EP2828363B1 - Pyrolysis apparatus and process - Google Patents

Pyrolysis apparatus and process Download PDF

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Publication number
EP2828363B1
EP2828363B1 EP13710380.0A EP13710380A EP2828363B1 EP 2828363 B1 EP2828363 B1 EP 2828363B1 EP 13710380 A EP13710380 A EP 13710380A EP 2828363 B1 EP2828363 B1 EP 2828363B1
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EP
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Prior art keywords
pyrolysis
process material
reaction chamber
gas
metal bath
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German (de)
French (fr)
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EP2828363A1 (en
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Horst Müller
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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
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/14—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot liquids, e.g. molten metals
    • 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
    • C10K3/02—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 catalytic treatment
    • C10K3/04—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 catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]

Definitions

  • the present invention relates to a pyrolysis device according to the preamble of claim 1.
  • the pyrolytic transformation proceeds through different and complex chemical reactions, which are not all clarified in detail.
  • wood gas, charcoal, high molecular weight aromatic hydrocarbons such as tars and minerals are produced in classic wood gasifiers wood vinegar.
  • the latter is a mixture of water, phenols, creosote, acetic acid, methanol, acetone, propionic acid, methyl acetate and other compounds.
  • the resulting tars are particularly disadvantageous for the known pyrolysis devices, as tears condense at temperatures below about 200 ° C and enforce piping, or occupy surfaces of valve seats, bearings and the like and thus lead to malfunction.
  • a device for pyrolytic degradation of industrial or household waste in which these in one in a Reaction vessel befindliches molten metal, in particular pig iron, are immersed continuously, using a dip tube is used.
  • the waste entry into the dip tube by means of a laterally arranged at this above the reaction chamber screw conveyor, wherein between the screw end and dip tube a shut-off device is provided in the form of a ball check valve, which is traversed by the waste.
  • a movable piston may be provided which presses the conveyed garbage into the melt. The gas is removed both above the melt and through slots in the dip tube above the reaction vessel.
  • the device task is solved in that the process material in the operating state by press cake forming the shut-off device, wherein the conveying direction of the screw conveyor is directed against the effective direction of the removal and wherein a sensor is arranged in the conveying direction in front of the screw conveyor, wherein the removal device is designed as a milling cutter.
  • the invention understands under process material carbonaceous material, such as wood, wood materials, straw, by-products and residues of agriculture and forestry and woodworking crafts, but also plastics, car tires, electronic waste, sewage sludge or Flussaushub (silt) with a correspondingly high organic content.
  • the invention is understood by Melt metal all molten metals that are liquid in a range above the tar formation temperature. Especially she understands a tin melt underneath. Metallic tin is nontoxic in large quantities per se, the toxicity of simple tin compounds and tin salts is low, so that it is a very reliable metal. The most extensive exclusion of air ensures that undiluted product gas is produced, which has a correspondingly high calorific value.
  • the invention proposes that the entry device has at least one in the near-bottom region of the reaction chamber endendendes immersion tube, which ends under operating conditions in the molten metal and through which the Prozeßguteintrag is successful, wherein the dip tube has no moving parts in the region of the reaction chamber.
  • immersion tube the invention means any hollow body which leads below the surface of the metal bath contained in the operating state in the reaction chamber. Due to the low-level introduction of the process material particularly long contact times between the pyrolysis and the metal bath are made possible, so that results in correspondingly high conversion rates of the process material. A particularly long service life of the device is made possible by the immersion tube having no moving parts in the region of the reaction chamber.
  • a simple, for example made of a ceramic, dip tube is sufficient to register the process material gravity-driven. There are no screws, pistons or the like required, the force of gravity is always reliable. Since it can be dispensed with the provision of feed forces and devices within the reaction chamber, the apparatus construction is further simplified, there must be no hydraulics, compressed air lines, motor drives or the like provided, protective measures for these parts can therefore also be omitted.
  • the entry device has a metering device for metering the process material into the dip tube.
  • a metering device for metering the process material into the dip tube.
  • a metering device according to the invention has a screw conveyor and a removal device, wherein the removal device is designed as a milling cutter.
  • Non-inventive metering devices would be, for example, a membrane, a folding device, a rotary valve with sufficiently large Zellkompartimenten or a Kollerrad with or without ring die, as it is known from Pelletiermaschienen. Generally, rotary, compartmented feeders are preferred.
  • the rotor of the rotary valve with a cutting edge, so as to avoid blocking of the possibly coarse-grained process material.
  • the supply of process material is either perpendicular to the axis of rotation of the rotor or tangential thereto. In the latter case, the process material is pushed back by the scraper or the cutting edge of the rotor blade something in the inlet to prevent jamming of the clippings between feeder and housing advantageous.
  • the entry device has a gastight closing shut-off device, so that it is ensured with great advantage that pressure built up in the reaction chamber can not relax via the metering device into the entry device.
  • This shut-off device advantageously also ensures that process material is provided with volume buffering, which improves the uniform operation of the device, since there is always sufficient input material. Due to the buffering and type of entry, it is simultaneously prevented that an excess of process material can reach the metering device and block it.
  • the design effort is further simplified in that the process material itself the Shut-off is forming, as a result of this very few components must be arranged in the feed. This is inventively possible by the process material is compressed in a supply line to the dip tube gland.
  • the invention enables a particularly robust and trouble-free working metering device.
  • the pelletizing of the process material prior to its use can be dispensed with.
  • Gas-tightness is understood according to the invention to mean a tightness which is sufficient to maintain the required operating pressure in the immersion tube. Absolute gas tightness is not required, albeit desirable, as it avoids, among other things, product losses.
  • the conveying direction of the screw conveyor is directed against the effective direction of the removal device, wherein a sensor is arranged in the conveying direction in front of the screw conveyor.
  • the driven auger conveys the process material in the direction of the dip tube. You can not only promote it according to the invention but also crush and / or compress, if this is desired or required process material. According to the invention would also be to arrange the screw conveyor in a separate flange, so that it can be easily replaced with changing process material against a better adapted to the new process material.
  • the type of screw conveyor is the invention first nachranging, the expert will choose among other things speed, inner and outer diameter, pitch and flight depth and wave number accordingly and the Adjust the filling level of the screw.
  • the promotion takes place against the resistance of the removal device, which in turn counteracts the conveying direction of the process material.
  • the removal device is inventively designed as a milling cutter.
  • the device has for this purpose a corresponding control with data and active lines, wherein the controller can be automated accordingly.
  • the reaction chamber is designed to be temperature-controlled, in particular has a heating device and / or a thermal insulation. This is needed to keep the metal bath at its working temperature to achieve or to achieve and maintain another, especially higher, working temperature.
  • the device is able to drive temperature programs.
  • the product discharge has a product gas aftertreatment device, in particular one or more dust collectors, gas coolers, condensate separators and / or chemical gas cleaning, it is advantageously ensured that only highly pure product gas leaves the device according to the invention, and secondly it ensures that solid products are separated off and can be made available for further use.
  • a chemical gas purification will always be desirable if problematic process material, in particular highly sulfur-containing or chlorine-containing biomass is used.
  • the entry of the process material into the tin bath by gravity takes place and / or the Pyrolyseguteintragsrate is in equilibrium with the pyrolysis of the pyrolysis and / or in which the metal bath boiling stones, in particular silicate boiling stones, preferably quartz sediments.
  • the last measure ensures that no larger bubbles of gas are formed, which eruptions break through the surface of the tin bath and tear tin droplets with it.
  • the product gas obtained is treated and recycled, in particular subjected to a hydrogen-producing catalytic water gas shift reaction.
  • material recycling is also possible with great advantage. This is because high-purity product gas is produced virtually dust-free.
  • moist biomass or moist pyrolysis can be used, so that the time required to carry out the shift reaction amount of water is already present in the system.
  • it may also be provided to additionally meter in water if necessary. Depending on the moisture of the biomass used, this water gas shift reaction may also already take place at least partially in the reaction chamber, in particular on coke residues which are present in the glowing state on the surface of the tin bath.
  • Fig. 1 shows a pyrolysis invention 1_with not inventive shut-off device. This can be connected on the product gas side with smaller combined heat and power plants in the order of 10 to 50 kW el , which burn the fuel gas generated in the pyrolysis 1. It can also be connected according to the invention with other units for power and / or heat generation, for example micro gas turbines, fuel cells or Stirling engines. Product entry side, the pyrolysis is connected to a Pyrolysegutvorrats inherent in Fig. 1 is shown schematically.
  • the aforementioned pyrolysis or process goods are kept in stock for continuous introduction, such as wood, wood pellets, wood materials, sewage sludge, or general biomass, especially biological by-products and residues such as straw, sunflower furs, energy crop residues. Due to the size of the plant a small amount of stock is sufficient.
  • the device of the invention is particularly interesting for the genesis near disposal of such biomass, for example, on the premises of a sawmill, carpentry or joinery or a garden or landscaping operation. Should with the Inventive apparatus metal recovery process are performed, the process material or Pyrolysegutvorrats constituer 17 is adjusted accordingly.
  • the process of the invention results in such process material that the metals contained in it dissolve in the tin bath, from which they are recovered.
  • pyrolysis are plastics, more or less processed electronic waste or the like.
  • the pyrolysis passes via pipes to the entry device 3.
  • This consists in this embodiment of the invention of a downpipe, which is gas-tight in the direction of the pipeline to Pyrolysegutvorratsmicer 17.
  • This gas-tight closure is achieved here by two pneumatic peristaltic pinch valves 18, 19 arranged at a distance from one another in the feed direction, which define between them an intermediate store 20 for pyrolysis goods and which are not in accordance with the invention.
  • the pyrolysis reaches after the second Schlauchquetschventil 19 to a metering device 7.
  • the dip tube 6 is in Fig. 2 described in more detail. It ends in the region of the bottom surface 21 of the reaction chamber 2 with an outlet surface oriented approximately parallel to the bottom surface 21.
  • the reaction chamber 2 has a thermal insulation 10 and a heater 9, both are outlined only on one side. According to the invention, the heating device 9 can also be arranged inside the reaction chamber 2, be integrated in the walls thereof or be on the outer wall side, as outlined.
  • the nature of the heater 9 is only relevant insofar as they are temperatures of at least 800 ° C in the reaction chamber. 2 produce and must be able to ensure long-term. However, the operating temperature of the reaction chamber 2 according to the invention may also be 900 ° C or significantly higher.
  • the fuel gas released from the pyrolysis gas collects in a gas space above the tin melt, from where it can be removed actively or passively. This gas space is completely filled by fuel gas, it contains no air fractions. This ensures a high calorific value of the generated heating gas. Above the surface of the tin bath in the region of the cover surface 22 of the reaction space 2, a product gas discharge line 4 is arranged.
  • the product gas discharge 4 has several components. Pipe sections lead from the reaction chamber to a dust collector 12. This serves to separate entrained coke and to reduce the dust load of the product gas. In this also a condensate 14 may be arranged. Depending on the pyrolysis, it may be necessary to provide a chemical gas cleaning 15, for example, to deposit sulfur and sulfur compounds, chlorine and chlorine compounds or nitrogen. This will always be the case when "difficult" biomass such as straw or the like is used. If necessary, a gas cooler 13 may be provided.
  • the product gas thus produced can be subjected not only to thermal but also to material recycling. Since the product gas is highly CO-containing, CO 2 and H 2 can be generated via suitable robust catalysts. In this case, it is particularly advantageous that moist biomass according to the invention can also be used which can provide the water required for this reaction. With great advantage, a drying step of the biomass stop before pyrolysis. This improves the overall energy balance of the device and the method according to the invention.
  • Fig. 2 shows a detail of the dip tube 6. This protrudes more or less perpendicularly from above into the cylindrical reaction chamber 2 and ends slightly above the bottom surface 21.
  • This dip tube 6 may be part of the reaction chamber 2 or a separate, inserted into it component. In any case, its functionality assigns it a membership in the entry device 3.
  • the dip tube 6 ends in the operating state of the device well below the surface of the metal bath. It contains no mechanical parts and can consist of a temperature-resistant ceramic.
  • the device When starting the device, it is first filled with molten metal to the level of the metal bath. From the metering device 7 conveyed carbonaceous Prozeßgut falls gravity driven on the melt and is pyrolyzed there to gases and coke. The resulting gases generate a pressure in the dip tube 6, which gradually displaces over time the liquid tin present there into the reaction chamber 2. In this embodiment, it is therefore particularly important that the gas pressure building up can not escape or only to a slight extent up in the rest of the entry device 3.
  • the spaced-apart Schlauchquetschventile 18, 19 provide together with the metering device 7 for the required level of gas tightness by the pressure in steps falls upwards, as if in the manner of a lock staircase to overcome a large difference in height.
  • the particle size of the coke is so small that it can be entrained by the emerging from the reaction chamber 2 gas flow. It has been found that there is no accumulation of coke in the reaction chamber 2. As described, it is inventively extremely advantageous if the rate of delivery of the process material corresponds to its conversion rate. In this case, an easy-to-control, stable, static system with constant revenues is formed.
  • the bottom end of the dip tube 6 may be simply cylindrical or have a widened, for example bell-like widened edge. This may possibly also be provided with a sieve-like perforated pipe wall in an end-side section. The invention is especially important that the end of the dip tube 6 ends well below the surface of the tin bath, so that the process material must pass through the entire metal bath.
  • more than one dip tube 6 may be provided per reaction space 2, for example two or three, in order to allow a more homogeneous entry.
  • An as far as possible vertically extending dip tube 6 is preferred, since in this case the process material gravity-driven can fall freely from the metering device 7 on the tin surface.
  • the passage surface of the dip tube 6 and the bottom surface of the reaction space 2 form an angle between them and are not parallel to each other. Such an angle results, for example, in a skewed arrangement of the pipe, or an L- or U-shaped bent pipe end. Regardless of what the final geometry of the dip tube 6 looks like, it must be ensured that no process material layer can build up on the tin surface, blocks the trailing material and interrupts the gasification and pyrolysis process via voids formation.
  • Fig. 3 again shows schematically and not to scale an inventive embodiment of the entry device 3.
  • Reaction chamber 2, dip tube 6, tin bath, gas discharge and process material within the reaction chamber are as in the previous figures and only schematically indicated.
  • the dip tube 6 kinks at its upper end in approximately horizontal and goes into the actual metering device.
  • This has a schematic hopper, which symbolizes any kind of supply of process material 4.
  • a sensor 25 is arranged, the data and is effectively connected to a system control, not shown.
  • the sensor is arranged so that it can measure from the device leaking gas, such as CO 2 , undisturbed by outside air.
  • the process material 4 trickles or falls into one or is transported to a screw conveyor 23, which in turn has a hollow screw shaft.
  • the screw conveyor 23 promotes toward the dip tube 6.
  • the drives for screw conveyor and removal device 24 are not shown.
  • the worm shaft is penetrated by a shaft of the removal device 24, here a cutter.
  • the cutter is axially displaceable and rotationally driven. Without drive, it forms a resistance to the conveyed in his direction process material 4 that forms a press cake or plug 26 before him.
  • process material 4 forms a press cake or plug 26 before him.
  • a press cake of different density and axial length is generated.
  • very different process items 4 can be processed so that the press cake 26 is approximately gas-tight and seals the interior of the device according to the invention from the outside world.
  • the process material entry into the melt is achieved by the cutter 24 working for a certain time.
  • Fig. 3 also shows a second heater assembly 9 according to the invention, namely three at the same angular distance from each other and concentrically arranged around the dip tube 6 and spatially fixed at their ends heating tubes that are running in the middle of the melt in the operating state, so that this turbulent melt is heated particularly effectively.
  • These heating tubes are preferably made of the same material as the dip tube 6 and may for example be electrically or heated gas.
  • the inventive method operates at very high operating temperatures, so that there is virtually no formation of tars.
  • the tar formation rate is below 10 g / Nm 3 .
  • the waiver according to the invention of moving mechanical parts in the region of the reaction chamber 2 reduces the technical sources of interference. Hot spots or short circuit currents will be the same avoided, such as the need for thermally and metallurgically resistant bearings or the like. Even smaller plant sizes can work economically, the device according to the invention and the method are easy to automate and user-friendly.
  • the tin used only has a vapor pressure of 1 * 10 -4 mbar, which makes it extremely suitable and has a long service life.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Processing Of Solid Wastes (AREA)

