WO2013139677A1 - Dispositif et procédé de pyrolyse - Google Patents

Dispositif et procédé de pyrolyse Download PDF

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Publication number
WO2013139677A1
WO2013139677A1 PCT/EP2013/055263 EP2013055263W WO2013139677A1 WO 2013139677 A1 WO2013139677 A1 WO 2013139677A1 EP 2013055263 W EP2013055263 W EP 2013055263W WO 2013139677 A1 WO2013139677 A1 WO 2013139677A1
Authority
WO
WIPO (PCT)
Prior art keywords
pyrolysis
reaction chamber
process material
gas
entry
Prior art date
Application number
PCT/EP2013/055263
Other languages
German (de)
English (en)
Inventor
Horst Müller
Original Assignee
Mueller Horst
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mueller Horst filed Critical Mueller Horst
Priority to EP13710380.0A priority Critical patent/EP2828363B1/fr
Publication of WO2013139677A1 publication Critical patent/WO2013139677A1/fr

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Classifications

    • 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, comprising a reaction chamber, a process material entry device into the reaction chamber and a product discharge, wherein the
  • Reaction chamber containing a molten metal under operating conditions and wherein the entry device process material in the operating conditions contained in the reaction chamber molten metal is almost entering the absence of air.
  • the pyrolytic transformation proceeds through different and complex chemical reactions, which are not all clarified in detail.
  • Wood vinegar 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, since tars condense at temperatures below about 200 ° C and enforce piping, or
  • Operating state contains a tin bath, is passed through the exclusion of air by means of a screw conveyor dried wood.
  • 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 achieved relatively long contact times between pyrolysis and tin bath and thus a tarerarmes, high calorific value
  • 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.
  • Transition region is located to a re-rising 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 Bleibad can not rise to the piston, if no pyrolysis product is conveyed.
  • a disadvantage of this prior art is the cumbersome and unsafe Pyrolysegutzubow.
  • a device for the pyrolytic degradation of industrial or household waste in which they are immersed in a molten metal in a reaction vessel, in particular pig iron, continuously, for which purpose 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 In the dip tube, a movable piston
  • Entry device at least one near the ground of the
  • Reaction chamber has open ended dip tube, the
  • Immersion tube in the region of the reaction chamber has no moving parts.
  • carbonaceous material such as wood, wood-based materials, Straw, by-products and residues of agriculture and forestry as well as the wood-processing craft, but also plastics, car tires, electronic waste, sewage sludge or river excavation (silt) with
  • 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.
  • 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, existing example of a ceramic dip tube is sufficient to enter the process material.
  • Entry device a metering device for dosing the
  • a metering device 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 could for example be a screw, a membrane, a folding device or the like, but according to the invention it is preferably a rotary valve with sufficiently large Zellkompartimenten or a Kollerrad with or without Ringmatrize, as it is known from Pelletiermaschienen. Generally, rotary, compartmented feeders are preferred.
  • the invention is also to provide 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. It is also conceivable
  • 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. If the metering device already ensures sufficient gastightness, the shut-off device according to the invention can be dispensed with. This further simplifies the design effort. 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, though desirable, as it inter alia
  • the process material in a supply line to the dip tube is compressed propfartig.
  • 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.
  • the invention further provides that the
  • Effective direction of the removal device is directed and 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 promotes that
  • 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 adjust the degree of filling of the screw. The promotion takes place against the resistance of the
  • 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
  • the removal device is designed as a milling cutter and in particular the worm shaft of the screw conveyor is penetrating.
  • 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.
  • 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.
  • Reaction chamber is designed to be tempered, in particular has a heating device and / or a thermal insulation. This is needed to keep the metal bath at its working temperature, to reach it or another, especially higher,
  • 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 purification, it is advantageously ensured on the one hand that only highly pure product gas leaves the device according to the invention, and on the other hand
