EP0052334B2 - Process for the production of solid, liquid and gaseous combustibles from organic materials - Google Patents
Process for the production of solid, liquid and gaseous combustibles from organic materials Download PDFInfo
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- EP0052334B2 EP0052334B2 EP81109604A EP81109604A EP0052334B2 EP 0052334 B2 EP0052334 B2 EP 0052334B2 EP 81109604 A EP81109604 A EP 81109604A EP 81109604 A EP81109604 A EP 81109604A EP 0052334 B2 EP0052334 B2 EP 0052334B2
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- conversion
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
Definitions
- the invention relates to a method for obtaining solid, liquid and gaseous fuels from organic material in granular or powdery form using elevated temperature and with the exclusion of air.
- Solid and liquid fuels are now almost exclusively obtained from fossil fuels such as coal and petroleum.
- the synthetic processes for the production of hydrocarbons e.g. Pier and Bergius coal hydrogenation or the so-called Fischer-Tropsch process are based on these fossil fuels, especially coal.
- coal is primarily made from vegetable material with a high cellulose content and petroleum from bacterial mass. Bacteria consist of 60 to 80% proteins and lipids. The heterofunctions originally present in the natural material, in particular the nitrogen, sulfur and oxygen functions, must therefore have been eliminated from these substances during the formation of petroleum. This should have been done under conditions where no carbon-carbon bonds were broken and oxidative or reductive processes were not required. So far, the assumed “natural reaction processes could not be imitated. In particular, no process has yet been found which would have made it possible to convert organic material, in particular organic material of plant or animal origin, into solid or liquid fuels under normal pressure and without involving reductive or oxidative processes.
- the invention is therefore based on the object of providing a process for the production of solid, liquid and gaseous fuels which does not rely on fossil fuels but the conversion of biomass of microbial, vegetable or animal origin, of sediments containing organic material or garbage at normal pressure and without the involvement of reduction and oxidation processes.
- the invention therefore relates to a method for obtaining solid, liquid and gaseous fuels from organic material in granular or powdery form using elevated temperature and with the exclusion of air, the gases and vapors escaping during heating being passed through suitable gas and liquid separators , maintains the conversion temperature until the gas and vapor evolution has essentially ended and isolates the solid conversion residue and the separated gases and liquids, which is characterized in that carbohydrates, lipids, proteins, plant, bacterial and algae masses are used as organic material, Fresh sludge, sewage sludge or digested sludge from sewage treatment plants or the organic components of domestic or industrial waste are used, and this material in the presence of a conversion catalyst at a speed of 5 to 30 ° C per minute to a conversion temperature of 200 heated up to 400 ° C.
- Aluminum oxide, an aluminum salt, phosphoric acid, phosphate, borate, silica gel, silicates, aluminum silicate or an oxide of a transition metal, or a mixture of these catalysts can be used as the catalyst.
- the oxide of a transition metal is preferably a Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn oxide, or a mixture of these oxides or a mixture of at least one of these oxides at least one of the aforementioned compounds.
- Aluminum oxide, montmorillonite, mixed catalysts made of aluminum oxide / copper oxide, aluminum oxide / vanadium pentoxide and aluminum oxide / nickel oxide have proven successful.
- the conversion temperature is preferably in the range of 250 to 350 ° C, more preferably the range of 280 to 330 ° C, a temperature of about 300 ° C is most preferred.
- the proportion of catalyst is generally 0.01 to 10% by weight, preferably 0.1 to 6% by weight, based on the weight of the organic material used.
- the starting material consists predominantly of cellulose and carbohydrates, for example of vegetable origin
- coal is obtained as the main product.
- the starting material consists mainly of proteins and lipids, eg from a biomass based on microorganisms
- the conversion product mainly consists of oils and hydrocarbons.
- 70 to 90% of the carbon originally present is converted into coal and oil.
- the remaining carbon emerges in gaseous form as a mixture of CO 2 , CO, CH 4 and lower hydrocarbons.
- the heat of combustion of the oils obtained is between 29 308 and 41 868 kJ (7000-10 000 kcal / kg) depending on the starting material, reaction conditions and catalyst.
- the heat of combustion of the coal formed is between 12,560 and 33,494 kJ (3000-8000 kcal / kg), depending on the amount of inorganic residues present in the coal.
- the oils obtained are free of inorganic residues and relatively low in sulfur (0.05 up to 1.0% S). In this respect, they can be compared to the best petroleum oils, which have a sulfur content of 0.3 to 6%.
- the process according to the invention is particularly suitable for the processing and conversion of sewage sludge and digested sludge, such as is produced in plants for biological wastewater treatment.
- This sludge is usually mechanically dewatered in filter presses or centrifuges down to a water content of around 40 to 60%. This proportion of water is significantly reduced either by drying in air or by heating, so that a dry, solid bulk material is obtained in powdery or granular form.
- This material is used in the process according to the invention.
- One heats up slowly in the absence of air the first thing that evaporates is the remaining water, which is condensed and collected.
- the elimination of hetero functions begins, which increases sharply from 250 ° C and slowly decreases again from 320 ° C.
- this gas serves as a protective gas, which prevents the entry of the air atmosphere.
