EP0277935B1 - Process for gasifying fuel with oxygen in a shaft furnace - Google Patents
Process for gasifying fuel with oxygen in a shaft furnace Download PDFInfo
- Publication number
- EP0277935B1 EP0277935B1 EP88890012A EP88890012A EP0277935B1 EP 0277935 B1 EP0277935 B1 EP 0277935B1 EP 88890012 A EP88890012 A EP 88890012A EP 88890012 A EP88890012 A EP 88890012A EP 0277935 B1 EP0277935 B1 EP 0277935B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- furnace
- gas
- oxygen
- product gas
- static bed
- 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.)
- Expired - Lifetime
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 28
- 239000001301 oxygen Substances 0.000 title claims description 28
- 229910052760 oxygen Inorganic materials 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 17
- 239000000446 fuel Substances 0.000 title claims description 10
- 239000007789 gas Substances 0.000 claims description 119
- 239000000463 material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 4
- 230000001419 dependent effect Effects 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims 7
- 239000000523 sample Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 14
- 150000002013 dioxins Chemical class 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 150000002240 furans Chemical class 0.000 description 6
- 238000002309 gasification Methods 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/06—Continuous processes
- C10J3/08—Continuous processes with ash-removal in liquid state
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/06—Continuous processes
- C10J3/16—Continuous processes simultaneously reacting oxygen and water with the carbonaceous material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
- C10K3/003—Reducing the tar content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
- C10J2200/152—Nozzles or lances for introducing gas, liquids or suspensions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
- C10J2200/158—Screws
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0959—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/12—Heating the gasifier
- C10J2300/1223—Heating the gasifier by burners
Definitions
- the invention relates to a process for the gasification of fuels with oxygen or oxygen-containing gases and, if appropriate, water vapor in a shaft-shaped furnace for receiving a solid charge, at the lower end of which there is a primary gas chamber charged with at least one burner, in which a fixed bed is formed by the charge. the charge material being gasified by the hot exhaust gases from the burner and the resulting gas being withdrawn from the furnace as product gas after passing through the fixed bed, and a device for carrying out the method.
- the product gas is largely free of tar in order to be able to use the product gas produced without further quenching for further use.
- it is not always possible to maintain sufficient tar freedom of the product gas e.g. not if the solid charge contains a high water content and / or a high volatile content.
- the object of the invention is to further develop the method described at the outset in such a way that the product gas is free from impurities which are harmful to the environment and restrict its possible use, such as tar or other higher hydrocarbons.
- This object is achieved in that an oxygen-containing gas is introduced into the space of the furnace located above the fixed bed and filled with product gas and a small part of the product gas is burned.
- the product gas temperature can be raised to approximately 1000 ° C. in a simple manner. Since generally higher hydrocarbons are completely destroyed at a temperature of approx. 1000 ° C and a residence time of approx. 2 s, the product gas is sufficiently tar-free.
- the temperature of the product gas is preferably measured in a product gas discharge line of the furnace and the oxygen-containing gas is fed in in an amount dependent on the measured temperature. This makes it possible to ensure the desired high temperature of the product gas with the smallest possible deviations by burning the minimum volume part of the product gas required for this.
- any dioxins or process products containing furan which may be formed are avoided by providing a further fixed bed behind the fixed bed of waste materials formed by the gas to be gasified, which bed is covered by the gas to be gasified in the direction of the primary gas chamber, through which the resulting gas passes through before being drawn off, and that the oxygen-containing gas is introduced above the further fixed bed and a small part of the product gas which has passed through the further fixed bed is burned.
- the gas supply line for the oxygen-containing gas preferably opens into the furnace with a plurality of openings, the openings being arranged distributed over the circumference of the furnace and preferably also at different height ranges of the furnace.
- FIGS. 1 and 2 each represent an embodiment of a shaft-shaped furnace in vertical section.
- the furnace 1 has a vertical upper section 2, preferably having a circular cross section, and a laterally angled lower section 3, which forms the primary gas chamber 4. Since the furnace 1 can be used without pressure or under pressure, its outer jacket 5 is designed accordingly, that is to say as a pressure vessel or as an ordinary gas-tight vessel.
- a container 8 having cooled walls 6, in particular walls 6 composed of tubes 7 through which coolant flows and constructed as a basket.
- the furnace 1 has a dividing wall 12 which extends downwards and is provided with internal cooling 11, the lower free edge 13 of which is approximately at the level of the connection 14 of the angled lower section 3 of the furnace 1 at its vertical Part 2 lies.
- the basket also has an inwardly projecting projection 15, which forms the upper boundary of the primary gas chamber 4 underneath.
- a feed line 16 for the charge material 17 to be gasified opens into the section 10 of the furnace, which feeds into the primary gas chamber 4 from a container 18 connected to this feed line 16 by means of a conveying device, such as a screw conveyor 19, to form a bulk material bed.
- a conveying device such as a screw conveyor 19
- the partition 12 is directed obliquely downwards, preferably at an angle of 30 to 45 ° to the primary gas chamber 4.
- the charge 17 to be gasified slides through the Supply line 16 via a sliding surface 21, which is cooled and provided with a refractory lining 22, up to the charging opening 23 opening into the primary gas chamber.
- the lower end 24 of the basket 8 is formed by an approximately horizontally directed support base 25, which also has internal cooling and whose free end, which projects into the primary gas chamber, is designed as a slag overflow weir 26.