Description

Die vorliegende Erfindung betrifft eine Pyrolysevorrichtung gemäß dem Oberbegriff von Anspruch 1.The present invention relates to a pyrolysis device according to the preamble of claim 1.

Es ist bekannt, mittels Pyrolyse aus höhermolekularem Prozeßgut niedermolekulare Produkte zu gewinnen, beispielsweise aus Holz Heizgase zu erzeugen. Ebenfalls bekannt ist, aus höhermolekularem Prozeßgut wie Altreifen, Kunststoffen oder der gleichen flüssige Kohlenwasserstoffe wie Öle zu gewinnen.It is known to obtain by means of pyrolysis of relatively high molecular weight process material low molecular weight products, for example, to produce from wood fuel gases. It is also known to win from higher molecular process material such as scrap tires, plastics or the same liquid hydrocarbons such as oils.

Die pyrolytische Umwandlung läuft dabei über unterschiedliche und komplexe chemische Reaktionen ab, die im Einzelnen nicht alle aufgeklärt sind. Beispielsweise entstehen aus Holz, das Zellulose, Lignin, Hemicellulose, Fette, Stärke, Zucker, Eiweiße, Phenole, Wachse, Pektine, Gerbstoffe, Sterine, Harze, Terpene und Mineralstoffe enthält, bei klassischen Holzvergasungsvorrichtungen Holzgas, Holzkohle, hochmolekulare aromatische Kohlenwasserstoffe wie Teere und Holzessig. Letzterer ist ein Gemisch aus Wasser, Phenolen, Kreosot, Essigsäure, Methanol, Aceton, Propionsäure, Methylacetat und weiteren Verbindungen. Die entstehenden Teere sind besonders nachteilig für die bekannten Pyrolysevorrichtungen, da Teere bei Temperaturen unterhalb von etwa 200°C auskondensieren und Rohrleitungen zusetzen, bzw. Oberflächen von Ventilsitzen, Lagern und dergleichen belegen und so zu Betriebsstörungen führen.The pyrolytic transformation proceeds through different and complex chemical reactions, which are not all clarified in detail. For example, in wood containing cellulose, lignin, hemicellulose, fats, starch, sugars, egg whites, phenols, waxes, pectins, tannins, sterols, resins, terpenes and minerals, wood gas, charcoal, high molecular weight aromatic hydrocarbons such as tars and minerals are produced in classic wood gasifiers wood vinegar. The latter is a mixture of water, phenols, creosote, acetic acid, methanol, acetone, propionic acid, methyl acetate and other compounds. The resulting tars are particularly disadvantageous for the known pyrolysis devices, as tears condense at temperatures below about 200 ° C and enforce piping, or occupy surfaces of valve seats, bearings and the like and thus lead to malfunction.

Vorrichtungen und Verfahren zur teerarmen Erzeugung von Produkten sind daher seit langem ein Ziel der Entwicklung.Devices and methods for tar-low production of products have therefore long been an objective of development.

Aus der DE 10 2005 053 526 A1 ist eine bei hohen Temperaturen annähernd luftfrei arbeitende Pyrolysevorrichtung bekannt, die im Betriebszustand ein Zinnbad enthält, durch das unter Luftausschluß mittels einer Förderschnecke getrocknetes Holz geführt wird. Der Eintrag erfolgt dabei so, daß das Pyrolysegut unter die Oberfläche des Zinnbades in dasselbe eingetragen wird, so daß es das Zinnbad durchdringen muß. Der Luftausschluß bewirkt einen hohen Brennwert des Produktgases, da kein inerter Stickstoff in hohen Volumenanteilen verdünnend wirken kann. Zinn hat den Vorteil eines sehr großen Temperaturbereiches, in dem es in flüssiger Phase existieren kann: Im Phasendiagramm reicht dieser Bereich vom niedrigen Schmelzpunkt bei 232°C bis zum hohen Siedepunkt bei 2.602°C. Hierdurch können ganz unterschiedliche Pyrolysetemperaturen realisiert werden. Vorteilhaft ist weiterhin der in diesem Bereich sehr geringe Dampfdruck, so daß kaum Zinn aus der Schmelze über das Produktgas mitgerissen und aus der Reaktionskammer entweichen kann. Dieser Stand der Technik erreicht so relativ lange Kontaktzeiten zwischen Pyrolysegut und Zinnbad und somit ein teerarmes, heizwertreiches Produktgas. Nachteilig an diesem Stand der Technik ist das Erfordernis einer die Reaktionskammer durchdringenden Förderschnecke für den Materialeintrag in das Zinnbad, bzw. unter die Oberfläche des Zinnbades.From the DE 10 2005 053 526 A1 is an approximately air-free at high temperatures pyrolysis known, which contains a tin bath in the operating condition, by the exclusion of air by means of a screw conveyor dried wood is performed. The entry takes place so that the pyrolysis is entered under the surface of the tin bath in the same, so that it must penetrate the tin bath. The exclusion of air causes a high calorific value of the product gas, since no inert nitrogen can dilute in high volumes. Tin has the advantage of a very large temperature range in which it can exist in the liquid phase: In the phase diagram, this range extends from the low melting point at 232 ° C to the high boiling point at 2,602 ° C. As a result, very different pyrolysis temperatures can be realized. A further advantage is the very low vapor pressure in this area, so that tin can hardly be entrained from the melt via the product gas and can escape from the reaction chamber. This prior art thus achieves relatively long contact times between the pyrolysis product and the tin bath and thus a tarry, high-calorific product gas. A disadvantage of this prior art is the requirement of a feed screw penetrating the reaction chamber for the material to be introduced into the tin bath or under the surface of the tin bath.