- the higher hydrocarbons and oils produced during the conversion escape as gases or vapors from the reaction vessel. They are usually condensed together and later refined.
- the conversion oil obtained in this way has the advantage over petroleum that it does not contain any difficult-to-use asphalts and tars. It can be evaporated quantitatively, which is advantageous for further processing, particularly in crack processes for the production of gasoline.
- Analytical studies of the conversion oil obtained according to the invention have also shown that the proportion of unbranched hydrocarbons and fatty acids can be up to 50%.
- the fensic acid fraction is easy to remove from the oil; it is a valuable industrial raw material, the price of which is currently much higher than that of petroleum. The same applies to the unbranched hydrocarbons.
- the fatty acids can also be converted into hydrocarbons in a known manner.
- the sulfur and nitrogen content of the coal residue is relatively low, so the coal can also be hydrated or used to generate water gas.
- the process according to the invention is advantageously carried out continuously by using the dry starting material, e.g. the dried sewage sludge, granular or as a powder continuously, e.g. with the help of a screw conveyor, conveyed through a heated reaction tube.
- the dry starting material e.g. the dried sewage sludge, granular or as a powder continuously, e.g. with the help of a screw conveyor, conveyed through a heated reaction tube.
- the conversion process is usually finished after 2 to 3 hours.
- NiO instead of V 2 0 5 , 0.1 g of NiO can also be added.
- Carbonaceous residue C 80.5%; H 2.4%; Heat of combustion 29 726 kJ / kg.
- Carbonaceous residue C 78.8%; H 3.2%; Heat of combustion 29 308 kJ / kg.
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Sludge (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Processing Of Solid Wastes (AREA)
- Coke Industry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Gewinnung von festen, flüssigen und gasförmigen Brennstoffen aus organischem Material in körniger bzw. pulvriger Form unter Anwendung erhöhter Temperatur und unter Luftausschluss.The invention relates to a method for obtaining solid, liquid and gaseous fuels from organic material in granular or powdery form using elevated temperature and with the exclusion of air.
Feste und flüssige Brennstoffe werden heute fast ausschliesslich aus fossilen Energieträgern, wie Kohle und Erdöl, gewonnen. Auch die synthetischen Verfahren zur Herstellung von Kohlenwasserstoffen, z.B. die Kohlehydrierung nach Pier und Bergius oder das sogenannte Fischer-Tropsch-Verfahren gehen von diesen fossilen Brennstoffen, insbesondere von Kohle, aus.Solid and liquid fuels are now almost exclusively obtained from fossil fuels such as coal and petroleum. The synthetic processes for the production of hydrocarbons, e.g. Pier and Bergius coal hydrogenation or the so-called Fischer-Tropsch process are based on these fossil fuels, especially coal.
Man nimmt heute an, dass Kohle vorwiegend aus pflanzlichem Material mit hohem Cellulosegehalt und Erdöl aus Bakterienmasse entstanden sind. Bakterien bestehen zu 60 bis 80% aus Proteinen und Lipiden. Aus diesen Substanzen müssen daher bei der Erdölentstehung die im natürlichen Material ursprünglich vorhandenen Heterofunktionen, insbesondere die Stickstoff-, Schwefel- und Sauerstoff-Funktion eliminiert worden sein. Dies müsste unter Bedingungen geschehen sein, bei denen keine Kohlenstoff-Kohlenstoff-Bindungen gespalten wurden und oxidative oder reduktive Prozesse nicht erforderlich waren. Die angenommenen « natürlichen Reaktionsabläufe konnten bisher nicht nachgeahmtwerden. Insbesondere wurde noch kein Verfahren gefunden, das die Umwandlung von organischem Material, insbesondere von organischem Material pflanzlichen oder tierischen Ursprungs, in feste oder flüssige Brennstoffe unter Normaldruck und ohne Einschaltung von reduktiven oder oxidativen Prozessen ermöglicht hätte.It is now assumed that coal is primarily made from vegetable material with a high cellulose content and petroleum from bacterial mass. Bacteria consist of 60 to 80% proteins and lipids. The heterofunctions originally present in the natural material, in particular the nitrogen, sulfur and oxygen functions, must therefore have been eliminated from these substances during the formation of petroleum. This should have been done under conditions where no carbon-carbon bonds were broken and oxidative or reductive processes were not required. So far, the assumed “natural reaction processes could not be imitated. In particular, no process has yet been found which would have made it possible to convert organic material, in particular organic material of plant or animal origin, into solid or liquid fuels under normal pressure and without involving reductive or oxidative processes.
Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zur Gewinnung von festen, flüssigen und gasförmigen Brennstoffen bereitzustellen, das nicht auf fossile Energieträger angewiesen ist sondern die Umwandlung von Biomassen mikrobiellen, pflanzlichen oder tierischen Ursprungs, von organisches Material enthaltenden Sedimenten oder Müll bei normalem Druck und ohne Einschaltung von Reduktions- und Oxidationsprozessen gestattet.The invention is therefore based on the object of providing a process for the production of solid, liquid and gaseous fuels which does not rely on fossil fuels but the conversion of biomass of microbial, vegetable or animal origin, of sediments containing organic material or garbage at normal pressure and without the involvement of reduction and oxidation processes.