  • Biomass is used.
  • the process task becomes pyrolysis in a process
  • the product gas obtained is processed and recycled, in particular a hydrogen-producing catalytic water gas shift reaction
  • Fig. 1 shows a schematic sketch of the device according to the invention
  • Fig. 2 shows a detail in the region of the dip tube
  • Fig. 3 shows a detail of the metering device in another embodiment.
  • 1 shows a pyrolysis device 1 according to the invention. This can be on the product gas side with smaller combined heat and power plants in the
  • Kept in stock for example wood, wood pellets,
  • 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
  • Pyrolysegutvorrats employer 17 passes the pyrolysis over pipelines to the entry device 3. This consists in this embodiment of the invention of a downpipe which in the direction of the pipe to
  • Pyrolysegutvorrats employer 17 is completed gas-tight. This gas-tight closure is achieved here by two spaced-apart in the feed direction pneumatic Schlauchquetschventile 18, 19, which define a buffer 20 for pyrolysis between them. The pyrolysis reaches after the second
  • the dip tube 6 takes the pyrolysis in portions in compartments or pockets and transfers it by rotation about an example orthogonal to the conveying direction oriented axis of rotation in the dip tube 6.
  • the dip tube 6 is described in Fig. 2 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 Heat insulation 10 and a heater 9 on, both are only sketched on one side.
  • 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 type of heater 9 is only relevant insofar as it must generate temperatures of at least 800 ° C in the reaction chamber 2 and must be able to ensure lasting.
  • Operating temperature of the reaction chamber 2 may according to the invention, however, also 900 ° C or significantly higher. That from the
  • Heating gas liberated from 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 area of the lid surface 22 of the reaction space 2 is a
  • Product gas discharge 4 arranged. This is a maximum distance from the exit surface of the dip tube and the entrance surface of the
  • 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, and if necessary, a gas cooler 13 may be provided thermal and material recycling. Since the product gas is highly CO-containing, it can be suitably robust
  • Catalysts CO 2 and H 2 are generated. It is particularly advantageous that moist biomass according to the invention can be used, which can provide the water required for this reaction. With great advantage, a drying step of the biomass before pyrolysis can be omitted. This improves the energetic
  • This dip tube 6 protrudes more or less perpendicularly from above into the cylindrical reaction space 2 and ends slightly above its 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.
  • a cooling is provided in addition to an optionally existing seal, so that its heat does not impart the above arranged components such as the metering device 7 or the pinch valves 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.
  • 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 can also be used per reaction space 2
  • Immersion tube 6 may be provided, for example, two or three, to allow a more homogeneous entry.
  • a vertically as possible vertically extending dip tube 6 is preferred, since in this the process material gravity-driven free from the metering device 7 on the
  • Tin surface can fall. It is also according to the invention, when the passage area of the dip tube 6 and the bottom surface of the
  • Reaction space 2 include 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 how the final geometry of the dip tube 6 looks, it must be ensured that no
  • Process material layer can build up on the tin surface
  • trailing material is blocked and interrupts the gasification and pyrolysis process through voids formation.
  • FIG. 3 again shows schematically and not to scale a particularly preferred 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 C0 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.
  • Conveying screw 23 promotes towards the dip tube 6.
  • the Drives for screw conveyor and removal device 24 are not shown.
  • the worm shaft is through a wave of
  • Abtragsvorraum 24 passes through, here a router.
  • 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 that forms a press cake or plug 26 before him.
  • 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 .
  • Hot spots or short circuit currents are avoided as well as the need for thermal and metallurgical
  • the device according to the invention and the method are easy to automate and user-friendly.
  • the tin used has only a vapor pressure of 1 * 10 "4 mbar at an operating temperature of 900 ° C, so that it is extremely suitable and has a long service life
  • exemplary pyrolysis was as pyrolysis bovine manure
  • Reaction chamber runs wherein the required water is introduced by wet biomass. With great advantage can therefore be omitted in the apparatus according to the invention, a drying step.