Aus der US 5,085,738 A sind eine Vorrichtung und ein Verfahren bekannt, bei dem geschredderte Altreifen mittels eines Kolbens in ein absteigendes Rohr gepresst werden, an dessen unterem Ende sich ein Übergangsbereich zu einem wieder aufsteigenden Reaktionsrohr befindet. Das aufsteigende Reaktionsrohr enthält ein luftabgeschlossenes Bleibad, durch das das Pyrolysegut aufgrund seiner geringeren Dichte aufsteigend hindurchtreten soll. Beide Rohre sind dabei so angeordnet, daß das Bleibad nicht bis zum Kolben ansteigen kann, wenn kein Pyrolysegut eingefördert wird. Nachteilig an diesem Stand der Technik ist die umständliche und unsichere Pyrolysegutzufuhr.From the US 5,085,738 A For example, a device and a method are known in which shredded old tires are pressed by means of a piston into a descending tube, at whose lower end there is a transition region to a resurgent reaction tube. The ascending reaction tube contains an air-sealed lead bath through which the pyrolysis is to pass in ascending order due to its lower density. Both tubes are arranged so that the lead bath can not rise to the piston when no pyrolysis is conveyed. A disadvantage of this prior art is the cumbersome and unsafe Pyrolysegutzufuhr.

Aus der DE 2 304 369 ist eine Vorrichtung zum pyrolytischen Abbau von Industrie- oder Haushaltsmüll bekannt, bei dem diese in eine in einem Reaktionsgefäß befindliche Metallschmelze, insbesondere Roheisen, kontinuierlich eingetaucht werden, wozu ein Tauchrohr verwendet wird. Der Abfalleintrag in das Tauchrohr erfolgt mittels eines seitlich an diesem oberhalb der Reaktionskammer angeordneten Schneckenförderers, wobei zwischen Schneckenende und Tauchrohr ein Absperrorgan in Form eines Kugelrückschlagventils vorgesehen ist, welches von dem Abfall durchwandert wird. Im Tauchrohr kann ein beweglicher Kolben vorgesehen sein, der den eingeförderten Müll in die Schmelze drückt. Die Gasentnahme erfolgt sowohl oberhalb der Schmelze als auch durch Schlitze im Tauchrohr oberhalb des Reaktionsgefäßes. Nachteilig an diesem Stand der Technik ist die umständliche und unsichere Pyrolysegutzufuhr.From the DE 2 304 369 a device for pyrolytic degradation of industrial or household waste is known, in which these in one in a Reaction vessel befindliches molten metal, in particular pig iron, are immersed continuously, using a dip tube is used. The waste entry into the dip tube by means of a laterally arranged at this above the reaction chamber screw conveyor, wherein between the screw end and dip tube a shut-off device is provided in the form of a ball check valve, which is traversed by the waste. In the dip tube, a movable piston may be provided which presses the conveyed garbage into the melt. The gas is removed both above the melt and through slots in the dip tube above the reaction vessel. A disadvantage of this prior art is the cumbersome and unsafe Pyrolysegutzufuhr.

Es ist daher Aufgabe der vorliegenden Erfindung, eine Pyrolysevorrichtung anzugeben, mit der konstruktiv unaufwendig und betriebssicher ein Heizgas hohen Brennwertes erzeugbar ist. Es ist weiter Aufgabe der Erfindung, ein entsprechendes Verfahren anzugeben.It is therefore an object of the present invention to provide a pyrolysis, with the structurally inexpensive and reliable, a fuel gas high fuel value can be generated. It is a further object of the invention to provide a corresponding method.

Die Vorrichtungsaufgabe wird dadurch gelöst, dass das Prozeßgut im Betriebszustand durch Presskuchenbildung die Absperrvorrichtung bildend ist, wobei die Förderrichtung der Förderschnecke gegen die Wirkrichtung der Abtragsvorrichtung gerichtet ist und wobei ein Sensor in Förderrichtung vor der Förderschnecke angeordnet ist, wobei die Abtragsvorrichtung als Fräser ausgebildet ist.The device task is solved in that the process material in the operating state by press cake forming the shut-off device, wherein the conveying direction of the screw conveyor is directed against the effective direction of the removal and wherein a sensor is arranged in the conveying direction in front of the screw conveyor, wherein the removal device is designed as a milling cutter.

Zunächst einmal versteht die Erfindung unter Prozeßgut kohlenstoffhaltiges Material, wie unter anderem Holz, Holzwerkstoffe, Stroh, Neben- und Reststoffe der Land- und Forstwirtschaft sowie des holzverarbeitenden Handwerks, aber auch Kunststoffe, Autoreifen, Elektronikschrott, Klärschlamm oder Flußaushub (Schlick) mit entsprechend hohem Organikanteil. Die Erfindung versteht unter Metallschmelze alle Metallschmelzen, die in einem Bereich flüssig sind, der oberhalb der Teerbildungstemperatur liegt. Ganz besonders versteht sie eine Zinnschmelze darunter. Metallisches Zinn ist auch in größeren Mengen an sich ungiftig, die Giftwirkung einfacher Zinnverbindungen und Zinnsalze ist gering, so daß es ein sehr betriebssicheres Metall darstellt. Durch den weitestgehenden Luftausschluß ist sichergestellt, daß unverdünntes Produktgas erzeugt wird, das einen entsprechend hohen Heizwert aufweist. Mit besonderem Vorteil schlägt die Erfindung vor, dass die Eintragsvorrichtung mindestens ein im bodennahen Bereich der Reaktionskammer offenendendes Tauchrohr aufweist, welches unter Betriebsbedingungen in der Metallschmelze endet und durch das der Prozeßguteintrag erfolgend ist, wobei das Tauchrohr im Bereich der Reaktionskammer keine beweglichen Teile aufweist. Unter Tauchrohr versteht die Erfindung jeglichen Hohlkörper, der unter die Oberfläche des im Betriebszustand in der Reaktionskammer enthaltenen Metallbades führt. Durch die bodennahe Einbringung des Prozeßgutes werden besonders lange Kontaktzeiten zwischen dem Pyrolysegut und dem Metallbad ermöglicht, so dass sich entsprechend hohe Umsatzraten des Prozeßgutes ergeben. Eine besonders lange Standzeit der Vorrichtung wird ermöglicht, indem das Tauchrohr im Bereich der Reaktionskammer keine beweglichen Teile aufweist. Ein einfaches, beispielsweise aus einer Keramik bestehendes, Tauchrohr ist ausreichend, um das Prozeßgut schwerkraftgetrieben einzutragen. Es sind keine Schnecken, Kolben oder dergleichen erforderlich, die Schwerkraft wirkt stets zuverlässig. Da auf die Bereitstellung von Einförderkräften und -vorrichtungen innerhalb der Reaktionskammer verzichtet werden kann, ist der apparative Aufbau weiter vereinfacht, es müssen keine Hydrauliken, Druckluftleitungen, motorische Antriebe oder dergleichen vorgesehen sein, Schutzmaßnahmen für diese Teile können daher ebenfalls entfallen.First of all, the invention understands under process material carbonaceous material, such as wood, wood materials, straw, by-products and residues of agriculture and forestry and woodworking crafts, but also plastics, car tires, electronic waste, sewage sludge or Flussaushub (silt) with a correspondingly high organic content. The invention is understood by Melt metal all molten metals that are liquid in a range above the tar formation temperature. Especially she understands a tin melt underneath. Metallic tin is nontoxic in large quantities per se, the toxicity of simple tin compounds and tin salts is low, so that it is a very reliable metal. The most extensive exclusion of air ensures that undiluted product gas is produced, which has a correspondingly high calorific value. With particular advantage, the invention proposes that the entry device has at least one in the near-bottom region of the reaction chamber endendendes immersion tube, which ends under operating conditions in the molten metal and through which the Prozeßguteintrag is successful, wherein the dip tube has no moving parts in the region of the reaction chamber. Under immersion tube, the invention means any hollow body which leads below the surface of the metal bath contained in the operating state in the reaction chamber. Due to the low-level introduction of the process material particularly long contact times between the pyrolysis and the metal bath are made possible, so that results in correspondingly high conversion rates of the process material. A particularly long service life of the device is made possible by the immersion tube having no moving parts in the region of the reaction chamber. A simple, for example made of a ceramic, dip tube is sufficient to register the process material gravity-driven. There are no screws, pistons or the like required, the force of gravity is always reliable. Since it can be dispensed with the provision of feed forces and devices within the reaction chamber, the apparatus construction is further simplified, there must be no hydraulics, compressed air lines, motor drives or the like provided, protective measures for these parts can therefore also be omitted.

Es ist außerdem vorgesehen, dass die Eintragsvorrichtung eine Dosiervorrichtung zur Dosierung des Prozeßgutes in das Tauchrohr aufweist. Mittels der erfindungsgemäßen Dosiervorrichtung wird nur die gewünschte Menge Prozeßgut fein dosiert in das Tauchrohr gefördert, wodurch besonders stabile Betriebszustände erreicht werden. Eine erfindungsgemäße Dosiervorrichtung weist eine Förderschnecke und eine Abtragsvorrichtung auf, wobei die Abtragsvorrichtung als Fräser ausgebildet ist. Nicht-erfindungsgemäße Dosiervorrichtungen wären beispielsweise auch eine Membran, eine Klappvorrichtung, eine Zellenradschleuse mit ausreichend großen Zellkompartimenten oder ein Kollerrad mit oder ohne Ringmatrize, wie es aus Pelletiermaschienen bekannt ist. Allgemein sind drehende, Kompartimente aufweisende Einfördervorrichtungen bevorzugt. Denkbar ist ebenfalls, den Rotor der Zellenradschleuse mit einer Schneidkante zu versehen, um so ein Blockieren des ggf. grobkörnigen Prozeßgutes zu vermeiden. Einlaufseitig wird die Prozeßgutzufuhr dabei entweder senkrecht zur Drehachse des Rotors oder tangential dazu erfolgen. Im letzteren Fall wird das Prozeßgut von dem Abstreifer beziehungsweise der Schneidkante des Rotorflügels etwas in den Einlauf zurückgedrängt, um ein Verklemmen des Schnittgutes zwischen Zellenrad und Gehäuse vorteilhaft zu verhindern.It is also contemplated that the entry device has a metering device for metering the process material into the dip tube. By means of the metering device according to the invention, only the desired amount of process material is metered finely dosed into the dip tube, whereby particularly stable operating conditions can be achieved. A metering device according to the invention has a screw conveyor and a removal device, wherein the removal device is designed as a milling cutter. Non-inventive metering devices would be, for example, a membrane, a folding device, a rotary valve with sufficiently large Zellkompartimenten or a Kollerrad with or without ring die, as it is known from Pelletiermaschienen. Generally, rotary, compartmented feeders are preferred. It is also conceivable to provide the rotor of the rotary valve with a cutting edge, so as to avoid blocking of the possibly coarse-grained process material. On the inlet side, the supply of process material is either perpendicular to the axis of rotation of the rotor or tangential thereto. In the latter case, the process material is pushed back by the scraper or the cutting edge of the rotor blade something in the inlet to prevent jamming of the clippings between feeder and housing advantageous.