Überraschenderweise wurde jetzt ein Verfahren gefunden, das die vorbezeichnete Aufgabe löst.Surprisingly, a method has now been found that solves the aforementioned task.
Die Erfindung betrifft deshalb ein Verfahren zur Gewinnung von festen, flüssigen und gasförmigen Brennstoffen aus organischem Material in körniger bzw. pulvriger Form unter Anwendung erhöhter Temperatur und unter Luftausschluss, wobei man die beim Erhitzen entweichenden Gase und Dämpfe durch geeignete Gas- und Flüssigkeits-Abscheider leitet, die Konvertierungstemperatur beibehält bis die Gas- und Dampfentwicklung im wesentlichen beendet ist und den festen Konvertierungsrückstand und die abgeschiedenen Gase und Flüssigkeiten isoliert, das dadurch gekennzeichnet ist, dass man als organisches Material Kohlenhydrate, Lipide, Proteine, Pflanzen-, Bakterien-, Algenmassen, Frischschlamm, Klärschlamm oder Faulschlamm aus Anlagen zur Abwasserreinigung oder die organischen Bestandteile von Haus- oder Industriemüll verwendet, und dieses Material in Anwesenheit eines Konvertierungskatalysators mit einer Geschwindigkeit von 5 bis 30°C pro Minute auf eine Konvertierungstemperatur von 200 bis 400°C erhitzt.The invention therefore relates to a method for obtaining solid, liquid and gaseous fuels from organic material in granular or powdery form using elevated temperature and with the exclusion of air, the gases and vapors escaping during heating being passed through suitable gas and liquid separators , maintains the conversion temperature until the gas and vapor evolution has essentially ended and isolates the solid conversion residue and the separated gases and liquids, which is characterized in that carbohydrates, lipids, proteins, plant, bacterial and algae masses are used as organic material, Fresh sludge, sewage sludge or digested sludge from sewage treatment plants or the organic components of domestic or industrial waste are used, and this material in the presence of a conversion catalyst at a speed of 5 to 30 ° C per minute to a conversion temperature of 200 heated up to 400 ° C.
Es istvortei Ihaft, dem organischen Ausgangsmaterial vor dem Erhitzen einen Konvertierungskatalysator zuzumischen. Als Katalysator kann man Aluminiumoxid, ein Aluminiumsalz, Phosphorsäure, Phosphat, Borat, Silicagel, Silikate, Aluminiumsilikat oder ein Oxid eines Übergangsmetalles, bzw. ein Gemisch dieser Katalysatoren verwenden. Als Oxid eines Übergangsmetalles verwendet man vorzugsweise ein Ti-, V-, Cr-, Mn-, Fe-, Co-, Ni-, Cu- oder Zn-Oxid, bzw. ein Gemisch dieser Oxide oder ein Gemisch mindestens eines dieser Oxide mit mindestens einer dervorhergenannten Verbindungen. Gut bewährt haben sich Aluminiumoxid, Montmorillonit, Mischkatalysatoren aus Aluminiumoxid/Kupferoxid, Aluminiumoxid/Vanadinpentoxid und Aluminiumoxid/Nickeloxid.It is advantageous to add a conversion catalyst to the organic starting material before heating. Aluminum oxide, an aluminum salt, phosphoric acid, phosphate, borate, silica gel, silicates, aluminum silicate or an oxide of a transition metal, or a mixture of these catalysts, can be used as the catalyst. The oxide of a transition metal is preferably a Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn oxide, or a mixture of these oxides or a mixture of at least one of these oxides at least one of the aforementioned compounds. Aluminum oxide, montmorillonite, mixed catalysts made of aluminum oxide / copper oxide, aluminum oxide / vanadium pentoxide and aluminum oxide / nickel oxide have proven successful.
Die Konvertierungstemperatur liegt vorzugsweise im Bereich von 250 bis 350°C, noch stärker bevorzugt ist der Bereich von 280 bis 330°C, eine Temperatur von etwa 300°C ist am stärksten bevorzugt.The conversion temperature is preferably in the range of 250 to 350 ° C, more preferably the range of 280 to 330 ° C, a temperature of about 300 ° C is most preferred.
Es istvorteilhaft, das organische Ausgangsmaterial mit einer Geschwindigkeit von 10 bis 20°C pro Minute auf Konvertierungstemperatur aufzuheizen.It is advantageous to heat the organic starting material to the conversion temperature at a rate of 10 to 20 ° C per minute.
Der Katalysatoranteil beträgt im allgemeinen 0,01 bis 10 Gew.-% vorzugsweise 0,1 bis 6 Gew.-%, bezogen auf das Gewicht des eingesetzten organischen Materiales.The proportion of catalyst is generally 0.01 to 10% by weight, preferably 0.1 to 6% by weight, based on the weight of the organic material used.