- a trough 27 which is filled with coolant 28 for granulating the slag 30 which passes over the overflow weir 26 and exits the primary gas chamber 4 through a passage opening 29.
- a burner 37 opens into the primary gas chamber 4, into which feeds 32, 33, 34 for fuels, oxygen (or air) and possibly water vapor open.
- the basket 8 is coated on the inside up to the height of the first third of its vertical part - its partition on both sides - with refractory material 22.
- the department 9 of the basket 8 and the container 18 each have at their upper end closable feed openings 36, 37 for the goods to be charged 17 and 38, respectively, by means of a lock 35.
- the section 9 which is further away from the burner 31 is provided near its upper end with a discharge line 39 for the product gas formed and opens into the primary gas chamber by means of a passage 40.
- the section 10 which is closer to the burner 31 opens into the primary gas chamber with the passage 40 adjacent charging opening 23.
- a gas feed line 41 for an oxygen-containing gas opens above the fixed bed formed by the charge 38 by means of a plurality of orifices 42 which are distributed over the circumference of the furnace 1.
- a plurality of orifices 42 are preferably also located at different heights in the space 43 of the furnace 1 through which the product gas flows.
- the control unit 46 provided is operatively connected to a temperature sensor 47 provided in the product gas discharge line 39.
- the function of the device is as follows:
- charging material 38 in particular coke
- charging material 38 is poured into the compartment 9 located further away from the burner 31, whereby a bed of bulk material with a first bed surface 49 facing the burner 31 is formed in accordance with the angle of repose 48 of the coke.
- This bed surface 49 starts from the lower edge 13 of the partition.
- Charge gas 17 to be gasified is then introduced into the section 10 of the basket closer to the burner 31, which charge material 17 forms a further bed of bulk goods, which covers the first bed of bulk goods and has a free bed surface 50 facing the burner 31, against which the burner jet 51 is directed .
- the charge material 17 to be gasified which is introduced into the section 10 closer to the burner 31 can be of inferior quality, for example brown coal, highly volatile hard coal, old tires or BRAM (fuel from waste).
- This charge 17 is gasified after igniting the burner 31, the water vapor contained in the charge taking part in the gasification reactions and higher hydrocarbons being cracked from the pyrolysis and the resulting raw gas as a result of the arrangement of the Gas extraction line 39 is forced in compartment 9, which is further away from burner 31, to pass through the bulk bed of coke, for example, located behind it.
- the raw gas is filtered so that the product gas leaving the department 9 has a high purity.
- the thickness 52 of the bulk bed of the charge 17 to be gasified depends on the thickness 52 of the bulk bed of the charge 17 to be gasified and on the setting of the primary gasification whether the charge 38 lying behind the second bulk bed 38, e.g. the coke, also gasified or used only or primarily as a filter for the raw gas passing through.
- an oxygen-containing gas e.g. Air
- the control valve 44 regulating the supply of the oxygen-containing gas is used to precisely set a specific temperature of the product gas. This control valve 44 is opened more or less via the control unit 46 depending on the temperature of the product gas determined by the temperature sensor 47, as a result of which more or less oxygen-containing gas in reaches the space 43 and more or less parts by volume of the product gas are burned.
- Waste oil and air are fed to the burner 31 as fuel and burned. Waste tires are introduced as the charge material 17 to be gasified; the fixed bed behind that too gasifying charge material 17, which is covered by this in the direction of the primary gas chamber 4, is formed by coke.
- the withdrawn product gas occurs in the conventional process, ie without introducing an oxygen-containing gas into room 43, in an amount of 2000 Nm3 / h and at a temperature of 890 ° C. Its analysis is shown in Table I.
- Tarry components were found in the product gas, which are indications of a higher hydrocarbon content, including dioxins.
- the product gas is free of tarry components; it was passed through a gas purification plant comprising a cyclone, a filter, a condensate separator and an ethylene glycol scrubber for the analysis of dioxins, furans and higher hydrocarbons.
- the cyclone dust, the filter dust, the condensate and the ethylene glycol were then analyzed for dioxins, furans and higher hydrocarbons. It was found that less than 0.05 ppb; less than 0.07 ppb in filter dust; the condensate contains less than 0.9 ppt and the ethylene glycol contains less than 0.1 ppt dioxins and furans.
- the levels of higher hydrocarbons are consistently below 10 ppt.
- the product gas thus produced is practically free of dioxins, furan-containing process products and higher hydrocarbons.
- the furnace 1 has in its vertical shaft part only a single section 9, in which the charge 17 to be gasified is introduced.
- the furnace shown in FIG. 2 corresponds to that of FIG. 1.
- Coke or coal for example, can be introduced as the charge material 17 to be gasified.
- coal, oxygen and steam are converted to a product gas, initially no oxygen being fed into the space 43 above the fixed bed, but only oxygen being introduced via the burner 31.
- the analysis of the resulting product gas is shown in Table III.
- Tarry components were found in the product gas, which are indications of a higher hydrocarbon content, including dioxins.
- the product gas is produced in an amount of 1876 Nm3 / h at a temperature of 754 ° C.
- the product gas is free of tarry components; it was passed through a gas purification plant comprising a cyclone, a filter, a condensate separator and an ethylene glycol scrubber for the analysis of dioxins, furans and higher hydrocarbons.
