 44 heating. In the upper region of the Re ⁇ actuator 41, a radiator 45 connects, which opens into a separator 46, which is arranged under a trigger 47.
  • FIG. 9 shows a graphic representation of cylinder pressure profiles in a biodiesel produced by the process according to the invention and a conventional, commercially available diesel fuel in a 1.9 l passenger car diesel engine at 4000 revolutions per minute, a torque of 90 Nm.
  • a device as shown in Figure 3 (only one reactor) comprising a stainless steel reactor with a reactor volume of 1,000 liters, which was preheated to a temperature of 36O 0 C, was continuously straw with a water content of about 8 wt .-% , which was comminuted to a particle size of 5 mm on average and preheated to a temperature of 100 ° C introduced. At the same time, such an amount was introduced at temperature of 360 0 C heated to a Tem ⁇ contact oil in the reactor such that the ratio of the straw to contact oil inside the reactor always about 1: 3.
  • the temperature drop caused by the addition of straw at a temperature of 100 0 C inside the reactor was compensated by a corresponding increase in the temperature of the supplied contact oil, so that the temperature inside the reactor was constant at about 360 ° C.
  • BP heavy oil is used with a boiling point of more than 200 0 C at atmospheric pressure.
  • the components were mixed in the reactor by means of a stirrer, where it can at the temperature of 360 ° C inside the reactor for thermal cleavage of the straw.
  • the gaseous phase in the reaction space was brought into contact by means of conventional tube bundle heat exchange and cooled by about 50 ° C., where it can condense high boilers.
  • Mit ⁇ means of a conventional cyclone, the high boilers were separated and, after they were cooled to a temperature of about 100 0 C, using an edge-gap filter from Mahle GmbH (type AF 7383-521-50700 / S1) and then by means of a Westfalia Separators (OTC2-02-137) freed of solids.
  • the high solids boilers were then sent to a heavy dump tank.
  • the high boilers have now been continuously introduced as a contactless oil into the reactor from the high-boiling tank, wherein the high boilers were preheated to a temperature of about 360 0 C.
  • the plant was operated continuously for several hours in the manner described above.
  • a sample of the separated low-boiling condensate obtained after several hours of operation of the plant was, after the still existing in the sample has been separated, burned as a fuel in a 1.9 L passenger car diesel engine.
  • the biodiesel fuel which is obtainable by the process according to the invention is superior to conventional fuels, as shown, inter alia, in a higher cylinder pressure than conventional biodiesel fuels.
  • first mechanical separation device preferably edge gap filter
  • 35 second mechanical separation device preferably Westfalia separator

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Processing Of Solid Wastes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP05770008A 2004-08-05 2005-08-05 THERMISCHE BIOMASSENVERöLUNG Withdrawn EP1789515A1 (de)

Applications Claiming Priority (2)

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DE102004038220A DE102004038220B4 (de) 2004-08-05 2004-08-05 Thermische Biomassenverölung
PCT/EP2005/008477 WO2006015804A1 (de) 2004-08-05 2005-08-05 Thermische biomassenverölung

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WO2006015804A1 (de) 2006-02-16
ZA200700984B (en) 2008-09-25
RU2384602C2 (ru) 2010-03-20
US7704381B2 (en) 2010-04-27
CN101035880A (zh) 2007-09-12
US20070261996A1 (en) 2007-11-15
DE102004038220B4 (de) 2009-07-23
BRPI0514100A (pt) 2008-05-27
RU2007107181A (ru) 2008-09-10
AU2005270353A1 (en) 2006-02-16
UA91344C2 (ru) 2010-07-26
CA2575910A1 (en) 2006-02-16
JP2008508413A (ja) 2008-03-21
DE102004038220A1 (de) 2006-03-16

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