Wenn das Ausgangsmaterial überwiegend aus Cellulose und Kohlehydraten besteht, z.B. pflanzlichen Ursprungs ist, so erhält man Kohle als Hauptprodukt. Besteht das Ausgangsmaterial hauptsächlich aus Proteinen und Lipiden, z.B. aus einer Biomasse auf der Basis von Mikroorganismen, so besteht das Konvertierungsprodukt hauptsächlich aus Ölen und Kohlenwasserstoffen. Insgesamt werden nach dem erfindungsgemässen Verfahren die eingesetzten Materialien zu 70 bis 90% des ursprünglich vorhandenen Kohlenstoffs in Kohle und Öl umgewandelt. Der restliche Kohlenstoff tritt gasförmig als Gemisch von CO2, CO, CH4 und niederen Kohlenwasserstoffen aus. Die Verbrennungswärme der erhaltenen Öle liegtje nach Ausgangsmaterial, Reaktionsbedingungen und Katalysator zwischen 29 308 und 41 868 kJ (7000-10 000 kcal/kg). Die Verbrennungswärme dergebildeten Kohle liegt zwischen 12 560 und 33 494 kJ (3000-8000 kcal/kg), in Abhängigkeit von der Menge der in der Kohle vorhandenen anorganischen Rückstände. Die erhaltenen Öle sind frei von anorganischen Rückständen und relativ schwefelarm (0,05 bis 1,0% S). Sie können in dieser Hinsicht mit den besten Erdölen verglichen werden, die Schwefelgehalte von 0,3 bis 6% aufweisen.If the starting material consists predominantly of cellulose and carbohydrates, for example of vegetable origin, then coal is obtained as the main product. If the starting material consists mainly of proteins and lipids, eg from a biomass based on microorganisms, the conversion product mainly consists of oils and hydrocarbons. Overall, according to the method according to the invention, 70 to 90% of the carbon originally present is converted into coal and oil. The remaining carbon emerges in gaseous form as a mixture of CO 2 , CO, CH 4 and lower hydrocarbons. The heat of combustion of the oils obtained is between 29 308 and 41 868 kJ (7000-10 000 kcal / kg) depending on the starting material, reaction conditions and catalyst. The heat of combustion of the coal formed is between 12,560 and 33,494 kJ (3000-8000 kcal / kg), depending on the amount of inorganic residues present in the coal. The oils obtained are free of inorganic residues and relatively low in sulfur (0.05 up to 1.0% S). In this respect, they can be compared to the best petroleum oils, which have a sulfur content of 0.3 to 6%.
Das erfindungsgemässe Verfahren eignet sich besonders zur Aufarbeitung und Umwandlung von Klärschlamm und Faulschlamm, wie er in Anlagen zur biologischen Abwasserreinigung entsteht. Dieser Schlamm wird meist in Filterpressen oder Zentrifugen mechanisch entwässert bis auf einen Wassergehalt von etwa 40 bis 60%. Dieser Wasseranteil wird entweder durch Trocknung an der Luft oder durch Erhitzen noch wesentlich reduziert, so dass man ein trockenes, festes Schüttgut in pulveriger oder körniger Form erhält. Dieses Material wird in das erfindungsgemässe Verfahren eingesetzt. Man heizt langsam unter Luftausschluss auf, dabei verdampft zuerst das restliche Wasser, welches kondensiert und aufgefangen wird. Bei etwa 180 bis 200°C beginnt die Eliminierung der Hetero-Funktionen, die ab 250°C stark zunimmt und ab 320°C wieder langsam abnimmt. Dabei entstehen Kohlendioxid, Kohlenmonoxid, Ammoniak, Salzsäure, Schwefelwasserstoff und niedere Kohlenwasserstoffe, vom Methan bis zum Hexan. Ammoniak, Chlorwasserstoff, Schwefelwasserstoff und ein Teil des Kohlendioxids kondensieren zusammen mit dem Wasser in ungefährlicher Form als Ammoniumsalze und werden so aus der Gasphase entfernt. Die austretenden Gase sind daher frei von basischen Substanzen und enthalten als Hauptkomponenten CO2, CO, CH4 und niedere Kohlenwasserstoffe. Aus einem kg Klärschlamm erhält man etwa 5 Liter Gas mit einem Brennwert von 18 600 kJ/m3.The process according to the invention is particularly suitable for the processing and conversion of sewage sludge and digested sludge, such as is produced in plants for biological wastewater treatment. This sludge is usually mechanically dewatered in filter presses or centrifuges down to a water content of around 40 to 60%. This proportion of water is significantly reduced either by drying in air or by heating, so that a dry, solid bulk material is obtained in powdery or granular form. This material is used in the process according to the invention. One heats up slowly in the absence of air, the first thing that evaporates is the remaining water, which is condensed and collected. At around 180 to 200 ° C, the elimination of hetero functions begins, which increases sharply from 250 ° C and slowly decreases again from 320 ° C. This creates carbon dioxide, carbon monoxide, ammonia, hydrochloric acid, hydrogen sulfide and lower hydrocarbons, from methane to hexane. Ammonia, hydrogen chloride, hydrogen sulfide and some of the carbon dioxide condense together with the water in harmless form as ammonium salts and are thus removed from the gas phase. The escaping gases are therefore free of basic substances and contain CO 2 , CO, CH 4 and lower hydrocarbons as main components. About 5 liters of gas with a calorific value of 18,600 kJ / m3 are obtained from one kg of sewage sludge.
