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EP 0 975 394 B1 |
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EUROPEAN PATENT SPECIFICATION |
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Mention of the grant of the patent: |
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26.06.2002 Bulletin 2002/26 |
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Date of filing: 10.04.1997 |
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International application number: |
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PCT/EP9701/797 |
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International publication number: |
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WO 9844/992 (15.10.1998 Gazette 1998/41) |
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PROCESS FOR THERMAL DESTRUCTION OF HAZARDOUS MATERIALS
VERFAHREN ZUR THERMISCHEN ZERSETZUNG VON SCHADSTOFFEN
PROCEDE DE DESTRUCTION THERMIQUE DE MATIERES DANGEREUSES
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Designated Contracting States: |
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AT BE CH DE DK ES FI FR GB LI SE |
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Date of publication of application: |
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02.02.2000 Bulletin 2000/05 |
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Proprietor: Acciai Speciali Terni S.p.A. |
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05100 Terni (IT) |
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Inventors: |
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- REPETTO, Eugenio
I-05100 Terni (IT)
- CAPODILUPO, Domenico
I-00040 Pomezia (IT)
- DULCETTI, Alessandro
I-00040 Rome (IT)
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Representative: Gervasi, Gemma, Dr. |
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Studio Brevetti e Marchi
NOTARBARTOLO & GERVASI S.r.l.,
Corso di Porta Vittoria, 9 20122 Milano 20122 Milano (IT) |
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References cited: :
EP-A- 0 713 054 FR-A- 2 689 213
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WO-A-95/04004 US-A- 4 574 714
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| Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
|
FIELD OF INVENTION
[0001] The present invention refers to a process for eliminating hazardous materials, and
more in particular regards a process for the thermal destruction of hazardous compounds,
in particular of organic nature, for example, chlorinated compounds, such as PCBs,
and materials polluted by such compounds. The invention moreover refers to a device
that is deemed to be optimal for carrying out said process.
STATE OF THE ART
[0002] Industry uses, or produces as residue or by-products, compounds which are very harmful
for the environment and for human health and which by now have accumulated in such
large quantities that an adequate disposal thereof has become necessary.
[0003] Many of such substances are moreover particularly stable, so that it is not possible
to rely on their spontaneous degradation to form harmless, or at least less dangerous,
products; indeed, frequently their products of scission are also extremely harmful.
This is the case with a large number of chlorinated organic compounds, which give
rise to dioxin or similar molecules.
[0004] The storage of such substances in dumps that are purposely designed and protected
is extremely costly and does not eliminate, but only shifts in time, the danger deriving
from their introduction into the environment. Furthermore, even such specially designed
dumps are subject to such calamities as floods and earthquakes, and/or are subject
to possible trespassing and/or the setting-up of conditions that may prove aggressive
for the containers of the stored substances.
[0005] It is therefore evident that storage is not a definitive and fully acceptable solution,
and that it is necessary to devise other solutions, if possible definitive ones, among
which particularly interesting ones are destruction or inertization by means of special
processes.
[0006] In the field of chlorinated aromatic compounds, techniques of thermic destruction
based on the use of special burners have been since now developed. Experience has,
however, shown such techniques to lack validity, in that, due to the relatively low
temperatures reached during combustion, the intermediate products of reaction recombine,
giving rise to other products that are no less aggressive, such as dioxin.
[0007] For this reason, low-temperature electro-chemical methods have been developed (typically
of around 100-200°C), which transform the harmful products into residues presenting
lower danger levels; these, however, must subsequently be sent on to special dumps.
In addition, these methods are effective only when the pollutant is present in low
concentrations, which, in the case of PCBs, must not exceed 30-40%.
[0008] It has therefore been proposed to use furnaces employing plasma torches as heat source.
The extremely high temperatures reached by plasma, i.e., over 5000°C, would ensure
complete cracking of the pollutant into molecules which are very simple and cannot
recombine to form particularly harmful products that are difficult to deal with.
[0009] US Patent 4.574.714 describes the use of a furnace containing a metal charge which
is melted and brought to a desired temperature by any means, such as induction heating,
electric arc, oxygen blowing and the like; the external source of heath is then turned
off and the waste material introduced with oxygen below the surface of the molten
bath. The high temperature of the bath (2500-4000 °F) dissociates the organic molecules
and the carbon thus released is oxidised to CO and CO
2.