- the cyclone dust, the filter dust, the condensate and the ethylene glycol were then analyzed for dioxins, furans and higher hydrocarbons. It was found that less than 0.05 ppb; less than 0.07 ppb in filter dust; the condensate contains less than 0.9 ppt and the ethylene glycol contains less than 0.1 ppt dioxins and furans.
- the levels of higher hydrocarbons are consistently below 10 ppt.
- the product gas thus obtained is practically free of dioxins and higher hydrocarbons.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Gasification And Melting Of Waste (AREA)
- Incineration Of Waste (AREA)
Description
Die Erfindung betrifft ein Verfahren zum Vergasen von Brennstoffen mit Sauerstoff oder sauerstoffhältigen Gasen und gegebenenfalls Wasserdampf in einem schachtförmigen Ofen zur Aufnahme eines festen Chargiergutes, an dessen unterem Ende eine mit mindestens einem Brenner beschickte Primärgaskammer vorgesehen ist, in der vom Chargiergut ein Festbett gebildet wird, wobei das Chargiergut von den heißen Abgasen des Brenners vergast wird und das entstehende Gas nach Durchtritt durch das Festbett aus dem Ofen als Produktgas abgezogen wird, sowie eine Vorrichtung zur Durchführung des Verfahrens.The invention relates to a process for the gasification of fuels with oxygen or oxygen-containing gases and, if appropriate, water vapor in a shaft-shaped furnace for receiving a solid charge, at the lower end of which there is a primary gas chamber charged with at least one burner, in which a fixed bed is formed by the charge. the charge material being gasified by the hot exhaust gases from the burner and the resulting gas being withdrawn from the furnace as product gas after passing through the fixed bed, and a device for carrying out the method.
Bei einem Verfahren dieser Art (bekannt beispielsweise aus der DE-C-458879) wird eine weitgehende Teerfreiheit des Produktgases angestrebt, um das erzeugte Produktgas ohne vorheriges Quenchen einer weiteren Nutzung zuführen zu können. Eine ausreichende Teerfreiheit des Produktgases ist jedoch nicht immer einzuhalten, z.B. dann nicht, wenn das feste Chargiergut einen hohen Wassergehalt und/oder einen hohen Gehalt an flüchtigen Bestandteilen enthält.In a method of this type (known, for example, from DE-C-458879), the product gas is largely free of tar in order to be able to use the product gas produced without further quenching for further use. However, it is not always possible to maintain sufficient tar freedom of the product gas, e.g. not if the solid charge contains a high water content and / or a high volatile content.
Die Erfindung stellt sich die Aufgabe, das eingangs beschriebene Verfahren dahingehend weiter zu entwickeln, daß das Produktgas frei ist von die Umwelt belastenden und seine Verwendungsmöglichkeit einschränkenden Verunreinigungen, wie Teer oder anderen höheren Kohlenwasserstoffen.The object of the invention is to further develop the method described at the outset in such a way that the product gas is free from impurities which are harmful to the environment and restrict its possible use, such as tar or other higher hydrocarbons.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß in den oberhalb des Festbettes befindlichen, vom Produktgas gefüllten Raum des Ofens ein sauerstoffhältiges Gas eingeleitet wird und ein geringer Teil des Produktgases verbrannt wird.This object is achieved in that an oxygen-containing gas is introduced into the space of the furnace located above the fixed bed and filled with product gas and a small part of the product gas is burned.
Durch Verbrennen eines geringen Teiles des Produktgases gelingt es in einfacher Weise, die Produktgastemperatur auf etwa 1000°C zu erhöhen. Da generell höhere Kohlenwasserstoffe bei einer Temperatur von ca. 1000°C und einer Verweilzeit von ca. 2 s vollständig zerstört werden, ist somit eine ausreichende Teerfreiheit des Produktgases gegeben.By burning a small part of the product gas, the product gas temperature can be raised to approximately 1000 ° C. in a simple manner. Since generally higher hydrocarbons are completely destroyed at a temperature of approx. 1000 ° C and a residence time of approx. 2 s, the product gas is sufficiently tar-free.
Zur Sicherstellung der für die Zerstörung der höheren Kohlenwasserstoffe notwendigen Temperatur des Produktgases auch bei wechselnden Betriebsbedingungen wird vorzugsweise in einer Produktgas-Abzugsleitung des Ofens die Temperatur des Produktgases gemessen und das sauerstoffhältige Gas in einer von der gemessenen Temperatur abhängigen Menge eingespeist. Hierdurch ist es möglich, die gewünschte hohe Temperatur des Produktgases mit möglichst geringen Abweichungen durch Verbrennen des hierzu geringst erforderlichen Volumsteiles des Produktgases zu gewährleisten.In order to ensure the temperature of the product gas necessary for the destruction of the higher hydrocarbons, even under changing operating conditions, the temperature of the product gas is preferably measured in a product gas discharge line of the furnace and the oxygen-containing gas is fed in in an amount dependent on the measured temperature. This makes it possible to ensure the desired high temperature of the product gas with the smallest possible deviations by burning the minimum volume part of the product gas required for this.