Da bei dererfindungsgemässen Niedrigtemperatur-Konvertierung - im Gegensatz zur Pyrolyse - im wesentlichen keine C-C-Bindungen gespalten werden, ist der geringe Gasanteil verständlich. Während des Konvertierungsprozesses dient dieses Gas als Schutzgas, welches den Zutritt der Luftatmosphäre verhindert.Since, in contrast to pyrolysis, essentially no C-C bonds are split in the low-temperature conversion according to the invention, the low gas content is understandable. During the conversion process, this gas serves as a protective gas, which prevents the entry of the air atmosphere.
Die bei der Konvertierung entstehenden höheren Kohlenwasserstoffe und Öle entweichen als Gase bzw. Dämpfe aus dem Reaktionsgefäss. Sie werden meist gemeinsam kondensiert und später raffiniert. Gegenüber dem Erdöl hat das so gewonnene Konvertierungsöl den Vorteil, dass es keine schwer verwertbaren Asphalte und Teere enthält. Es ist quantitativ verdampfbar, was für die Weiterverarbeitung, insbesondere bei Crack-Prozessen zur Benzingewinnung, von Vorteil ist. Analytische Untersuchungen des erfindungsgemäss gewonnenen Konvertierungsöles haben ausserdem gezeigt, dass der Anteil an unverzweigten Kohlenwasserstoffen und Fettsäuren bis zu 50% betragen kann. Die Fensäure-Fraktion lässt sich aus dem Öl einfach entfernen, sie ist ein wertvoller industrieller Ausgangsstoff, dessen Preis zur Zeit wesentlich höher liegt als der von Erdöl. Das gleiche gilt für die unverzweigten Kohlenwasserstoffe. Falls gewünscht, können die Fettsäuren aber auch auf bekannte Weise in Kohlenwasserstoffe umgewandelt werden.The higher hydrocarbons and oils produced during the conversion escape as gases or vapors from the reaction vessel. They are usually condensed together and later refined. The conversion oil obtained in this way has the advantage over petroleum that it does not contain any difficult-to-use asphalts and tars. It can be evaporated quantitatively, which is advantageous for further processing, particularly in crack processes for the production of gasoline. Analytical studies of the conversion oil obtained according to the invention have also shown that the proportion of unbranched hydrocarbons and fatty acids can be up to 50%. The fensic acid fraction is easy to remove from the oil; it is a valuable industrial raw material, the price of which is currently much higher than that of petroleum. The same applies to the unbranched hydrocarbons. If desired, the fatty acids can also be converted into hydrocarbons in a known manner.
Da bei der Konvertierung von Klärschlamm die darin enthaltenen Kohlenstoffverbindungen zum grösseren Teil in Öl umgewandelt werden, ist der am Ende des Konvertierungsprozesses anfallende Rückstand relativ kohlenstoffarm. Er kann aber trotzdem direkt verbrannt werden, wenn die üblichen Sicherheitsmassnahmen in Bezug auf eventuell vorhandene Schwermetalle, insbesondere Quecksilber und Cadmium, eingehalten werden.Since the conversion of sewage sludge largely converts the carbon compounds it contains into oil, the residue that arises at the end of the conversion process is relatively low in carbon. However, it can still be burned directly if the usual safety measures with regard to any heavy metals, in particular mercury and cadmium, are observed.
Der Schwefel- und Stickstoffgehalt des Kohlerückstandes ist relativ gering, die Kohle kann daher auch aufhydriert werden oder zur Erzeugung von Wassergas verwendet werden.The sulfur and nitrogen content of the coal residue is relatively low, so the coal can also be hydrated or used to generate water gas.
Das erfindungsgemässe Verfahren wird vorteilhafterweise kontinuierlich durchgeführt, indem man das trockene Ausgangsmaterial, z.B. den getrockneten Klärschlamm, körnig oder als Pulver kontinuierlich, z.B. mit Hilfe einer Förderschnekke, durch ein beheiztes Reaktionsrohr befördert.The process according to the invention is advantageously carried out continuously by using the dry starting material, e.g. the dried sewage sludge, granular or as a powder continuously, e.g. with the help of a screw conveyor, conveyed through a heated reaction tube.
Der Konvertierungsprozess ist meist nach 2 bis 3 Stunden beendet.The conversion process is usually finished after 2 to 3 hours.
Wenn Klärschlamm in die Konvertierung eingesetzt wird, ist eine Zugabe von Katalysatormaterial meist überflüssig, da die im Klärschlamm vorhandenen anorganischen Bestandteile meist ausreichende Mengen an Silikaten, Aluminiumverbindungen und Übergangsmetalle enthalten. Die grosstechnische Konvertierung dieses Materiales wird dadurch wesentlich erleichtert.If sewage sludge is used in the conversion, the addition of catalyst material is usually superfluous, since the inorganic constituents present in the sewage sludge usually contain sufficient amounts of silicates, aluminum compounds and transition metals. This greatly facilitates the large-scale conversion of this material.
Die nachfolgenden Beispiele dienen zur weiteren Erläuterung der Erfindung.The following examples serve to explain the invention further.