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

Abstract

La présente invention concerne un dispositif de pyrolyse (1) présentant une chambre de réaction (2), un dispositif d'introduction (3) relié à la chambre de réaction (2) pour le produit à traiter (4) et une conduite d'évacuation (5) de produit reliée à la chambre de réaction (2). Dans les conditions de fonctionnement, la chambre de réaction (2) contient une masse fondue métallique. Le dispositif d'introduction (3) introduit quasiment à l'abri de l'air le produit à traiter (4) dans la masse fondue métallique contenue dans les conditions de réaction dans la chambre de réaction (2). L'invention est caractérisée en ce que le dispositif d'introduction (3) présente au moins un tube plongeant (6) ouvert se terminant dans une zone à proximité du fond de la chambre de réaction (2), le tube plongeant (6) ne présentant pas de pièces mobiles dans la zone de la chambre de réaction (2). Elle concerne en outre un procédé correspondant.
PCT/EP2013/055263 2012-03-20 2013-03-14 Dispositif et procédé de pyrolyse WO2013139677A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13710380.0A EP2828363B1 (fr) 2012-03-20 2013-03-14 Dispositif et procédé de pyrolyse

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012102324.7 2012-03-20
DE102012102324A DE102012102324A1 (de) 2012-03-20 2012-03-20 Pyrolysevorrichtung und -verfahren

Publications (1)

Publication Number Publication Date
WO2013139677A1 true WO2013139677A1 (fr) 2013-09-26

Family

ID=47901083

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Application Number Title Priority Date Filing Date
PCT/EP2013/055263 WO2013139677A1 (fr) 2012-03-20 2013-03-14 Dispositif et procédé de pyrolyse

Country Status (3)

Country Link
EP (1) EP2828363B1 (fr)
DE (1) DE102012102324A1 (fr)
WO (1) WO2013139677A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT524054A4 (de) * 2021-02-23 2022-02-15 Radmat Ag Verfahren zum Verarbeiten einer nichtmetallischen Schmelze

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR688529A (fr) * 1929-04-10 1930-08-26 Procédé de distillation et de gazéification de combustibles
DE2304369B1 (de) * 1973-01-26 1974-05-09 Mannesmann Ag, 4000 Duesseldorf Verfahren und Vorrichtung zum pyrolytischen Aufbau von Abfallstoffen
JPS59124992A (ja) * 1982-12-29 1984-07-19 Sankyo Yuki Kk 廃合成高分子化合物の燃料化方法
EP0693305A1 (fr) * 1994-07-21 1996-01-24 Rockwell International Corporation Destruction par sel fondu de matériaux composites

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085738A (en) 1989-04-24 1992-02-04 Harris Windel L Method and apparatus for thermal conversion of organic matter
DE102005053526A1 (de) 2005-11-08 2007-05-10 Müller, Horst Vorrichtung zur Erzeugung von Brenngas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR688529A (fr) * 1929-04-10 1930-08-26 Procédé de distillation et de gazéification de combustibles
DE2304369B1 (de) * 1973-01-26 1974-05-09 Mannesmann Ag, 4000 Duesseldorf Verfahren und Vorrichtung zum pyrolytischen Aufbau von Abfallstoffen
JPS59124992A (ja) * 1982-12-29 1984-07-19 Sankyo Yuki Kk 廃合成高分子化合物の燃料化方法
EP0693305A1 (fr) * 1994-07-21 1996-01-24 Rockwell International Corporation Destruction par sel fondu de matériaux composites

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT524054A4 (de) * 2021-02-23 2022-02-15 Radmat Ag Verfahren zum Verarbeiten einer nichtmetallischen Schmelze
AT524054B1 (de) * 2021-02-23 2022-02-15 Radmat Ag Verfahren zum Verarbeiten einer nichtmetallischen Schmelze

Also Published As

Publication number Publication date
EP2828363B1 (fr) 2018-06-20
EP2828363A1 (fr) 2015-01-28
DE102012102324A1 (de) 2013-09-26

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