Aus der EP-A-0194252 ist es bekannt, als Chargiergut minderwertige Brennstoffe einzusetzen und diese zu einem hochwertigen Produktgas zu vergasen. Dabei möglicherweise gebildete Dioxine oder furanhaltige Prozeßprodukte werden gemäß einer bevorzugten Variante des erfindungsgemäßen Verfahrens dadurch vermieden, daß hinter dem vom zu vergasenden Chargiergut gebildeten Festbett aus Abfallstoffen ein weiteres Festbett, das vom zu vergasenden Chargiergut in Richtung zur Primärgaskammer überdeckt wird, vorgesehen ist, durch das das entstehende Gas vor dem Abziehen hindurchtritt, und daß das sauerstoffhältige Gas oberhalb des weiteren Festbettes eingeleitet und ein geringer Teil des durch das weitere Festbett hindurchgetretenen Produktgases verbrannt wird.From EP-A-0194252 it is known to use inferior fuels as the charge and to gasify them to a high-quality product gas. According to a preferred variant of the process according to the invention, any dioxins or process products containing furan which may be formed are avoided by providing a further fixed bed behind the fixed bed of waste materials formed by the gas to be gasified, which bed is covered by the gas to be gasified in the direction of the primary gas chamber, through which the resulting gas passes through before being drawn off, and that the oxygen-containing gas is introduced above the further fixed bed and a small part of the product gas which has passed through the further fixed bed is burned.
Durch Erhöhung der Produktgastemperatur auf etwa 1000°C ist nämlich die vollständige Zerstörung von Dioxinen und furanhaltigen Prozeßprodukten gewährleistet.By increasing the product gas temperature to around 1000 ° C the complete destruction of dioxins and furan-containing process products is guaranteed.
Zur Erhöhung der Produktgastemperatur auf etwa 1000°C genügt es, innerhalb des Ofens 0,5 bis 8 Vol.% des Produktgases zu verbrennen.To increase the product gas temperature to around 1000 ° C, it is sufficient to burn 0.5 to 8% by volume of the product gas inside the furnace.
Eine Vorrichtung zur Durchführung des erfindungsgemäßen Verfahrens mit einem Ofen zur Aufnahme eines festen Chargiergutes, einer Produktgasabzugsleitung am oberen Ende eines schachtförmigen Abteiles des Ofens, einer mit dem schachtförmigen Abteil des Ofens an dessen unterem Ende über einen Durchtritt in Verbindung stehenden Primärgaskammer, in der ein Brenner vorgesehen ist, der Zuführungen für Sauerstoff oder sauerstoffhältige Gase sowie für Brennstoffe und gegebenenfalls Wasserdampf aufweist, und mit einem am unteren Ende des Ofens angeordneten Stützboden mit Überlaufwehr zur Aufnahme von Schlacke, ist dadurch gekennzeichnet, daß im oberen Bereich des schachtförmigen Abteiles des Ofens mindestens eine Gaszuführungsleitung für ein sauerstoffhältiges Gas einmündet, in der ein Regelventil vorgesehen ist, welches über eine Steuereinheit mit einem in der Produktgasabzugsleitung vorgesehenen Temperaturmeßfühler in Verbindung steht.A device for carrying out the method according to the invention with a furnace for receiving a solid charge, a product gas discharge line at the upper end of a shaft-shaped compartment of the furnace, a primary gas chamber connected to the shaft-shaped compartment of the furnace at its lower end via a passage, in which a burner is provided, which has feeds for oxygen or oxygen-containing gases as well as for fuels and possibly water vapor, and with a support base arranged at the lower end of the furnace with an overflow weir for receiving slag, is characterized in that at least one in the upper region of the shaft-shaped compartment of the furnace Gas supply line for an oxygen-containing gas opens, in which a control valve is provided, which is connected via a control unit to a temperature sensor provided in the product gas discharge line.
Um die hohe Produktgastemperatur in etwa in dem gesamten oberhalb des Festbettes befindlichen Raum des Ofens sicherzustellen, mündet vorzugsweise die Gaszuführungsleitung für das sauerstoffhältige Gas mit mehreren Einmündungen in den Ofen, wobei die Einmündungen über den Umfang des Ofens verteilt angeordnet sind und vorzugsweise auch in unterschiedlichen Höhenbereichen des Ofens liegen.In order to ensure the high product gas temperature in approximately the entire space of the furnace located above the fixed bed, the gas supply line for the oxygen-containing gas preferably opens into the furnace with a plurality of openings, the openings being arranged distributed over the circumference of the furnace and preferably also at different height ranges of the furnace.
Die Erfindung ist nachfolgend anhand zweier Ausführungsbeispiele näher beschrieben, wobei die Fig. 1 und 2 jeweils eine Ausführungsform eines schachtförmigen Ofens im Vertikalschnitt darstellen.The invention is based on two Embodiments described in more detail, wherein FIGS. 1 and 2 each represent an embodiment of a shaft-shaped furnace in vertical section.