Außerdem weist die Eintragsvorrichtung eine gasdicht schließende Absperrvorrichtung-auf, sodass mit großem Vorteil sichergestellt ist, dass in der Reaktionskammer aufgebauter Druck nicht über die Dosiervorrichtung in die Eintragsvorrichtung entspannen kann. Diese Absperrvorrichtung stellt mit Vorteil auch sicher, dass Prozeßgut volumengepuffert zur Verfügung gestellt wird, was den gleichmäßigen Betrieb der Vorrichtung verbessert, da stets ausreichend Eintragsgut vorliegt. Durch die Pufferung und Art des Eintrages wird gleichzeitig verhindert, dass ein Übermaß an Prozeßgut auf die Dosiervorrichtung gelangen und diese blockieren kann. Der konstruktive Aufwand wird weiter dadurch vereinfacht, dass das Prozeßgut selbst die Absperrvorrichtung bildend ist, da hierdurch besonders wenige Bauteile im Zufuhrweg angeordnet sein müssen. Dies ist erfindungsgemäß möglich, indem das Prozeßgut in einer Zufuhrleitung zum Tauchrohr propfartig verdichtet ist. Über die Dichte und über die Länge des Propfes wird so mit Vorteil auch bei unterschiedlichen tauchrohrseitigen Gasdrücken eine Gasdichtheit erreicht. Gesonderte Rückschlagventile, Balgdichtungen oder Schlauchquetschventile können ebenso entfallen, wie deren Steuerungen, Antriebe und dergleichen Konstruktionsmerkmale mehr. Durch diese Maßnahme ermöglicht die Erfindung eine besonders robuste und störungsfrei arbeitende Dosiervorrichtung. Mit Vorteil kann so auch die Pelletierung des Prozeßgutes vor dessen Einsatz entfallen. Unter Gasdichtheit wird erfindungsgemäß dabei eine Dichtheit verstanden, die ausreichend ist, um den erforderlichen Betriebsdruck in dem Tauchrohr aufrechtzuerhalten. Absolute Gasdichtheit ist nicht erforderlich, wenn auch wünschenswert, da sie unter anderem Produktverluste vermeidet.In addition, the entry device has a gastight closing shut-off device, so that it is ensured with great advantage that pressure built up in the reaction chamber can not relax via the metering device into the entry device. This shut-off device advantageously also ensures that process material is provided with volume buffering, which improves the uniform operation of the device, since there is always sufficient input material. Due to the buffering and type of entry, it is simultaneously prevented that an excess of process material can reach the metering device and block it. The design effort is further simplified in that the process material itself the Shut-off is forming, as a result of this very few components must be arranged in the feed. This is inventively possible by the process material is compressed in a supply line to the dip tube gland. About the density and the length of the gudgeon gas tightness is thus achieved with advantage even at different dip tube side gas pressures. Separate check valves, bellows seals or pinch valves can be omitted as well as their controls, drives and the like design features more. By this measure, the invention enables a particularly robust and trouble-free working metering device. Advantageously, the pelletizing of the process material prior to its use can be dispensed with. Gas-tightness is understood according to the invention to mean a tightness which is sufficient to maintain the required operating pressure in the immersion tube. Absolute gas tightness is not required, albeit desirable, as it avoids, among other things, product losses.

Es ist erfindungsgemäß weiter vorgesehen, dass-die Förderrichtung der Förderschnecke gegen die Wirkrichtung der Abtragsvorrichtung gerichtet ist, wobei ein Sensor in Förderrichtung vor der Förderschnecke angeordnet ist. Diese Anordnung von nur drei robusten Bauteilen ergibt eine besonders gut arbeitende Dosiervorrichtung. Die angetriebene Förderschnecke fördert das Prozeßgut in Richtung des Tauchrohres. Sie kann es dabei erfindungsgemäß nicht nur fördern sondern auch zerkleinern und/oder verdichten, falls dies prozeßgutbedingt gewünscht oder benötigt ist. Erfindungsgemäß wäre ebenfalls, die Förderschnecke in einem separaten Flanschabschnitt anzuordnen, so daß diese bei wechselndem Prozeßgut gegen eine an das neue Prozeßgut besser angepasste einfach ausgetauscht werden kann. Die Art des Schneckenförderes ist der Erfindung zunächst nachranging, der Fachmann wird unter anderem Drehzahl, Innen- und Außendurchmesser, Steigung und Gangtiefe sowie Wellenzahl entsprechend wählen und den Füllgrad der Schnecke anpassen. Die Förderung erfolgt gegen den Widerstand der Abtragsvorrichtung, die ihrerseits entgegen der Förderrichtung des Prozeßgutes wirkt. Die Abtragsvorrichtung ist erfindungsgemäß als Fräser ausgebildet. Durch die entgegengesetzte Wirkrichtung der beiden Bauteile kann sowohl die Pfropflänge als auch die Propfdichte dem im Tauchrohr herrschenden Gasdruck angepaßt werden. Ist die Gasdichtheit des Prozeßgutpropfes zu gering, wird Gas aus der Reaktionskammer hindurch dringen und zum Sensor gelangen, der der Einfachheit halber beispielsweise nur eine typische Gaskomponente misst, beispielsweise CO oder CO2. Eine exakte Quantifizierung ist nicht zwingend erforderlich, die Bestimmung der Anwesenheit von CO oder CO2 wäre ausreichend. Misst der Sensor einen Gasdurchtritt, wird entweder die Abtragsleistung verringert oder die Förderleistung erhöht oder eine Mischung aus beidem angewandt. Die Vorrichtung verfügt hierzu über eine entsprechende Steuerung mit Daten- und Wirkleitungen, wobei die Steuerung entsprechend automatisiert sein kann.It is inventively further provided that the conveying direction of the screw conveyor is directed against the effective direction of the removal device, wherein a sensor is arranged in the conveying direction in front of the screw conveyor. This arrangement of only three robust components results in a particularly well-working metering device. The driven auger conveys the process material in the direction of the dip tube. You can not only promote it according to the invention but also crush and / or compress, if this is desired or required process material. According to the invention would also be to arrange the screw conveyor in a separate flange, so that it can be easily replaced with changing process material against a better adapted to the new process material. The type of screw conveyor is the invention first nachranging, the expert will choose among other things speed, inner and outer diameter, pitch and flight depth and wave number accordingly and the Adjust the filling level of the screw. The promotion takes place against the resistance of the removal device, which in turn counteracts the conveying direction of the process material. The removal device is inventively designed as a milling cutter. By the opposite effective direction of the two components, both the graft length and the graft density can be adapted to the pressure prevailing in the dip tube gas pressure. If the gas tightness of the Prozeßgutpropfes too low, gas will penetrate from the reaction chamber and pass to the sensor, which measures the sake of simplicity, for example, only a typical gas component, such as CO or CO 2 . An exact quantification is not mandatory, the determination of the presence of CO or CO 2 would be sufficient. If the sensor measures a gas passage, either the removal rate is reduced or the delivery rate is increased or a mixture of the two is used. The device has for this purpose a corresponding control with data and active lines, wherein the controller can be automated accordingly.

Besonders vorteilhaft ist, wenn die Abtragsvorrichtung die Schneckenwelle der Förderschnecke durchsetzend ist. Eine solche Anordnung benötigt lediglich einen Antrieb für die Rotation des Fräsers und einen für dessen Axialbewegung entlang der Förderrichtung, bzw. der Schneckenwelle. Damit können mit Vorteil alle Antriebe, also auch der der Förderschnecke, räumlich möglichst entfernt von der Reaktionskammer am selben Ort und somit besonders wartungsfreundlich angeordnet sein. Durch das Durchsetzen der Antriebswelle des Fräsers baut diese Vorrichtung kurz und ist im Block zu Wartungszwecken entnehmbar.It is particularly advantageous if the removal device is penetrating the worm shaft of the screw conveyor. Such an arrangement requires only one drive for the rotation of the milling cutter and one for its axial movement along the conveying direction, or the worm shaft. Thus, all drives, including those of the screw conveyor, can advantageously be arranged spatially as far away as possible from the reaction chamber at the same location and thus particularly easy to maintain. By enforcing the drive shaft of the cutter, this device builds short and is removed in the block for maintenance purposes.

In Ausgestaltung der Erfindung ist vorgesehen, dass die Reaktionskammer temperierbar ausgebildet ist, insbesondere eine Heizvorrichtung und/oder eine Wärmeisolierung aufweist. Diese wird benötigt, um das Metallbad auf seine Arbeitstemperatur zu halten, diese zu erreichen beziehungsweise eine andere, insbesondere höhere, Arbeitstemperatur zu erreichen und zu halten. Mit anderen Worten ist die Vorrichtung in der Lage, Temperaturprogramme zu fahren.In an embodiment of the invention it is provided that the reaction chamber is designed to be temperature-controlled, in particular has a heating device and / or a thermal insulation. This is needed to keep the metal bath at its working temperature to achieve or to achieve and maintain another, especially higher, working temperature. In other words, the device is able to drive temperature programs.

Weist die Produktableitung eine Produktgasnachbehandlungsvorrichtung auf, insbesondere eine oder mehrere Staubabscheider, Gaskühler, Kondensatabscheider und/oder eine chemische Gasreinigung, ist zum einen mit Vorteil sichergestellt, dass nur hochreines Produktgas die erfindungsgemäße Vorrichtung verläßt, und zum anderen ist sichergestellt, dass feste Produkte abgeschieden und zur weiteren Verwertung zur Verfügung gestellt werden können. Eine chemische Gasreinigung wird immer dann gewünscht sein, wenn problematisches Prozeßgut, insbesondere stark schwefelhaltige oder chlorhaltige Biomasse eingesetzt wird.If the product discharge has a product gas aftertreatment device, in particular one or more dust collectors, gas coolers, condensate separators and / or chemical gas cleaning, it is advantageously ensured that only highly pure product gas leaves the device according to the invention, and secondly it ensures that solid products are separated off and can be made available for further use. A chemical gas purification will always be desirable if problematic process material, in particular highly sulfur-containing or chlorine-containing biomass is used.