[0010] Such techniques, however, are slow in asserting themselves, basically because they
do not guarantee that the pollutants are exposed to the high temperatures of the plasma
for periods of time sufficiently long to ensure their complete destruction. In addition,
plasma techniques are still somewhat costly, and the means necessary are delicate
and difficult to maintain.
SUMMARY OF THE INVENTION
[0011] A purpose of present invention is thus to provide a reliable process for destroying
hazardous compounds, in particular those of organic nature, such as chlorinated aromatic
molecules, like PCBs.
[0012] Another purpose of this invention is also to guarantee that these pollutants, whether
gaseous, liquid, or solid, will be completely eliminated even in concentrations of
up to 100%.
[0013] Another purpose of the invention is to provide a simple and reliable device, operating
with consolidated technologies, for putting the process into practice according to
the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The process for the thermal destruction of hazardous materials according to the present
invention is characterized in claim 1.
[0015] The ratio between the internal free volume of the furnace and the volume of the metal
bath is preferably between 5:1 and 2:1. By "internal free volume inside of the furnace"
is meant the internal volume of the furnace that is not occupied by the metal bath
or by components such as electrodes, slag, and the like, i.e., the volume that is
effectively available for the gases developed by combustion of the materials to be
destroyed. A high value of this ratio allows said combustion gases to remain inside
the furnace, subjected to the action of intense heating of the electric arc, of the
metal bath and of the walls of the furnace itself, for a sufficiently long time to
guarantee their reduction into innocuous or elementary gases. This time in which the
gases remain inside the furnace is in excess of 3 seconds, and preferably over 6 seconds
or, even more preferably, is between 8 and 15 seconds.
[0016] The furnace is obviously devised in such a way as to prevent any leakage of harmful
gases; for example, it can be sealed, or preferably work in negative pressure. The
material to be destroyed, which may be liquid, gaseous, or solid (in small-sized pieces),
is directly fed into the area of the electric arc, where there exist plasma conditions
or conditions that may be plasma-like, through an electrode having an axial hole in
which there is inserted, in such a way as to be free to move, a special lance that
can, if necessary, be cooled. Alternatively, if the material to be destroyed is in
solid form, in pieces of sizes that are too large to be introduced through the electrode,
it can be fed in the furnace, using special means of loading, directly into the molten
bath.
[0017] It is preferable to create specifically in the electric arc area a true plasma by
feeding in a suitable gas, for example nitrogen or argon, through an annular passage
created between the internal walls of the electrode, provided with an axial hole,
and the external walls of the lance that can move freely inside the electrode.
[0018] The combined action of the arc, the molten bath and the walls of the furnace guarantees
both a particularly high treatment temperature and an exposure time that is amply
sufficient, as mentioned above, for the complete dissociation of the materials to
be treated according to the invention.
[0019] Preferably, inside the furnace an oxidizing atmosphere is generated by sending in
air or oxygen to favour the transformation of the residue of combustion of the materials
being treated into innocuous compounds or anyway compounds that may readily be treated
using normal chemical means.
[0020] In the case where, due to the complexity or to the general characteristics of the
molecules to be destroyed reasonable doubts could be raised with reference to adequacy
of treatment times, it is possible to use means, such as the so-called foamed slags,
which trap within them the gases developed by the thermal destruction of the materials
being treated, slowing down their path towards the outlet from the furnace, and it
is thus possible to increase the control over the necessary treatment for eliminating
some of the outgoing materials, such as particulate, hydrochloric acid, and the like.
[0021] The device that allows the embodiment of the process according to the present invention
is an ordinary electric-arc furnace, as used in steelmaking, suitably modified, by
means of gas-tight sealing or operation in negative pressure, to prevent any gas leakage
into the environment, and is characterized by the use of at least one electrode having
an axial hole and carrying in said hole a cooled metal lance that is free to move
axially for feeding in the material to be treated.
[0022] It is also possible to make an annular passage between said holed electrode and said
lance that is free to move in said hole in order to introduce into the arc zone also
a gas suitable for the formation of a plasma.