100 g Albumin werden 3 Stunden lang unter Luftausschluss auf 230°C erhitzt. Es werden 30 g Öl und 42 g festes, kohleartiges Produkt erhalten.100 g of albumin are heated to 230 ° C. for 3 hours in the absence of air. 30 g of oil and 42 g of solid, coal-like product are obtained.
Öl: C 70.5%; H 12.1%; Verbrennungswärme 31 401 kJ/kgOil: C 70.5%; H 12.1%; Heat of combustion 31 401 kJ / kg
Kohlerückstand C 79%; Verbrennungswärme 34 332 kJ/kg.Coal residue C 79%; Heat of combustion 34 332 kJ / kg.
100 g getrockneter Klärschlamm (C 44%; H 6,66%; N 8,39%, 20% Rückstand) werden bei 320 °C 2,5 Stunden unter Luftausschluss erhitzt. Es werden 35 g Öl und 41 g festes, kohlehaltiges Produkt erhalten.100 g of dried sewage sludge (C 44%; H 6.66%; N 8.39%, 20% residue) are heated at 320 ° C for 2.5 hours with the exclusion of air. 35 g of oil and 41 g of solid, carbonaceous product are obtained.
Öl: C 66.1 %; H 8.4%; N 7.5%; S 0.32%. Verbrennungswärme 29 726 kJ/kg.Oil: C 66.1%; H 8.4%; N 7.5%; S 0.32%. Heat of combustion 29 726 kJ / kg.
Kohlerückstand: 35.39% C; 1.7% H; 5,76% N.Coal residue: 35.39% C; 1.7% H; 5.76% N.
Rückstand: 49.85%; Verbrennungwärme 12 980 kJ/kg.Arrears: 49.85%; Heat of combustion 12 980 kJ / kg.
100 g getrockneter Klärschlamm werden mit 5 g A1203 und 0,1 g CuO vermischt und 3 Stunden auf 300 °C unter Luftausschluss erhitzt. Es werden 42 g Öl und 39 g kohlehaltiges Festprodukt erhalten.100 g of dried sewage sludge are mixed with 5 g of A1 2 0 3 and 0.1 g of CuO and heated at 300 ° C. for 3 hours with the exclusion of air. 42 g of oil and 39 g of carbon-containing solid product are obtained.
Öl: C 75,9%; H 10.2%; N 2.08%; S 0.05%; Verbrennungswärme: 37 263 kJ/kg.Oil: C 75.9%; H 10.2%; N 2.08%; S 0.05%; Heat of combustion: 37 263 kJ / kg.
Kohlehaltiger Rückstand: C 40.1%; H 1.8%; N 4.8%; S 1.26%;Carbonaceous residue: C 40.1%; H 1.8%; N 4.8%; S 1.26%;
Rückstand 42.5%; Verbrennungswärme 15 073 kJ/kg.Residue 42.5%; Heat of combustion 15 073 kJ / kg.
100 g getrocknete Bakterienmasse (Streptomyces species) werden mit 5 g wasserfreiem Montmorillonit 2 Stunden auf 350°C unter Luftausschluss erhitzt. Es werden 47 g Öl und 34 g fester kohlehaltiger Rückstand erhalten.100 g of dried bacterial mass (Streptomyces species) are heated with 5 g of anhydrous montmorillonite for 2 hours at 350 ° C in the absence of air. 47 g of oil and 34 g of solid carbonaceous residue are obtained.
Öl: C 62%; H 12.5%; N 3.2%; S 0.3%; Verbrennungswärme 32 657 kJ/kg.Oil: C 62%; H 12.5%; N 3.2%; S 0.3%; Heat of combustion 32 657 kJ / kg.
Kohlehaltiger Rückstand: C 52%; H 1.5%; N 3.2%; S 0.5%;Carbonaceous residue: C 52%; H 1.5%; N 3.2%; S 0.5%;
Rückstand 30.7%, Verbrennungswärme 21 353 kJ/kg.Residue 30.7%, heat of combustion 21 353 kJ / kg.
100 g getrockneter Klärschlamm werden mit 1 g A1203 und 0,01 g V205 vermengt und auf400°C unter Luftausschluss 3 Stunden lang erhitzt. Es werden 33 g Öl und 59 g Rückstand erhalten.100 g of dried sewage sludge are mixed with 1 g of A1 2 0 3 and 0.01 g of V 2 0 5 and heated to 400 ° C with the exclusion of air for 3 hours. 33 g of oil and 59 g of residue are obtained.
Öl: C 75.2%; H 11.2%; N 5.06%; S 0.15%.Oil: C 75.2%; H 11.2%; N 5.06%; S 0.15%.
Kohlehaltiger Rückstand: C 37.2%; H 1.6%; Rückstand 47.2%.Carbonaceous residue: C 37.2%; H 1.6%; Arrears 47.2%.
Anstelle von V205 können auch 0,1 g NiO zugegeben werden.Instead of V 2 0 5 , 0.1 g of NiO can also be added.