Die Verfahrensaufgabe wird bei einem Verfahren zu Pyrolyse kohlenstoffhaltigen Pyrolysegutes, bei dem in einer Reaktionskammer ein Metallbad unter Luftabschluss gehalten wird und Prozeßgut kontinuierlich in das Metallbad unter dessen Oberfläche eingetragen wird und dabei der Eintrag ohne Einsatz beweglicher Teile im Bereich des Metallbades erfolgt und bei dem das Prozeßgut vom Ort der Pyrolyse durch das Metallbad hindurchtritt, um zu einer Produktableitung zu gelangen, dadurch gelöst, dass das Prozeßgut vor Eintrag in das Metallbad einen annähernd gasdichten Verschluß der Eintragsvorrichtung durch Presskuchenbildung bildend ist, indem eine Förderschnecke gegen die Wirkrichtung einer Abtragsvorrichtung fördernd ist, wobei die Abtragsvorrichtung als Fräser ausgebildet ist und der Fräser den Presskuchen fräsend abtragend ist. Die Vorteile dieses Verfahrens wurden bereits vorstehend bei der erfindungsgemäßen Vorrichtung geschildert.The process task is in a process for pyrolysis carbonaceous pyrolysis good, in which a metal bath is kept in a reaction chamber under exclusion of air and process material is continuously introduced into the metal bath below the surface while the entry takes place without the use of moving parts in the metal bath and in the Process material from the site of the pyrolysis passes through the metal bath, in order to achieve a product discharge, achieved in that the process material before entry into the metal bath is an approximately gas-tight closure of the entry device by press cake forming by a screw conveyor against the direction of action of a removal device is promotional wherein the removal device is designed as a milling cutter and the milling cutter is milling away the press cake. The advantages of this method have already been described above in the device according to the invention.

In Ausgestaltung dieses Verfahrens ist vorgesehen, dass der Eintrag des Prozeßgutes in das Zinnbad mittels Schwerkraft erfolgt und/oder die Pyrolyseguteintragsrate im Gleichgewicht mit der Pyrolyserate des Pyrolysegutes ist und/oder bei dem das Metallbad Siedesteinchen aufweist, insbesondere silikatische Siedesteinchen, bevorzugt Quarzsiedesteinchen. Insbesondere die letzte Maßnahme stellt sicher, dass keine größeren Gasblasen entstehen, die eruptionsartig die Oberfläche des Zinnbades durchstoßen und Zinntröpfchen mit sich reißen könnten.In an embodiment of this method it is provided that the entry of the process material into the tin bath by gravity takes place and / or the Pyrolyseguteintragsrate is in equilibrium with the pyrolysis of the pyrolysis and / or in which the metal bath boiling stones, in particular silicate boiling stones, preferably quartz sediments. In particular, the last measure ensures that no larger bubbles of gas are formed, which eruptions break through the surface of the tin bath and tear tin droplets with it.

In Ausgestaltung des Verfahrens ist vorgesehen, dass das erhaltene Produktgas aufbereitet und stofflich verwertet wird, insbesondere einer wasserstofferzeugenden katalytischen Wassergas-Shiftreaktion unterworfen wird. Neben der zuvor erwähnten thermischen Verwertung des Produktgases in BHKW oder dergleichen ist hier mit großem Vorteil auch eine stoffliche Verwertung möglich. Dies liegt daran, dass hochreines Produktgas praktisch staubfrei erzeugt wird. Zudem kann auch feuchte Biomasse oder feuchtes Pyrolysegut eingesetzt werden, so daß die zur Durchführung der Shift-Reaktion erforderliche Wassermenge bereits im System vorliegt. Erfindungsgemäß kann auch vorgesehen sein, im Bedarfsfall zusätzlich Wasser einzudosieren. Je nach Feuchtigkeit der eingesetzten Biomasse kann diese Wassergas-Shiftreaktion auch bereits mindestens teilweise in der Reaktionskammer ablaufen, insbesondere an Koksrückständen, die an der Oberfläche des Zinnbades in glühendem Zustand vorliegen.In an embodiment of the method it is provided that the product gas obtained is treated and recycled, in particular subjected to a hydrogen-producing catalytic water gas shift reaction. In addition to the aforementioned thermal utilization of the product gas in CHP or the like, material recycling is also possible with great advantage. This is because high-purity product gas is produced virtually dust-free. In addition, moist biomass or moist pyrolysis can be used, so that the time required to carry out the shift reaction amount of water is already present in the system. According to the invention, it may also be provided to additionally meter in water if necessary. Depending on the moisture of the biomass used, this water gas shift reaction may also already take place at least partially in the reaction chamber, in particular on coke residues which are present in the glowing state on the surface of the tin bath.

Die Erfindung wird in einer bevorzugten Ausführungsform unter Bezugnahme auf eine Zeichnung beispielhaft beschrieben, wobei weitere vorteilhafte Einzelheiten den Figuren der Zeichnung zu entnehmen sind. Funktionsmäßig gleiche Teile sind dabei mit denselben Bezugszeichen versehen.The invention will be described by way of example in a preferred embodiment with reference to a drawing, wherein further advantageous details are shown in the figures of the drawing. Functionally identical parts are provided with the same reference numerals.

Die Figuren der Zeichnung zeigen im Einzelnen:

  • Fig. 1 zeigt eine schematische Skizze einer erfindungsgemäßen Vorrichtung mit nicht-erfindungsgemäßer Absperrvorrichtung und
  • Fig. 2 ein Detail im Bereich des Tauchrohres und
  • Fig. 3 ein Detail der Dosiervorrichtung in erfindungsgemäßer Ausführungsform.
The figures of the drawing show in detail:
  • Fig. 1 shows a schematic diagram of a device according to the invention with non-inventive shut-off device and
  • Fig. 2 a detail in the area of the dip tube and
  • Fig. 3 a detail of the metering device according to the invention embodiment.