[0023] Preferably this electrode has a mixed structure, with the lower part, which is closer
to the molten bath and is expendable, made of graphite, and with the upper part made
of metal and cooled by water.
[0024] The furnace may also communicate with a gas-tight chamber equipped with devices for
feeding into the furnace the materials that are to be treated, if these are solid
and are of such a size or consistency as to prevent their introduction through the
lance.
[0025] The furnace according to the invention may be of the direct-current, single-electrode
type and with conductive hearth.
1. Process for the thermal destruction of hazardous materials, in which said materials
are exposed in a furnace to radiant heat from the metal bath and from furnace walls,
characterised in that the material itself is introduced into the electric arc of an operating electric
arc furnace of the type used in steel making, which contains a molten metal bath,
for example cast iron or steel having a temperature of above 1300°C, and in the internal
free volume of said furnace the gases resulting from combustion of said material are
exposed to the irradiating action of mainly the electric arc, for a time above 3 seconds.
2. Process according to claim 1, characterised in that in the area of the electric arc plasma conditions are created by feeding a suitable
gas.
3. Process according to claim 1, characterised in that the material to be treated is fed through a lance which is introduced axially and
is free to move inside a hollow electrode used to form said electric arc.
4. Process according to claim 2, characterised in that said gas is chosen from between nitrogen and argon and is fed in through an annular
passage defined between the internal walls of said hollow electrode and the external
walls of said lance.
5. Process according to claim 1, characterised in that said time is in excess of 6 seconds, and preferably between 8 and 15 seconds.
6. Device for thermal destruction of toxic-harmful materials, consisting of an electric-arc
furnace of the type used in steelmaking, sealed or operated in negative pressure to
prevent any gas leakage into the environment, characterised by the use, to form the electric arc, of at least one electrode having an axial hole
and bearing in said hole a metal lance that is free to move axially for feeding the
material to be treated directly into the area of the electric arc.
7. Device according to Claim 6, characterised by the presence between the holed electrode and the lance that can move freely inside
the electrode, of an annular passage for feeding into the area of the electric arc
a suitable gas for the formation of a plasma.
8. Device according to Claim 6, characterised in that said electrode has a mixed structure, with the lower part, which is closer to the
molten metal bath and is expendable, made of graphite, and with the upper part made
of metal and cooled by water.
9. Device according to Claim 6, characterised in that it is further equipped with a gas-tight chamber communicating with the inside of
the furnace, equipped with devices for feeding into the furnace solid materials that
are to undergo treatment.
1. Verfahren zur thermischen Zersetzung gefährlicher Stoffe, worin die Stoffe in einem
Ofen der Wärmestrahlung aus einem Metallbad und aus den Ofenwänden ausgesetzt werden,
dadurch gekennzeichnet, daß der Stoff selbst in den Lichtbogen eines in Betrieb befindlichen Lichtbogenofens
des Typs eingeführt wird, der bei der Stahlherstellung verwendet wird und ein geschmolzenes
Metallbad enthält, z.B. Gußeisen oder Stahl mit einer Temperatur von über 1.300°C,
und daß im inneren freien Volumen des Ofens die aus der Verbrennung des Stoffes resultierenden
Gase der Strahlungswirkung hauptsächlich des Lichtbogens für eine Dauer von mehr als
3 Sekunden ausgesetzt werden.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß im Bereich des Lichtbogens Plasmabedingungen durch Zuführen eines geeigneten Gases
geschaffen werden.
3. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß der zu behandelnde Stoff durch eine Lanze zugeführt wird, die axial eingeführt wird
und sich frei innerhalb einer hohlen Elektrode bewegen kann, die zur Bildung des Lichtbogens
verwendet wird.
4. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß das Gas aus St-ickstoff und Argon ausgewählt wird und durch einen ringförmigen Durchgang
zugeführt wird, der zwischen den Innenwänden der hohlen Elektrode und den Außenwänden
der Lanze definiert wird.
5. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die Dauer mehr als 6 Sekunden und bevorzugt zwischen 8 und 15 Sekunden beträgt.