Der Ofen 1 weist einen vertikalen oberen, vorzugsweise einen Kreisquerschnitt aufweisenden Abschnitt 2 und einen seitlich abgewinkelten unteren Abschnitt 3, der die Primärgaskammer 4 bildet, auf. Da der Ofen 1 drucklos oder unter Druck einsetzbar ist, ist sein Außenmantel 5 dementsprechend, also als Druckbehälter oder als gewöhnlicher gasdichter Behälter ausgebildet.The furnace 1 has a vertical
Innerhalb des Außenmantels 5 ist ein gekühlte Wände 6 aufweisender, insbesondere aus kühlmitteldurchflossenen Rohren 7 zusammengesetzte Wände 6 aufweisender und als Korb ausgebildeter Behälter 8 vorgesehen. Zur Bildung zweier Abteilungen 9, 10 weist der Ofen 1 eine sich nach unten zu erstreckende, mit einer Innenkühlung 11 versehene Trennwand 12 auf, deren untere freie Kante 13 etwa in der Höhe des Anschlusses 14 des abgewinkelten unteren Abschnittes 3 des Ofens 1 an dessen vertikalem Teil 2 liegt. In dieser Höhe weist der Korb weiters einen nach innen ragenden Vorsprung 15 auf, welcher die obere Begrenzung der darunterliegenden Primärgaskammer 4 bildet.Provided within the
In die Abteilung 10 des Ofens mündet eine Zuleitung 16 für das zu vergasende Chargiergut 17, welches aus einem an diese Zuleitung 16 angeschlossenen Behälter 18 mittels einer Fördereinrichtung, wie einer Förderschnecke 19 zur Ausbildung eines Schüttgutbettes in die Primärgaskammer 4 einfließt. Die Trennwand 12 ist ausgehend von der brennerseitigen Wand 20 des Korbes schräg nach unten, vorzugsweise in einem Winkel von 30 bis 45° zur Primärgaskammer 4 hin gerichtet.A
Das zu vergasende Chargiergut 17 gleitet durch die Zuleitung 16 über eine Gleitfläche 21, die gekühlt und mit einer feuerfesten Auskleidung 22 versehen ist, bis zur in die Primärgaskammer mündenden Chargieröffnung 23.The
Das untere Ende 24 des Korbes 8 wird von einem etwa horizontal gerichteten Stützboden 25, der ebenfalls eine Innenkühlung aufweist und dessen freies, in die Primärgaskammer ragendes Ende als Schlackenüberlaufwehr 26 ausgebildet ist, gebildet. Unterhalb des Stützbodens 25 ist eine Wanne 27 vorgesehen, die mit Kühlmittel 28 zur Granulierung der über das Überlaufwehr 26 übertretenden und durch eine Durchtrittsöffnung 29 aus der Primärgaskammer 4 austretenden Schlacke 30 gefüllt ist.The
Oberhalb des Schlackenüberlaufwehrs 26 mündet in die Primärgaskammer 4 ein Brenner 37, in den Zuführungen 32, 33, 34 für Brennstoffe, Sauerstoff (oder Luft) und gegebenenfalls Wasserdampf münden.Above the
Der Korb 8 ist bis in die Höhe des ersten Drittels seines vertikalen Teiles innenseitig ― seine Trennwand beidseitig ― mit feuerfestem Material 22 beschichtet. Die Abteilung 9 des Korbes 8 und der Behälter 18 weisen an ihrem oberen Ende jeweils mittels einer Schleuse 35 verschließbare Zufuhröffnungen 36, 37 für das Chargiergut 17 bzw. 38 auf. Die vom Brenner 31 entfernter liegende Abteilung 9 ist nahe bei ihrem oberen Ende mit einer Abzugsleitung 39 für das entstehende Produktgas versehen und mündet in die Primärgaskammer mittels eines Durchtrittes 40. Die näher zum Brenner 31 liegende Abteilung 10 mündet in die Primärgaskammer mit der dem Durchtritt 40 benachbarten Chargieröffnung 23.The
Im oberen Drittel der Abteilung 9 mündet oberhalb des vom Chargiergut 38 gebildeten Festbettes eine Gaszuführungsleitung 41 für ein sauerstoffhältiges Gas mittels mehrerer, über den Umfang des Ofens 1 verteilt angeordneter Einmündungen 42. Vorzugsweise liegen mehrere Einmündungen 42 auch in unterschiedlichen Höhenbereichen des vom Produktgas durchströmten Raumes 43 des Ofens 1. In der Gaszuführungsleitung 41 ist ein Regelventil 44 vorgesehen, welches über eine in einer Steuerleitung 45 vorgesehene Steuereinheit 46 mit einem in der Produktgasabzugsleitung 39 vorgesehenen Temperaturmeßfühler 47 in Wirkverbindung steht.In the upper third of the
Die Funktion der Vorrichtung ist folgende:The function of the device is as follows:
Zunächst wird in die vom Brenner 31 entfernter liegende Abteilung 9 Chargiergut 38, insbesondere Koks, eingefüllt, wodurch sich entsprechend dem Schüttwinkel 48 des Kokses ein Schüttgutbett mit einer dem Brenner 31 zugewandten ersten Schüttungsfläche 49 bildet. Diese Schüttungsfläche 49 geht von der unteren Kante 13 der Trennwand aus.First of all, charging material 38, in particular coke, is poured into the
Anschließend wird zu vergasendes Chargiergut 17 in die näher zum Brenner 31 liegende Abteilung 10 des Korbes eingebracht, welches Chargiergut 17 ein weiteres Schüttgutbett bildet, welches das erste Schüttgutbett überdeckt und eine dem Brenner 31 zugewandte freie Schüttungsfläche 50 aufweist, gegen die der Brennerstrahl 51 gerichtet ist.