Fig. 1 zeigt eine erfindungsgemäße Pyrolysevorrichtung 1_mit nicht erfindungsgemäßer Absperrvorrichtung. Diese kann produktgasseitig mit kleineren Blockheizkraftwerken in der Größenordnung von 10 bis 50 kWel verbunden sein, die das in der Pyrolysevorrichtung 1 erzeugte Heizgas verbrennen. Sie kann erfindungsgemäß auch mit anderen Aggregaten zur Strom- und/oder Wärmeerzeugung verbunden sein, beispielsweise Mikrogasturbinen, Brennstoffzellen oder Stirlingmotoren. Produkteintragsseitig ist die Pyrolysevorrichtung mit einem Pyrolysegutvorratsbehälter 17 verbunden ausgebildet, der in Fig. 1 schematisch dargestellt ist. In diesem werden die zuvor genannten Pyrolyse- oder Prozeßgüter zur kontinuierlichen Einförderung vorrätig gehalten, beispielsweise Holz, Holzpellets, Holzwerkstoffe, Klärschlamm, oder allgemeiner Biomasse, insbesondere biologische Neben- und Reststoffe wie Stroh, Sonnenblumenspelzen, Energiepflanzenreste. Aufgrund der Größe der Anlage reicht eine Kleinmengenbevorratung aus. Damit wird die erfindungsgemäße Vorrichtung besonders interessant für die entstehungsnahe Entsorgung derartiger Biomasse, beispielsweise auf dem Betriebsgelände eines Sägewerkes, Zimmerei oder Schreinerei oder eines Garten- oder Landschaftsbaubetriebes. Sollen mit der erfindungsgemäßen Vorrichtung Metallwiedergewinnungsverfahren durchgeführt werden, ist der Prozeßgut- oder Pyrolysegutvorratsbehälter 17 entsprechend anzupassen. Das erfindungsgemäße Verfahren führt bei einem solchen Prozeßgut dazu, daß sich die in ihm enthaltenen Metalle im Zinnbad lösen, aus dem sie wiedergewonnen werden. Die Gewinnung eines Heizgases ist in diesem Fall nachrangig, der Einsatzzweck der Vorrichtung ändert sich entsprechend. Derartiges Pyrolysegut sind Kunststoffe, mehr oder weniger aufbereiteter Elektronikschrott oder dergleichen. Vom Pyrolysegutvorratsbehälter 17 gelangt das Pyrolysegut über Rohrleitungen zur Eintragsvorrichtung 3. Diese besteht bei dieser Ausführungsform der Erfindung aus einem Fallrohr, das in Richtung der Rohrleitung zum Pyrolysegutvorratsbehälter 17 gasdicht abgeschlossen ist. Dieser gasdichte Abschluss wird hier durch zwei voneinander in Zufuhrrichtung beabstandet angeordnete pneumatische Schlauchquetschventile 18, 19 erreicht, die zwischen sich einen Zwischenspeicher 20 für Pyrolysegut definieren und die nicht erfindungsgemäß sind. Das Pyrolysegut gelangt nach dem zweiten Schlauchquetschventil 19 auf eine Dosiervorrichtung 7. Diese nimmt das Pyrolysegut portionsweise in Kompartimente oder Taschen auf und überführt es durch eine Drehung um eine beispielsweise orthogonal zur Förderrichtung orientierte Drehachse in das Tauchrohr 6. Das Tauchrohr 6 wird in Fig. 2 näher beschrieben. Es endet im Bereich der Bodenfläche 21 der Reaktionskammer 2 mit einer in etwa parallel zur Bodenfläche 21 ausgerichteten Austrittsfläche. Die Reaktionskammer 2 weist eine Wärmeisolierung 10 und eine Heizvorrichtung 9 auf, beide sind nur einseitig skizziert. Die Heizvorrichtung 9 kann erfindungsgemäß auch im Inneren der Reaktionskammer 2 angeordnet sein, in dessen Wände integriert sein oder sich auf der äußeren Wandseite befinden, wie skizziert. Die Art der Heizvorrichtung 9 ist nur insofern von Belang, als das sie Temperaturen von mindestens 800°C in der Reaktionskammer 2 erzeugen und dauerhaft gewährleisten können muß. Die Betriebstemperatur der Reaktionskammer 2 kann erfindungsgemäß jedoch auch 900°C oder deutlich darüber betragen. Das aus dem Pyrolysegut freigesetzte Heizgas sammelt sich in einem Gasraum oberhalb der Zinnschmelze, von wo es aktiv oder passiv entnommen werden kann. Dieser Gasraum ist vollständig von Heizgas gefüllt, er enthält keinerlei Luftanteile. Dies gewährleistet einen hohen Brennwert des erzeugten Heizgases. Oberhalb der Oberfläche des Zinnbades im Bereich der Deckelfläche 22 des Reaktionsraumes 2 ist eine Produktgasableitung 4 angeordnet. Damit ist ein maximaler Abstand von Austrittsfläche des Tauchrohres und Eintrittsfläche der Produktgasableitung 4 gewährleistet, so daß das Prozeßgut das gesamte Zinnbad durchdringen muß, wodurch sehr lange Kontaktzeiten zur Metallschmelze erzeugt werden. Die Produktgasableitung 4 weist mehrere Bauteile auf. Rohrabschnitte führen von der Reaktionskammer zu einem Staubabscheider 12. Dieser dient dazu, mitgerissenen Koks abzuscheiden und die Staubbelastung des Produktgases zu reduzieren. In diesem kann auch ein Kondensatabscheider 14 angeordnet sein. Je nach Pyrolysegut kann es erforderlich werden, auch eine chemische Gasreinigung 15 vorzusehen, um beispielsweise Schwefel und Schwefelverbindungen, Chlor und Chlorverbindungen oder Stickstoff abzuscheiden. Dies wird immer dann der Fall sein, wenn "schwierige" Biomasse wie Stroh oder dergleichen eingesetzt werden. Falls erforderlich, kann ein Gaskühler 13 vorgesehen sein. Das so erzeugte Produktgas kann neben der thermischen auch einer stofflichen Verwertung unterzogen werden. Da das Produktgas stark CO-haltig ist, können über geeignete robuste Katalysatoren CO2 und H2 erzeugt werden. Hierbei ist es besonders vorteilhaft, daß erfindungsgemäß-auch feuchte Biomasse eingesetzt werden kann, die das für diese Reaktion benötigte Wasser zur Verfügung stellen kann. Mit großem Vorteil kann ein Trocknungsschritt der Biomasse vor der Pyrolyse unterbleiben. Dies verbessert die energetische Gesamtbilanz der Vorrichtung und des erfindungsgemäßen Verfahrens. Fig. 1 shows a pyrolysis invention 1_with not inventive shut-off device. This can be connected on the product gas side with smaller combined heat and power plants in the order of 10 to 50 kW el , which burn the fuel gas generated in the pyrolysis 1. It can also be connected according to the invention with other units for power and / or heat generation, for example micro gas turbines, fuel cells or Stirling engines. Product entry side, the pyrolysis is connected to a Pyrolysegutvorratsbehälter 17, which in Fig. 1 is shown schematically. In this, the aforementioned pyrolysis or process goods are kept in stock for continuous introduction, such as wood, wood pellets, wood materials, sewage sludge, or general biomass, especially biological by-products and residues such as straw, sunflower furs, energy crop residues. Due to the size of the plant a small amount of stock is sufficient. Thus, the device of the invention is particularly interesting for the genesis near disposal of such biomass, for example, on the premises of a sawmill, carpentry or joinery or a garden or landscaping operation. Should with the Inventive apparatus metal recovery process are performed, the process material or Pyrolysegutvorratsbehälter 17 is adjusted accordingly. The process of the invention results in such process material that the metals contained in it dissolve in the tin bath, from which they are recovered. The recovery of a fuel gas is in this case subordinate, the purpose of the device changes accordingly. Such pyrolysis are plastics, more or less processed electronic waste or the like. From Pyrolysegutvorratsbehälter 17 the pyrolysis passes via pipes to the entry device 3. This consists in this embodiment of the invention of a downpipe, which is gas-tight in the direction of the pipeline to Pyrolysegutvorratsbehälter 17. This gas-tight closure is achieved here by two pneumatic peristaltic pinch valves 18, 19 arranged at a distance from one another in the feed direction, which define between them an intermediate store 20 for pyrolysis goods and which are not in accordance with the invention. The pyrolysis reaches after the second Schlauchquetschventil 19 to a metering device 7. This takes the pyrolysis in portions in compartments or pockets and transferred by rotation about an example orthogonal to the direction of rotation oriented axis of rotation in the dip tube 6. The dip tube 6 is in Fig. 2 described in more detail. It ends in the region of the bottom surface 21 of the reaction chamber 2 with an outlet surface oriented approximately parallel to the bottom surface 21. The reaction chamber 2 has a thermal insulation 10 and a heater 9, both are outlined only on one side. According to the invention, the heating device 9 can also be arranged inside the reaction chamber 2, be integrated in the walls thereof or be on the outer wall side, as outlined. The nature of the heater 9 is only relevant insofar as they are temperatures of at least 800 ° C in the reaction chamber. 2 produce and must be able to ensure long-term. However, the operating temperature of the reaction chamber 2 according to the invention may also be 900 ° C or significantly higher. The fuel gas released from the pyrolysis gas collects in a gas space above the tin melt, from where it can be removed actively or passively. This gas space is completely filled by fuel gas, it contains no air fractions. This ensures a high calorific value of the generated heating gas. Above the surface of the tin bath in the region of the cover surface 22 of the reaction space 2, a product gas discharge line 4 is arranged. Thus, a maximum distance from the exit surface of the dip tube and the inlet surface of the product gas discharge line 4 is ensured, so that the process material must penetrate the entire tin bath, whereby very long contact times are generated to the molten metal. The product gas discharge 4 has several components. Pipe sections lead from the reaction chamber to a dust collector 12. This serves to separate entrained coke and to reduce the dust load of the product gas. In this also a condensate 14 may be arranged. Depending on the pyrolysis, it may be necessary to provide a chemical gas cleaning 15, for example, to deposit sulfur and sulfur compounds, chlorine and chlorine compounds or nitrogen. This will always be the case when "difficult" biomass such as straw or the like is used. If necessary, a gas cooler 13 may be provided. The product gas thus produced can be subjected not only to thermal but also to material recycling. Since the product gas is highly CO-containing, CO 2 and H 2 can be generated via suitable robust catalysts. In this case, it is particularly advantageous that moist biomass according to the invention can also be used which can provide the water required for this reaction. With great advantage, a drying step of the biomass stop before pyrolysis. This improves the overall energy balance of the device and the method according to the invention.

Fig. 2 zeigt ein Detail des Tauchrohres 6. Dieses ragt mehr oder weniger senkrecht von oben in den zylindrischen Reaktionsraum 2 hinein und endet etwas oberhalb von dessen Bodenfläche 21. Dieses Tauchrohr 6 kann Bauteil des Reaktionsraumes 2 sein oder ein davon separates, in ihn eingesetztes Bauteil. In jedem Fall weist ihm seine Funktionalität eine Zugehörigkeit zur Eintragsvorrichtung 3 zu. Im Durchtrittsbereich des Tauchrohres 6 durch die Wandung des Reaktionsraumes 2 ist neben einer gegebenenfalls vorhandenen Dichtung auch eine Kühlung vorgesehen, damit sich dessen Wärme nicht den oberhalb angeordneten Bauteilen wie der Dosiervorrichtung 7 oder den nicht erfindungsgemäßen Schlauchquetschventilen 18, 19 mitteilt. Das Tauchrohr 6 endet im Betriebszustand der Vorrichtung deutlich unterhalb der Oberfläche des Metallbades. Es enthält keine mechanischen Teile und kann aus einer temperaturbeständigen Keramik bestehen. Beim Anfahren der Vorrichtung ist es zunächst mit Metallschmelze bis zur Höhe des Metallbades gefüllt. Von der Dosiervorrichtung 7 eingefördertes kohlenstoffhaltiges Prozeßgut fällt schwerkraftgetrieben auf die Schmelze und wird dort zu Gasen und Koks pyrolysiert. Die entstehenden Gase erzeugen einen Druck im Tauchrohr 6, der mit der Zeit nach und nach das dort vorhandene flüssige Zinn in die Reaktionskammer 2 verdrängt. Bei dieser Ausführungsform ist es daher besonders wichtig, daß der sich aufbauende Gasdruck nicht oder nur in geringem Maße nach oben in die restliche Eintragsvorrichtung 3 entweichen kann. Die voneinander beabstandeten Schlauchquetschventile 18, 19 sorgen zusammen mit der Dosiervorrichtung 7 für das erforderliche Maß an Gasdichtheit, indem der Druck in Stufen nach oben absinkt, gleichsam nach Art einer Schleusentreppe zur Überwindung eines großen Höhenunterschiedes. Ist der aufgebaute Gasdruck so hoch, daß das Tauchrohr 6 vollständig oder annähernd vollständig frei von flüssigem Zinn ist, führt weiteres Einfördern von Prozeßgut dazu, daß das Prozeßgut nunmehr schwerkraftgetrieben bis in den bodennahen Bereich des Tauchrohres 6 fällt und erst dort auf die Schmelze trifft. Das dann entstehende Gas tritt nach unten um den Rand des Tauchrohres 6 herum in das Metallbad ein und durch dieses hindurch. Gleiches gilt für den Feststoff, der in das Metallbad mitgerissen wird und durch dieses hindurchtreten muß. Auf diese Weise erzeugt die Vorrichtung lange Kontaktzeiten, eine vollständige Umhüllung des Pyrolysegutes durch das Zinnbad und damit eine annähernd vollständige Pyrolyse und Entgasung des Prozeßgutes, das seinerseits vollständig in Koks, bzw. Koksstaub umgewandelt wird. Die Teilchengröße des Koks ist so gering, daß diese durch den aus der Reaktionskammer 2 austretenden Gasstrom mitgerissen werden kann. Es hat sich gezeigt, dass es in der Reaktionskammer 2 nicht zu einer Anreicherung an Koks kommt. Wie geschildert, ist es erfindungsgemäß äußerst vorteilhaft, wenn die Einförderungsrate des Prozeßgutes seiner Umsetzungsrate entspricht. In diesem Fall bildet sich ein leicht zu beherrschendes, stabiles, statisches System mit konstanten Umsätzen aus. Das bodenseitige Ende des Tauchrohres 6 kann einfach zylindrisch ausgebildet sein oder einen aufgeweiteten, beispielsweise glockenartig aufgeweiteten, Rand aufweisen. Dieser kann ggf. auch mit einer siebartig durchbrochenen Rohrwand in einem endseitigen Abschnitt versehen sein. Der Erfindung ist vor allem wichtig, daß das Ende des Tauchrohres 6 deutlich unterhalb der Oberfläche des Zinnbades endet, so daß das Prozeßgut durch das gesamte Metallbad hindurchtreten muß. Erfindungsgemäß können pro Reaktionsraum 2 auch mehr als ein Tauchrohr 6 vorgesehen sein, beispielsweise zwei oder drei, um einen homogenere Eintrag zu ermöglichen. Ein möglichst genau vertikal verlaufendes Tauchrohr 6 ist bevorzugt, da bei diesem das Prozeßgut schwerkraftgetrieben frei von der Dosiervorrichtung 7 auf die Zinnoberfläche fallen kann. Es ist ebenfalls erfindungsgemäß, dass die Durchtrittsfläche des Tauchrohres 6 und die Bodenfläche des Reaktionsraumes 2 einen Winkel zwischen sich einschließen und nicht parallel zueinander sind. Ein solcher Winkel ergibt sich beispielsweise bei einer windschiefen Anordnung des Rohres, oder einen L- oder u-förmig gebogenem Rohrende. Unabhängig davon, wie die Endgeometrie des Tauchrohres 6 aussieht, muß sichergestellt sein, daß sich keine Prozeßgutschicht auf der Zinnoberfläche aufbauen kann, die nachfallendes Material blockiert und über Lunkerbildung den Vergasung- und Pyrolyseprozess unterbricht. Fig. 2 shows a detail of the dip tube 6. This protrudes more or less perpendicularly from above into the cylindrical reaction chamber 2 and ends slightly above the bottom surface 21. This dip tube 6 may be part of the reaction chamber 2 or a separate, inserted into it component. In any case, its functionality assigns it a membership in the entry device 3. In the passage region of the dip tube 6 through the wall of the reaction chamber 2 in addition to a possibly existing seal and cooling is provided so that its heat does not communicate with the above-arranged components such as the metering device 7 or the non-inventive Schlauchquetschventilen 18, 19. The dip tube 6 ends in the operating state of the device well below the surface of the metal bath. It contains no mechanical parts and can consist of a temperature-resistant ceramic. When starting the device, it is first filled with molten metal to the level of the metal bath. From the metering device 7 conveyed carbonaceous Prozeßgut falls gravity driven on the melt and is pyrolyzed there to gases and coke. The resulting gases generate a pressure in the dip tube 6, which gradually displaces over time the liquid tin present there into the reaction chamber 2. In this embodiment, it is therefore particularly important that the gas pressure building up can not escape or only to a slight extent up in the rest of the entry device 3. The spaced-apart Schlauchquetschventile 18, 19 provide together with the metering device 7 for the required level of gas tightness by the pressure in steps falls upwards, as if in the manner of a lock staircase to overcome a large difference in height. Is the built-up gas pressure so high that the dip tube 6 completely or almost completely free of liquid tin is, further conveying of process material leads to the process material gravity now falls into the near-ground region of the dip tube 6 and only there meets the melt. The resulting gas enters the metal bath down around the edge of the dip tube 6 and passes therethrough. The same applies to the solid, which is entrained in the metal bath and must pass through it. In this way, the device generates long contact times, a complete enclosure of the pyrolysis material through the tin bath and thus an approximately complete pyrolysis and degassing of the process material, which in turn is completely converted into coke, or coke dust. The particle size of the coke is so small that it can be entrained by the emerging from the reaction chamber 2 gas flow. It has been found that there is no accumulation of coke in the reaction chamber 2. As described, it is inventively extremely advantageous if the rate of delivery of the process material corresponds to its conversion rate. In this case, an easy-to-control, stable, static system with constant revenues is formed. The bottom end of the dip tube 6 may be simply cylindrical or have a widened, for example bell-like widened edge. This may possibly also be provided with a sieve-like perforated pipe wall in an end-side section. The invention is especially important that the end of the dip tube 6 ends well below the surface of the tin bath, so that the process material must pass through the entire metal bath. According to the invention, more than one dip tube 6 may be provided per reaction space 2, for example two or three, in order to allow a more homogeneous entry. An as far as possible vertically extending dip tube 6 is preferred, since in this case the process material gravity-driven can fall freely from the metering device 7 on the tin surface. It is too According to the invention, that the passage surface of the dip tube 6 and the bottom surface of the reaction space 2 form an angle between them and are not parallel to each other. Such an angle results, for example, in a skewed arrangement of the pipe, or an L- or U-shaped bent pipe end. Regardless of what the final geometry of the dip tube 6 looks like, it must be ensured that no process material layer can build up on the tin surface, blocks the trailing material and interrupts the gasification and pyrolysis process via voids formation.