6. Vorrichtung zur thermischen Zersetzung toxischschädlicher Stoffe, die aus einem Lichtbogenofen
des Typs besteht, der bei der Stahlherstellung verwendet wird, versiegelt oder unter
negativem Druck betrieben, um eine etwaige Gasleckage in die Umgebung zu verhindern,
gekennzeichnet durch die Verwendung, zur Bildung des Lichtbogens, wenigstens einer Elektrode mit einem
axialen Loch, die in dem Loch eine Metalllanze führt, die sich axial frei bewegen
kann, um den zu behandelnden Stoff direkt in den Bereich des Lichtbogens zu führen.
7. Vorrichtung gemäß Anspruch 6, gekennzeichnet durch das Vorhandensein eines ringförmigen Durchgangs zwischen der hohlen Elektrode und
der Lanze, die sich frei innerhalb der Elektrode bewegen kann, zur Zufuhr eines geeigneten
Gases zur Bildung eines Plasmas in dem Bereich des Lichtbogens.
8. Vorrichtung gemäß Anspruch 6, dadurch gekennzeichnet, daß die Elektrode eine Mischstruktur aufweist, wobei der untere Teil, der sich näher
zum geschmolzenen Metallbad befindet und entbehrlich ist, aus Graphit hergestellt
ist, und der obere aus Metall hergestellt ist und durch Wasser gekühlt ist.
9. Vorrichtung gemäß Anspruch 6, dadurch gekennzeichnet, daß sie ferner mit einer gasdichten Kammer ausgerüstet ist, die mit dem Inneren des Ofens
in Verbindung steht, ausgerüstet mit Vorrichtungen zur Zufuhr fester Stoffe, die die
Behandlung erfahren sollen, in den Ofen.
1. Procédé pour la destruction de matières dangereuses, dans lequel lesdites matières
sont exposées dans un four à la chaleur radiante du bain de métal et des parois, caractérisé en ce que la matière elle-même est introduite dans l'arc électrique d'un four à arc électrique
du type utilisé dans la fabrication de l'acier, qui contient un bain de métal fondu,
par exemple de fonte ou d'acier ayant une température supérieure à 1.300°C, et dans
le volume interne libre duquel four les gaz provenant de la combustion de ladite matière
sont exposés à l'action irradiante principalement de l'arc électrique, pendant une
période de temps supérieure à 3 secondes.
2. Procédé selon la revendication 1, caractérisé en ce que des conditions de plasma sont créées dans la zone de l'arc électrique par apport
d'un gaz approprié.
3. Procédé selon la revendication 1, caractérisé en ce que la matière à traiter est introduite par une lance qui est engagée axialement et est
libre de se déplacer à l'intérieur d'une électrode creuse utilisée pour former ledit
arc électrique.
4. Procédé selon la revendication 2, caractérisé en ce que ledit gaz est choisi parmi l'azote et l'argon et est introduit par un passage annulaire
défini entre les parois internes de ladite électrode creuse et les parois externes
de ladite lance.
5. Procedé selon la revendication 1, caractérisé en ce que ladite période de temps est supérieure à 6 secondes et de préférence entre 8 et 15
secondes.
6. Dispositif pour la destruction thermique de matières toxiques nuisibles, constitué
d'un four à arc électrique du type utilisé dans la fabrication de l'acier, scellé
ou fonctionnant sous pression négative pour empêcher toute fuite de gaz dans l'environnement,
caractérisé par l'utilisation, pour former un arc électrique, d'au moins une électrode ayant un trou
axial et portant dans ledit trou une lance de métal qui est libre de se déplacer axialement
pour introduire la matière à traiter directement dans la zone de l'arc électrique.
7. Dispositif selon la revendication 6, caractérisé par la présence, entre l'électrode creuse et la lance qui peut être déplacée librement
à l'intérieur de l'électrode, d'un passage annulaire pour introduire un gaz approprié
à la formation du plasma dans la zone de l'arc électrique.
8. Dispositif selon la revendication 6, caractérisé en ce que ladite électrode a une structure mixte, la partie inférieure qui est plus proche
du bain de métal fondu et est extensible, étant faite en graphite, et la partie supérieure
étant faite en métal et refroidie par eau.
9. Dispositif selon la revendication 6, caractérisé en ce qu'il est en outre équipé d'une chambre étanche aux gaz communiquant avec l'intérieur
du four, équipé de dispositifs pour introduire dans le four des matières solides qui
doivent subir le traitement.