Das in die näher zum Brenner 31 liegende Abteilung 10 eingeführte zu vergasende Chargiergut 17 kann von minderer Qualität sein, beispielsweise Braunkohle, hochflüchtige Steinkohle, Altreifen oder BRAM (Brennstoff aus Müll). Dieses Chargiergut 17 wird nach Zünden des Brenners 31 vergast, wobei der im Chargiergut enthaltene Wasserdampf an den Vergasungsreaktionen teilnimmt und höhere Kohlenwasserstoffe aus der Pyrolyse gecrackt werden und das entstehende Rohgas infolge der Anordnung der Gasabzugsleitung 39 in der vom Brenner 31 entfernter liegenden Abteilung 9 gezwungen wird, durch das dahinterliegende Schüttgutbett aus beispielsweise Koks hindurchzutreten. Beim Durchtritt durch den Koks wird das Rohgas gefiltert, so daß das die Abteilung 9 verlassende Produktgas eine große Reinheit aufweist.The
Von der Dicke 52 des Schüttgutbettes des zu vergasenden Chargiergutes 17 und von der Einstellung der Primärvergasung hängt es ab, ob das hinter dem zweiten Schüttgutbett liegende Chargiergut 38, z.B. der Koks, ebenfalls vergast oder lediglich bzw. in erster Linie als Filter für das hindurchtretende Rohgas dient.It depends on the
Durch Einleitung eines sauerstoffhältigen Gases, wie z.B. Luft, durch die Gaszuführungsleitung in den oberhalb des Festbettes vorhandenen Raum 43 der Abteilung 9 gelingt es, die Temperatur des Produktgases zu erhöhen, wobei durch Verbrennen von jeweils 30 cm³ Rohgas die Temperatur des Produktgases um etwa 100°C erhöht wird. Zur genauen Einstellung einer bestimmten Temperatur des Produktgases dient das die Zufuhr des sauerstoffhältigen Gases regelnde Regelventil 44. Dieses Regelventil 44 wird je nach der von dem Temperaturmeßfühler 47 festgestellten Temperatur des Produktgases über die Steuereinheit 46 mehr oder weniger geöffnet, wodurch mehr oder weniger sauerstoffhältiges Gas in den Raum 43 gelangt und mehr oder weniger Volumsanteile des Produktgases verbrannt werden.By introducing an oxygen-containing gas, e.g. Air, through the gas supply line into the
Nachfolgend ist anhand eines Beispieles die Vergasung von minderwertigem Brennstoff erläutert:The gasification of low-quality fuel is explained below using an example:
Dem Brenner 31 wird als Brennstoff Altöl und Luft zugeführt und verbrannt. Als zu vergasendes Chargiergut 17 sind Altreifen eingebracht; das Festbett hinter dem zu vergasenden Chargiergut 17, das von diesem in Richtung zur Primärgaskammer 4 überdeckt ist, ist von Koks gebildet.Waste oil and air are fed to the
Das abgezogene Produktgas fällt beim herkömmlichen Verfahren, also ohne Einleitung eines sauerstoffhältigen Gases in den Raum 43, in einer Menge von 2000 Nm³/h und mit einer Temperatur von 890°C an. Seine Analyse ist in Tabelle I wiedergegeben.
Im Produktgas wurden teerige Komponenten gefunden, die Anzeichen für einen Gehalt an höheren Kohlenwasserstoffen einschließlich Dioxinen sind.Tarry components were found in the product gas, which are indications of a higher hydrocarbon content, including dioxins.
Zur Vermeidung von Dioxinen und furanhaltigen Prozeßprodukten werden dem in Tabelle I beschriebenen Produktgas innerhalb des Ofens 1 66,9 Nm³/h Luft durch die Gaszuführungsleitung 41 zugeführt. Hierdurch steigt die Rohgastemperatur auf ca. 1000°C. Die Menge des Produktgases beträgt 2055 Nm³/h. Die Analyse des Produktgases ist in Tabelle II wiedergegeben.
Das Produktgas ist frei von teerigen Komponenten; es wurde zwecks Analyse von Dioxinen, Furanen und höheren Kohlenwasserstoffen durch eine Gasreinigungsanlage, die einen Zyklon, ein Filter, einen Kondensatabscheider und einen Äthylenglycolwäscher aufwies, hindurchgeleitet. Anschließend wurden der Zyklonstaub, der Filterstaub, das Kondensat und das Äthylenglycol auf Dioxine, Furane und höhere Kohlenwasserstoffe analysiert. Es wurde gefunden, daß im Zyklonstaub weniger als 0,05 ppb; im Filterstaub weniger als 0,07 ppb; im Kondensat weniger als 0,9 ppt und im Äthylenglycol weniger als 0,1 ppt Dioxine und Furane vorhanden sind. Die Gehalte an höheren Kohlenwasserstoffen liegen durchwegs unter 10 ppt.The product gas is free of tarry components; it was passed through a gas purification plant comprising a cyclone, a filter, a condensate separator and an ethylene glycol scrubber for the analysis of dioxins, furans and higher hydrocarbons. The cyclone dust, the filter dust, the condensate and the ethylene glycol were then analyzed for dioxins, furans and higher hydrocarbons. It was found that less than 0.05 ppb; less than 0.07 ppb in filter dust; the condensate contains less than 0.9 ppt and the ethylene glycol contains less than 0.1 ppt dioxins and furans. The levels of higher hydrocarbons are consistently below 10 ppt.