Fig. 3 zeigt wiederum schematisch und nicht maßstabsgetreu eine erfindungsgemäße Ausführungsform der Eintragsvorrichtung 3. Reaktionskammer 2, Tauchrohr 6, Zinnbad, Gasableitung und Prozeßgut innerhalb der Reaktionskammer sind wie in den vorherigen Figuren und nur schematisch angedeutet. Das Tauchrohr 6 knickt an seinem oberen Ende in etwa horizontal ab und geht in die eigentliche Dosiervorrichtung über. Diese weist einen schematischen Einfülltrichter auf, der eine irgendwie geartete Zufuhr an Prozeßgut 4 symbolisiert. In dessen Bereich ist ein Sensor 25 angeordnet, der Daten- und wirkmäßig mit einer nicht dargestellten Anlagensteuerung verbunden ist. Der Sensor ist so angeordnet, daß er aus der Vorrichtung austretendes Gas, beispielsweise CO2, von Außenluft ungestört messen kann. Das Prozeßgut 4 rieselt oder fällt in eine oder wird zu einer Förderschnecke 23 transportiert, die ihrerseits wiederum eine hohle Schneckenwelle aufweist. Die Förderschnecke 23 fördert in Richtung auf das Tauchrohr 6 zu. Die Antriebe für Förderschnecke und Abtragsvorrichtung 24 sind nicht dargestellt. Die Schneckenwelle ist durch eine Welle der Abtragsvorrichtung 24 durchsetzt, hier einem Fräser. Der Fräser ist axial verschieblich und rotatorisch angetrieben ausgebildet. Ohne Antrieb bildet er einen Widerstand für das in seine Richtung geförderte Prozeßgut 4, daß vor ihm einen Presskuchen oder Pfropf 26 bildet. Je nach Förderleistung der Förderschnecke 23 und der axialen Strecke zwischen Schneckenende und Fräser wird so ein Presskuchen unterschiedlicher Dichte und axialer Länge erzeugt. Hierdurch können unterschiedlichste Prozeßgüter 4 so verarbeitet werden, daß der Presskuchen 26 annähernd gasdicht ist und den Innenraum der erfindungsgemäßen Vorrichtung von der Außenwelt abdichtet. Der Prozeßguteintrag in die Schmelze wird erreicht, indem der Fräser 24 für eine bestimmte Zeit arbeitet. Er kann dabei zusätzlich auch einen axialen Weg in Richtung auf das Förderschneckenende zurücklegen, um den Presskuchen 26 zu verkürzen. Durch Wahl von Fräsgeschwindigkeit, Fräsdauer, axialem Vorschub und Förderleistung der Förderschnecke 23 stehen dem Bediener ausreichend Parameter zur Steuerung der Anlage zur Verfügung. Durch die fräsende Abtragung des Prozeßgutes 4 vom Presskuchen 26 wird gleichzeitig mit großem Vorteil eine Zerkleinerung und damit Oberflächenvergrößerung des Prozeßgutes 4 erreicht, was zu einer besonders ruhigen, gleichmäßigen und steten Vergasung führt. Fig. 3 zeigt auch eine erfindungsgemäße zweite Heizungsanordnung 9, nämlich drei im gleichen Winkelabstand zueinander und konzentrisch um das Tauchrohr 6 angeordnete und an ihren Enden räumlich fixierte Heizrohre, die im Betriebszustand mitten durch die Schmelze verlaufend sind, so daß diese turbulente Schmelze besonders effektiv erhitzt wird. Diese Heizrohre sind vorzugsweise aus demselben Material wie das Tauchrohr 6 und können beispielsweise elektrisch- oder heizgasbetrieben sein. Fig. 3 again shows schematically and not to scale an inventive embodiment of the entry device 3. Reaction chamber 2, dip tube 6, tin bath, gas discharge and process material within the reaction chamber are as in the previous figures and only schematically indicated. The dip tube 6 kinks at its upper end in approximately horizontal and goes into the actual metering device. This has a schematic hopper, which symbolizes any kind of supply of process material 4. In its area a sensor 25 is arranged, the data and is effectively connected to a system control, not shown. The sensor is arranged so that it can measure from the device leaking gas, such as CO 2 , undisturbed by outside air. The process material 4 trickles or falls into one or is transported to a screw conveyor 23, which in turn has a hollow screw shaft. The screw conveyor 23 promotes toward the dip tube 6. The drives for screw conveyor and removal device 24 are not shown. The worm shaft is penetrated by a shaft of the removal device 24, here a cutter. The cutter is axially displaceable and rotationally driven. Without drive, it forms a resistance to the conveyed in his direction process material 4 that forms a press cake or plug 26 before him. Depending on Delivery of the screw conveyor 23 and the axial distance between the screw end and cutter so a press cake of different density and axial length is generated. As a result, very different process items 4 can be processed so that the press cake 26 is approximately gas-tight and seals the interior of the device according to the invention from the outside world. The process material entry into the melt is achieved by the cutter 24 working for a certain time. In addition, he can also cover an axial path in the direction of the auger end to shorten the press cake 26. By selecting the milling speed, milling duration, axial feed and delivery rate of the screw conveyor 23, the operator has sufficient parameters for controlling the system. Due to the milling removal of the process material 4 from the press cake 26 is a crushing and thus surface enlargement of the process material 4 is achieved at the same time with great advantage, resulting in a particularly quiet, steady and steady gasification. Fig. 3 also shows a second heater assembly 9 according to the invention, namely three at the same angular distance from each other and concentrically arranged around the dip tube 6 and spatially fixed at their ends heating tubes that are running in the middle of the melt in the operating state, so that this turbulent melt is heated particularly effectively. These heating tubes are preferably made of the same material as the dip tube 6 and may for example be electrically or heated gas.