100 g Klärschlamm werden mit 1 g A1203 vermengt und 2 Stunden auf 280 °C erhitzt. Es werden 29 g Öl und 51 g festes, kohlehaltiges Produkt erhalten.100 g sewage sludge are mixed with 1 g A1 2 0 3 and heated to 280 ° C for 2 hours. 29 g of oil and 51 g of solid, carbonaceous product are obtained.
Öl: C 70.2%; H 10.1 %; N 6.1 %; S 0.4%; Verbrennungswärme 29 098 kJ/kg.Oil: C 70.2%; H 10.1%; N 6.1%; S 0.4%; Heat of combustion 29 098 kJ / kg.
Kohlehaltiger Rückstand: C 38.9%; H 3.3%; N 6.4%; S 1.4%.Carbonaceous residue: C 38.9%; H 3.3%; N 6.4%; S 1.4%.
Rückstand 42.1%.Residue 42.1%.
100 g Cellulose werden unter Luftausschluss 3 Stunden bei 250°C erhitzt. Es werden 5 g Öl und 50 g kohlehaltiger Rückstand erhalten.100 g of cellulose are heated at 250 ° C. for 3 hours with the exclusion of air. 5 g of oil and 50 g of carbonaceous residue are obtained.
Kohlehaltiger Rückstand: C 80.5%; H 2.4%; Verbrennungswärme 29 726 kJ/kg.Carbonaceous residue: C 80.5%; H 2.4%; Heat of combustion 29 726 kJ / kg.
100 g Stärke werden mit 5 g Al2O3 unter Luftausschluss 3 Stunden lang auf 210°C erhitzt. Ausbeute 52 g kohlehaltiger Rückstand und 4 g Öl.100 g of starch are heated to 210 ° C. for 3 hours with 5 g of Al 2 O 3 in the absence of air. Yield 52 g of carbonaceous residue and 4 g of oil.
Kohlehaltiger Rückstand: C 78.8%; H 3.2%; Verbrennungswärme 29 308 kJ/kg.Carbonaceous residue: C 78.8%; H 3.2%; Heat of combustion 29 308 kJ / kg.
100 g feinvermahlener, getrockneter Hausmüll werden mit 1 g Al2O3 und 0,1 g CuO vermengt und 4 Stunden unter Luftausschluss auf 360°C erhitzt. Es werden 20 g Öl und 51 g kohlehaltiger Rückstand erhalten.100 g of finely ground, dried household waste are mixed with 1 g of Al 2 O 3 and 0.1 g of CuO and heated to 360 ° C. for 4 hours with the exclusion of air. 20 g of oil and 51 g of carbonaceous residue are obtained.
Öl: C 71.2%; H 11.3%; N 1.0%; S 0.3%.Oil: C 71.2%; H 11.3%; N 1.0%; S 0.3%.
Kohlehaltiger Rückstand: C 43.4%; H 3.75%, N 1.5%; S 0.7%;Carbonaceous residue: C 43.4%; H 3.75%, N 1.5%; S 0.7%;
Rückstand 37.0%.Residue 37.0%.
Claims (9)
characterized in that
carbohydrates, lipides, proteines; vegetable, bac- teriae,algae masses; fresh sludge, sewage sludge or fermentation sludge from waste water purifying plants or the organic components of private or industrial garbage are used as organic material and that this material is heated in the presence of a conversion catalyst at a rate of 5 to 30°C per minute up to a conversion temperature of 200 to 400°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81109604T ATE20759T1 (en) | 1980-11-14 | 1981-11-10 | PROCESSES FOR OBTAINING SOLID, LIQUID AND GASEOUS FUELS FROM ORGANIC MATERIAL. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803042964 DE3042964A1 (en) | 1980-11-14 | 1980-11-14 | METHOD FOR ELIMINATING HETEROATOMES FROM BIOLOGICAL MATERIAL AND ORGANIC SEDIMENTS FOR CONVERTING TO SOLID AND LIQUID FUELS |
| DE3042964 | 1980-11-14 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0052334A2 EP0052334A2 (en) | 1982-05-26 |
| EP0052334A3 EP0052334A3 (en) | 1982-11-10 |
| EP0052334B1 EP0052334B1 (en) | 1986-07-16 |
| EP0052334B2 true EP0052334B2 (en) | 1994-05-11 |
Family
ID=6116767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81109604A Expired - Lifetime EP0052334B2 (en) | 1980-11-14 | 1981-11-10 | Process for the production of solid, liquid and gaseous combustibles from organic materials |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5114541A (en) |
| EP (1) | EP0052334B2 (en) |
| JP (1) | JPS57111380A (en) |
| AT (1) | ATE20759T1 (en) |
| CA (1) | CA1182062A (en) |
| DE (2) | DE3042964A1 (en) |
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| IT1171542B (en) * | 1981-09-21 | 1987-06-10 | Marco Vincenzo De | RUBBER TRANSFORMATION DEVICE PLASTIC MATERIALS AND URBAN WASTE WITH RECOVERY OF MIXTURES OF LIQUID HYDROCARBONS AND COAL AND COMBUSTION PROCEDURE |
| US5630854A (en) * | 1982-05-20 | 1997-05-20 | Battelle Memorial Institute | Method for catalytic destruction of organic materials |