Das so hergestellte Produktgas ist somit praktisch frei von Dioxinen, furanhältigen Prozeßprodukten und höheren Kohlenwasserstoffen.The product gas thus produced is practically free of dioxins, furan-containing process products and higher hydrocarbons.
Gemäß der in Fig. 2 dargestellten Ausführungsform weist der Ofen 1′ in seinem vertikalen Schachtteil lediglich eine einzige Abteilung 9 auf, in die das zu vergasende Chargiergut 17 eingebracht ist. In seinen sonstigen Merkmalen entspricht der in Fig. 2 dargestellte Ofen dem der Fig. 1. Als zu vergasendes Chargiergut 17 kann beispielsweise Koks oder Kohle eingebracht sein.According to the embodiment shown in Fig. 2, the furnace 1 'has in its vertical shaft part only a
Anhand des nachstehend beschriebenen Ausführungsbeispieles ist die Vergasung von Kohle erläutert:The gasification of coal is explained using the exemplary embodiment described below:
In dem Ofen 1′ werden Öl, Kohle, Sauerstoff und Dampf zu einem Produktgas umgesetzt, wobei zunächst in den Raum 43 oberhalb des Festbettes kein Sauerstoff zugeführt wird, sondern Sauerstoff lediglich über den Brenner 31 eingeleitet wird. Die Analyse des dabei entstehenden Produktgases ist in Tabelle III wiedergegeben.
Im Produktgas wurden teerige Komponenten gefunden, die Anzeichen für einen Gehalt an höheren Kohlenwasserstoffen einschließlich Dioxinen sind.Tarry components were found in the product gas, which are indications of a higher hydrocarbon content, including dioxins.
Das Produktgas fällt in einer Menge von 1876 Nm³/h mit einer Temperatur von 754°C an.The product gas is produced in an amount of 1876 Nm³ / h at a temperature of 754 ° C.
Um das Produktgas frei von Teer zu halten, wird oberhalb des Festbettes über die Gaszuführungsleitung 41 Luft in einer Menge von 186 Nm³/h eingeblasen, die Produktgastemperatur steigt hierdurch auf ca. 1000°C; das Produktgas fällt in einer Menge von 2025 Nm³/h an; seine Analyse ist in Tabelle IV wiedergegeben.
Das Produktgas ist frei von teerigen Komponenten; es wurde zwecks Analyse von Dioxinen, Furanen und höheren Kohlenwasserstoffen durch eine Gasreinigungsanlage, die einen Zyklon, ein Filter, einen Kondensatabscheider und einen Äthylenglycolwäscher aufwies, hindurchgeleitet. Anschließend wurden der Zyklonstaub, der Filterstaub, das Kondensat und das Äthylenglycol auf Dioxine, Furane und höhere Kohlenwasserstoffe analysiert. Es wurde gefunden, daß im Zyklonstaub weniger als 0,05 ppb; im Filterstaub weniger als 0,07 ppb; im Kondensat weniger als 0,9 ppt und im Äthylenglycol weniger als 0,1 ppt Dioxine und Furane vorhanden sind. Die Gehalte an höheren Kohlenwasserstoffen liegen durchwegs unter 10 ppt.The product gas is free of tarry components; it was passed through a gas purification plant comprising a cyclone, a filter, a condensate separator and an ethylene glycol scrubber for the analysis of dioxins, furans and higher hydrocarbons. The cyclone dust, the filter dust, the condensate and the ethylene glycol were then analyzed for dioxins, furans and higher hydrocarbons. It was found that less than 0.05 ppb; less than 0.07 ppb in filter dust; the condensate contains less than 0.9 ppt and the ethylene glycol contains less than 0.1 ppt dioxins and furans. The levels of higher hydrocarbons are consistently below 10 ppt.
Das so erhaltene Produktgas ist somit praktisch frei von Dioxinen und höheren Kohlenwasserstoffen.The product gas thus obtained is practically free of dioxins and higher hydrocarbons.