Im Gegensatz zu bekannten Verfahren arbeitet das erfindungsgemäße Verfahren bei sehr hohen Arbeitstemperaturen, sodass es praktisch nicht zur Bildung von Teeren kommt. Die Teerbildungsrate liegt unterhalb von 10 g/Nm3. Der erfindungsgemäße Verzicht auf bewegte mechanische Teile im Bereich der Reaktionskammer 2 reduziert die technischen Störquellen. Hotspots oder Kurzschlussströmungen werden genauso vermieden, wie die Notwendigkeit thermisch und metallurgisch widerstandsfähiger Lager oder dergleichen. Auch kleinere Anlagengrößen können wirtschaftlich arbeiten, die erfindungsgemäße Vorrichtung und das Verfahren sind einfach automatisierbar und bedienerfreundlich. Das eingesetzte Zinn hat bei einer Betriebstemperatur von 900°C lediglich einen Dampfdruck von 1*10-4 mbar, sodass es hervorragend geeignet ist und eine lange Standzeit aufweist. Feststoffe und Produktgas trennen sich sehr gut vom Zinn, es gibt kaum Gaslöslichkeiten. Bei einem beispielhaften Pyrolysegang wurde als Pyrolysegut Rinderdung eingesetzt, dies ergab die permanente Produktgaszusammensetzung (in Vol.-%): Tabelle 1 N2 H2 O2 CO CO2 CH4 Wasser CxHy 1,3 26,1 0,2 24,9 31,3 9,0 3,0 4,2 In contrast to known methods, the inventive method operates at very high operating temperatures, so that there is virtually no formation of tars. The tar formation rate is below 10 g / Nm 3 . The waiver according to the invention of moving mechanical parts in the region of the reaction chamber 2 reduces the technical sources of interference. Hot spots or short circuit currents will be the same avoided, such as the need for thermally and metallurgically resistant bearings or the like. Even smaller plant sizes can work economically, the device according to the invention and the method are easy to automate and user-friendly. At an operating temperature of 900 ° C, the tin used only has a vapor pressure of 1 * 10 -4 mbar, which makes it extremely suitable and has a long service life. Solids and product gas separate very well from the tin, there is hardly any gas solubility. In an exemplary pyrolysis process, bovine manure was used as the pyrolysis product, which resulted in the permanent product gas composition (in% by volume): Table 1 N 2 H 2 O 2 CO CO 2 CH 4 water C x H y 1.3 26.1 0.2 24.9 31.3 9.0 3.0 4.2

Weiterhin wurden Holz, Stroh, Kirschkerne und Kunststoff als Pyrolysegut eingesetzt. In jedem Fall wurden sehr hohe Ausbeuten an Synthesegas (CO, H2) von ca. 68 bis 81 Vol.-% erreicht. Die Summe der brenntechnisch verwertbaren Gase liegt zwischen 83 und 91 Vol.-%. Einzelheiten sind der Tabelle 2 zu entnehmen, Angaben in Vol.-%: Tabelle 2 Holz (40% H2O) Holz (16% H2O) Stroh Kirschkerne Kunststoff H2 39 47 43 43 59 CO 30 34 32 32 6 CH4 11 7 7 11 25 CxHy 3 0 5 5 8 CO2 17 12 12 9 2 Furthermore, wood, straw, cherry stones and plastic were used as pyrolysis. In each case, very high yields of synthesis gas (CO, H 2 ) of about 68 to 81% by volume were achieved. The sum of combustible gases is between 83 and 91 Vol .-%. Details are given in Table 2, data in% by volume: Table 2 Wood (40% H 2 O) Wood (16% H 2 O) straw Kirschkerne plastic H 2 39 47 43 43 59 CO 30 34 32 32 6 CH 4 11 7 7 11 25 C x H y 3 0 5 5 8th CO 2 17 12 12 9 2

Mit großem Vorteil kann erfindungsgemäß eine Vortrocknung des Prozeßgutes unterbleiben, selbst Wassergehalte von 40 Vol.-% sind unschädlich. Dies verbessert die energetische Gesamtbilanz des Verfahrens und der Vorrichtung.With great advantage, a pre-drying of the process material according to the invention can be omitted, even water contents of 40 vol .-% are harmless. This improves the overall energy balance of the method and the device.

Generell werden sehr hohe Volumenanteile an Wasserstoff, Methan und CO erzielt. Es wurde eine Zinnkonzentration von 5,3*10-7 mg/Nm3 gemessen. Es konnte kein Teer erfasst werden, sodass die Verwertung des erfindungsgemäß erzeugten Produktgases in einem Gasmotor problemlos möglich ist. Wie die in den Tabellen aufgeführten Werte zeigen, ergibt sich eine sehr hohe Ausbeute an Synthesegas (CO, H2) von ca. 60 - 65 Vol%. Dies ist auch ein Zeichen dafür, daß die Wassergas-Shiftreaktion von H2O und CO zu H2 und CO2 bereits in der Reaktionskammer abläuft, wobei das benötigte Wasser durch feuchte Biomasse eingetragen wird. Mit großem Vorteil kann daher bei der erfindungsgemäßen Vorrichtung ein Trocknungsschritt unterbleiben.In general, very high volume fractions of hydrogen, methane and CO are achieved. A tin concentration of 5.3 * 10 -7 mg / Nm 3 was measured. No tar could be detected, so that the utilization of the product gas produced according to the invention in a gas engine is easily possible. As the values listed in the tables show, there is a very high yield of synthesis gas (CO, H 2 ) of about 60-65% by volume. This is also a sign that the water gas shift reaction of H 2 O and CO to H 2 and CO 2 already takes place in the reaction chamber, the required water being introduced by moist biomass. With great advantage can therefore be omitted in the apparatus according to the invention, a drying step.

BEZUGSZEICHENLISTELIST OF REFERENCE NUMBERS

11
Pyrolysevorrichtungpyrolysis
22
Reaktionskammerreaction chamber
33
Eintragsvorrichtungentry device
44
Prozeßgutprocess material
55
Produktableitungproduct withdrawal
66
Tauchrohrdip tube
77
Dosiervorrichtungmetering
88th
AbsperrvorrichtungShut-off
99
Heizvorrichtungheater
1010
Wärmeisolierungthermal insulation
1111
ProduktgasnachbehandlungsvorrichtungProduct gas after-treatment device
1212
Staubabscheiderdust collector
1313
Gaskühlergas cooler
1414
Kondensatabscheidercondensate
1515
chemische Gasreinigungchemical gas cleaning
1616
SiedesteinchenBoiling chips
1717
PyrolysegutvorratsbehälterPyrolysegutvorratsbehälter
1818
SchlaubeschquetschventilSchlaubeschquetschventil
1919
SchlauchquetschventilPinch
2020
Zwischenspeichercache
2121
Bodenflächefloor area
2222
Deckelflächecover surface
2323
FörderschneckeAuger
2424
Abtragsvorrichtungsubtractive
2525
Sensorsensor
2626
Presskuchenpress cake

Claims (8)

  1. A pyrolysis device (1), comprising a reaction chamber (2), an injection device (3) for process material (4), which is connected to the reaction chamber (2)) and comprising a product discharge line (5) which is connected to the reaction chamber (2),
    Whereby the reaction chamber (2) is containing a molten metal bath under operating conditions,
    Whereby the injection device (3) under operating conditions is injecting process material (4) almost in the absence of air into the molten metal bath contained in the reaction chamber (2),
    whereby the injection device (3) comprises at least one immersion tube (6), which is openly ending in the bottom region of the reaction chamber (2);
    the immersion tube (6) does not have any moving parts in the area of the reaction chamber (2),
    wherein the injection of the process material under operating conditions is gravity driven through the immersion pipe,
    whereby the injection device (3) comprises a dosing device (7) for dosing the process material injection into the immersion tube (6),
    whereby the injection device (3) has a gas tight cutoff device (8),
    whereby the dosing device (7) comprises a screw conveyor (23) and a discharge device (24), characterized in that the process material (4) forms the cutoff device (8) in the operating mode by forming a press cake, wherein the direction of conveyance of the screw conveyor (23) is in the opposite direction from the acting direction of the discharge device (24), and wherein a sensor (25) is arranged upstream from the screw conveyor (23) in the direction of conveyance, the discharge device (24) being embodied as a milling cutter.
  2. The pyrolysis device (1) according to claim 1, characterized in that the discharge device (24) passes through the screw shaft of the screw conveyor (23).
  3. The pyrolysis device (1) according to any one of the preceding claims, characterized in that the reaction chamber (2) is designed to be thermally regulable, in particular comprising a heating device (9) and/or thermal insulation (10).
  4. The pyrolysis device (1) according to any one of the preceding claims, characterized in that the product discharge line (5) comprises a product gas aftertreatment device (11), in particular one or more vacuum devices (12), gas coolers (13), condensate separators (14), chemical gas purification (15).
  5. A method for pyrolysis of carbon-containing pyrolysis material, wherein a metal bath is kept in a reaction chamber (2) in the absence of air, process material is entered continuously into the metal bath beneath its surface, and the input takes place without using any moving parts in the area of the metal bath, and wherein the process material passes through the metal bath from the location of the pyrolysis, to arrive at a product discharge line, wherein, before the process material is entered into the metal bath, the input of the process material takes place by gravity driven falling in the immersion tube, and wherein the process material forms an almost airtight closure of the input device by forming a press cake, in that a screw conveyor (23) has a conveying effect in the direction opposite the direction of action of a discharge device (24), wherein the discharge device (24) is embodied as a milling cutter, and the milling cutter mills and cuts the press cake.
  6. The method according to claim 5, wherein the rate of input of the pyrolysis material is in equilibrium with the rate of pyrolysis of the pyrolysis material.
  7. The method according to any one of claims 5 to 6, wherein the metal bath comprises boiling stones (16), in particular silicates.
  8. The method according to any one of claims 5 to 7, wherein the resulting product gas is processed, in particular being subjected to a catalytic water-gas shift reaction to produce hydrogen.
EP13710380.0A 2012-03-20 2013-03-14 Pyrolysis apparatus and process Not-in-force EP2828363B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012102324A DE102012102324A1 (en) 2012-03-20 2012-03-20 Pyrolysis device and method
PCT/EP2013/055263 WO2013139677A1 (en) 2012-03-20 2013-03-14 Pyrolysis apparatus and process

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EP2828363A1 EP2828363A1 (en) 2015-01-28
EP2828363B1 true EP2828363B1 (en) 2018-06-20

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DE (1) DE102012102324A1 (en)
WO (1) WO2013139677A1 (en)

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AT524054B1 (en) * 2021-02-23 2022-02-15 Radmat Ag Process for processing a non-metallic melt

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Publication number Priority date Publication date Assignee Title
FR688529A (en) * 1929-04-10 1930-08-26 Fuel distillation and gasification process
DE2304369C2 (en) * 1973-01-26 1974-12-12 Mannesmann Ag, 4000 Duesseldorf Method and device for the pyrolytic build-up of waste materials
JPS59124992A (en) * 1982-12-29 1984-07-19 Sankyo Yuki Kk Conversion of waste high-molecular weight compound to fuel
US5085738A (en) 1989-04-24 1992-02-04 Harris Windel L Method and apparatus for thermal conversion of organic matter
CA2140822A1 (en) * 1994-07-21 1996-01-22 Gary D. Schnittgrund Molten salt destruction of composite materials
DE102005053526A1 (en) 2005-11-08 2007-05-10 Müller, Horst Apparatus for producing fuel gas

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EP2828363A1 (en) 2015-01-28
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