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| DE3231203A1 (en) * | 1982-08-21 | 1984-02-23 | Rolf W. 2863 Ritterhude Lindemann | Process for the catalytic reforming of pyrolysates from solid fuels and organic wastes |
| DE3303360A1 (en) * | 1983-02-02 | 1984-08-09 | Hölter, Heinz, Dipl.-Ing., 4390 Gladbeck | Pyrolysis of waste with the addition of residual substances from the treatment of fossil fuels |
| CA1225062A (en) * | 1983-09-13 | 1987-08-04 | Trevor R. Bridle | Processes and apparatus for the conversion of sludges |
| DE3340971A1 (en) * | 1983-11-11 | 1985-05-23 | Johannes Dipl.-Ing. 6200 Wiesbaden Linneborn | Process for producing liquid combustible media consisting of at least two components |
| JPS60179489A (en) * | 1984-02-24 | 1985-09-13 | Ataka Kogyo Kk | Conversion of organic sludge to energy |
| JPS60179491A (en) * | 1984-02-24 | 1985-09-13 | Ataka Kogyo Kk | Conversion of organic sludge to energy |
| JPS60179490A (en) * | 1984-02-24 | 1985-09-13 | Ataka Kogyo Kk | Conversion of organic sludge to energy |
| DE3412536A1 (en) * | 1984-04-04 | 1985-10-31 | Fried. Krupp Gmbh, 4300 Essen | METHOD FOR PRODUCING HYDROCARBONS FROM CLEANING SLUDGE |
| GB8511587D0 (en) * | 1985-05-08 | 1985-06-12 | Shell Int Research | Producing hydrocarbon-containing liquids |
| EP0325662B1 (en) * | 1988-01-23 | 1993-03-31 | Alfred Bolz GmbH & Co. KG | Process and apparatus for the recuperation of fuels from organic material |
| DE3805302A1 (en) * | 1988-02-20 | 1989-08-31 | Theo Stenau | PLANT FOR OPERATING A LOW-TEMPERATURE CONVERSION PROCESS |
| DE3806732A1 (en) * | 1988-03-02 | 1989-11-09 | Andersen Kjeld | METHOD FOR GASIFICATION OF ORGANIC MATERIAL IN SYNTHESEGAS OR GASOFMY OR LIQUID HYDROCARBONS OR FOR REMOVING ORGANIC MATERIAL IN WASTEWATER |
| DE3815776A1 (en) * | 1988-05-07 | 1989-11-16 | Hein Ruck | Manufacture of charcoal and other products from renewable raw materials, in particular the banana plant |
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| JP7638523B2 (en) * | 2021-10-12 | 2025-03-04 | Ｇ－８ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｔｒａｄｉｎｇ 株式会社 | Method and apparatus for producing useful substances |
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| DE624843C (en) * | 1926-04-23 | 1936-01-30 | I G Farbenindustrie Akt Ges | Conversion of resins into hydrocarbons |
| US3962044A (en) * | 1972-07-05 | 1976-06-08 | The Regents Of The University Of California | Heat treating excreta and products thereof |
| JPS5839194B2 (en) * | 1975-04-14 | 1983-08-27 | カブシキガイシヤ エバラセイサクシヨ | Yuukibutsu no Netsubunkaihouhou Oyobi Netsubunkaisouchi |
| US4111800A (en) * | 1976-10-06 | 1978-09-05 | Harendza Harinxma Alfred J | Process for treating municipal solid waste and raw sewage sludge |
| JPS544903A (en) * | 1977-06-14 | 1979-01-16 | Agency Of Ind Science & Technol | Method of recovering oils from condensed water formed on thermal decomposition of municipal waste |
| US4300009A (en) * | 1978-12-28 | 1981-11-10 | Mobil Oil Corporation | Conversion of biological material to liquid fuels |
| US4298350A (en) * | 1979-09-17 | 1981-11-03 | Occidental Research Corporation | Method of embrittling waste |
-
1980
- 1980-11-14 DE DE19803042964 patent/DE3042964A1/en not_active Withdrawn
-
1981
- 1981-11-10 DE DE8181109604T patent/DE3174939D1/en not_active Expired
- 1981-11-10 AT AT81109604T patent/ATE20759T1/en not_active IP Right Cessation
- 1981-11-10 EP EP81109604A patent/EP0052334B2/en not_active Expired - Lifetime
- 1981-11-13 CA CA000390057A patent/CA1182062A/en not_active Expired
- 1981-11-13 JP JP56182970A patent/JPS57111380A/en active Granted
-
1991
- 1991-05-13 US US07/698,897 patent/US5114541A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATE20759T1 (en) | 1986-08-15 |
| CA1182062A (en) | 1985-02-05 |
| DE3174939D1 (en) | 1986-08-21 |
| EP0052334A3 (en) | 1982-11-10 |
| EP0052334A2 (en) | 1982-05-26 |
| DE3042964A1 (en) | 1982-07-01 |
| JPS57111380A (en) | 1982-07-10 |
| JPH0461037B2 (en) | 1992-09-29 |
| US5114541A (en) | 1992-05-19 |
| EP0052334B1 (en) | 1986-07-16 |
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