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT177/87 | 1987-01-29 | ||
AT0017787A AT388925B (en) | 1987-01-29 | 1987-01-29 | METHOD FOR GASIFYING FUELS WITH OXYGEN IN A SHAFT-SHAPED OVEN |
Publications (2)
Publication Number | Publication Date |
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EP0277935A1 EP0277935A1 (en) | 1988-08-10 |
EP0277935B1 true EP0277935B1 (en) | 1991-11-06 |
Family
ID=3483585
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP88890012A Expired - Lifetime EP0277935B1 (en) | 1987-01-29 | 1988-01-25 | Process for gasifying fuel with oxygen in a shaft furnace |
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US (1) | US4776285A (en) |
EP (1) | EP0277935B1 (en) |
JP (1) | JPH0631340B2 (en) |
AT (1) | AT388925B (en) |
DE (1) | DE3865979D1 (en) |
GR (1) | GR3003717T3 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT382388B (en) * | 1985-03-08 | 1987-02-25 | Voest Alpine Ag | DEVICE FOR THE GASIFICATION OF FUELS |
AT398121B (en) * | 1990-10-09 | 1994-09-26 | Voest Alpine Ind Anlagen | WASTE COMBUSTION METHOD |
AT397808B (en) * | 1992-04-22 | 1994-07-25 | Oemv Ag | METHOD FOR PRESSURE GASIFICATION OF ORGANIC SUBSTANCES, e.g. PLASTIC MIXTURES |
FR2734741B1 (en) * | 1995-05-31 | 1997-08-22 | Beaumartin Sa | PROCESS FOR RECYCLING TREATED WOOD AND INSTALLATION FOR IMPLEMENTING THE PROCESS |
FI112798B (en) * | 1999-07-28 | 2004-01-15 | Valtion Teknillinen | Process and plant for gasification of a carbonaceous fuel in a fixed bed gasifier |
DE19960882A1 (en) * | 1999-12-17 | 2001-06-21 | Kloeckner Humboldt Wedag | Reaction chamber used for thermal treatment of calorific waste material, e.g. car tires, wood waste and household waste has housing with inlet for waste material |
DE10007115C2 (en) * | 2000-02-17 | 2002-06-27 | Masch Und Stahlbau Gmbh Rolan | Process and reactor for gasifying and melting feedstocks with descending gas flow |
US6497187B2 (en) | 2001-03-16 | 2002-12-24 | Gas Technology Institute | Advanced NOX reduction for boilers |
DE102004016993B4 (en) * | 2004-04-02 | 2014-11-06 | Kbi International Ltd. | Thermal waste treatment reactor with a feed channel and thermal waste treatment process |
DE102007006979B4 (en) * | 2007-02-07 | 2009-09-24 | Technische Universität Bergakademie Freiberg | Slag bath gasification process |
US8580151B2 (en) * | 2009-12-18 | 2013-11-12 | Lummus Technology Inc. | Flux addition as a filter conditioner |
IT201600100814A1 (en) * | 2016-10-07 | 2018-04-07 | Processi Innovativi S R L | Process and plant for the production of waste syngas, preferably industrial or municipal waste and related associated products. |
Family Cites Families (14)
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DE458879C (en) * | 1922-02-12 | 1928-04-21 | Conrad Arnemann Dipl Ing | Process for gasifying and charring of queasy, pit-moist fuels, such as raw lignite |
GB336356A (en) * | 1929-08-22 | 1930-10-16 | Babcock & Wilcox Co | Improvements in relation to boiler furnaces |
DE897610C (en) * | 1951-04-17 | 1953-11-23 | Koppers Gmbh Heinrich | Process for generating gases |
US3820964A (en) * | 1972-05-30 | 1974-06-28 | Cons Natural Gas Svc | Refuse gasification process and apparatus |
JPS5318828A (en) * | 1976-08-04 | 1978-02-21 | Takuma Co Ltd | Combustible carbon combustion furnace |
US4323366A (en) * | 1978-12-29 | 1982-04-06 | Voest-Alpine Ag | Apparatus for the gasification of coal |
JPS5839464A (en) * | 1981-09-04 | 1983-03-08 | Silver Seiko Ltd | Printer |
DD212087A1 (en) * | 1982-12-09 | 1984-08-01 | Inst F Energetik Zentralst F R | PROCESS FOR OVERHEATING CHARGED RAW GASES |
DE3312863C2 (en) * | 1983-04-09 | 1986-12-04 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Combustion chamber for burning exhaust gases |
JPS59168657U (en) * | 1983-04-26 | 1984-11-12 | 豊島 透 | Gas generator hot air generator |
FR2551453B1 (en) * | 1983-08-31 | 1985-10-11 | Fives Cail Babcock | COAL GASIFIER IN HIGH-PRESSURE FLUIDIZED BED |
DE3335544A1 (en) * | 1983-09-28 | 1985-04-04 | Herwig 1000 Berlin Michel-Kim | REACTOR DEVICE FOR GENERATING GENERATOR GAS FROM COMBUSTIBLE WASTE PRODUCTS |
AT383139B (en) * | 1984-12-18 | 1987-05-25 | Waagner Biro Ag | METHOD FOR OVERHEATING THE GASIFICATION RAW GAS FROM BITUMINOUS FUELS AND DEVICE FOR CARRYING OUT THE METHOD |
AT382388B (en) * | 1985-03-08 | 1987-02-25 | Voest Alpine Ag | DEVICE FOR THE GASIFICATION OF FUELS |
-
1987
- 1987-01-29 AT AT0017787A patent/AT388925B/en not_active IP Right Cessation
-
1988
- 1988-01-15 US US07/144,506 patent/US4776285A/en not_active Expired - Fee Related
- 1988-01-22 JP JP63013483A patent/JPH0631340B2/en not_active Expired - Lifetime
- 1988-01-25 DE DE8888890012T patent/DE3865979D1/en not_active Expired - Lifetime
- 1988-01-25 EP EP88890012A patent/EP0277935B1/en not_active Expired - Lifetime
-
1992
- 1992-02-04 GR GR920400153T patent/GR3003717T3/el unknown
Also Published As
Publication number | Publication date |
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US4776285A (en) | 1988-10-11 |
AT388925B (en) | 1989-09-25 |
JPS63193989A (en) | 1988-08-11 |
DE3865979D1 (en) | 1991-12-12 |
ATA17787A (en) | 1989-02-15 |
JPH0631340B2 (en) | 1994-04-27 |
EP0277935A1 (en) | 1988-08-10 |
GR3003717T3 (en) | 1993-03-16 |
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