The present invention relates to an innovative pyrolysis device of the microwave-type for the disposal of polymeric materials, especially at end of life, such as, in particular, end-of-life tires (often and notoriously designated by the acronym ELT), and dedicated to the recovery of component materials.
It is firstly worth noting that pyrolysis (or cracking) is a thermochemical decomposition process of organic materials obtained by applying heat in the complete absence of an oxidizing agent (normally oxygen).
In essence, by heating the material in the presence of oxygen, a combustion occurs which generates heat and, negatively or at least problematically, which produces oxidized gaseous compounds; conversely, by performing the same heating in conditions of total absence of oxygen, the material undergoes a breakdown of the original chemical bonds with the formation of simpler molecules.
One of the main pyrolysis processes currently exploited on a large scale is that defined in industrial chemistry as cracking (process means of which light paraffin hydrocarbons are obtained due to the breaking of heavy paraffin hydrocarbon molecules), as well as the thermal treatment of waste by exploiting, in this case, temperatures between 400° C. and 800° C. (typically 500-600° C.).
In particular, waste pyrolysis converts the material to be treated from solid state (so-called char component) into liquid products (so-called tar or pyrolysis oils) and/or gaseous products (syngas), which can be used as fuel or as raw materials intended for successive chemical processes. The solid carbonaceous residue which is obtained can be further refined by providing products such as, for example, activated charcoal.
As known, the management of large amounts of waste has become an environmental issue of huge proportions and so the strategy adopted by European Community (or European Union) lawmakers for waste management is to consider waste disposal, however appropriate and effectively performed, to be taken into account only as the last resort.
Lawmakers, particularly on European Community level, firstly encourage waste reduction at the source, which means using prevention to minimize the production of waste and, alternatively, reuse in original form, recycling and recovery of materials and energy.
For used tires, for example, reuse in original form (either directly or following rebuilding pretreatments) is currently considered the Best Practicable Environmental Option in the waste management hierarchy.
However, due to the increasingly widespread use of low-profile, high-performance tires (required to meet the needs of driving stability in bad or extreme weather conditions), the average life of tires is significantly decreasing, with consequent increase of the amount intended for disposal, and an ever-greater portion of used tires appears inadequate for rebuilding or for total recovery by recycling.
Reference will be precisely made hereinafter to this because, contrarily to other types of waste (such as, for example, glass, packaging, metals and paper), used tires are difficult to recycle: the complete recycling of used tires—i.e. the operation which includes industrially processing used tires to produce new ones—is not currently achievable.
When tires can no longer be used as such or intended to be rebuilt, they must inevitably be disposed of as waste.
Indeed, the disposal of ELTs in landfills has been banned in Italy since 2006 (by means of Legislative Decree 152/2006 which transposes European Community Directive 199/31/EC); so, for example in Italy, for over a decade, end-of-life tires have been partially reused—cut or whole—for various applications or, by processing them by thermal treatment, are exploited for the recovery of materials and/or energy. Tires are made of materials which may be notoriously reused in new production processes.
By virtue of industrial tire cutting and granulation processes (e.g. mechanical crushing or cryogenic processes, electrothermal processes), it is possible to separate the various components (rubber, steel and fiber), thus obtaining a material which can be used in different manners: tiles, soundproofing panels, sports surfaces, shoe soles, wheels for forklift trucks, road paving and components for cars, just to mention some of the most common and known applications.
However, this operative solution allows disposing of only some of the tires which cannot be rebuilt, i.e. precisely those called ELTs.
An alternative to this is represented by the recovery of materials and/or energy by means of thermal treatments, such as, typically and generally, incineration, waste-to-energy (i.e. incineration with energy recovery) or pyrolysis, performed on ELTs. The first of such thermal treatments, i.e. incineration, includes the use of incinerators in waste management, with a view to disposal, which employ a high-temperature combustion process which provides, as final products, gaseous effluent, ashes and dust.
As a function of the specific technology used in the respective combustion chamber, it is possible to distinguish various types of incinerators, such as, for example, grid incinerators which have a combustion chamber in which movable or fixed metal grids are used (the material combustion occurs above them).
Such an operating solution of known type has some recognized disadvantages and drawbacks, in particular:
As regards thermal treatment of waste to energy, instead, according to the waste management hierarchy defined by European Directive 2008/98/EC, incineration with high-efficiency energy recovery is placed on the fourth level of priority after prevention, preparation for reuse and recovery of materials, while it precedes final disposal in controlled landfills.
As known, in the most modern incineration plants (waste-to-energy plants), the heat developed during waste combustion is recovered and used to produce steam.
It is worth emphasizing that, as regards waste in general, waste-to-energy is a little used disposal type due to the low calorific value of the waste, to the extent of making it unattractive because it is not very efficient.
The features making an end-of-life tire an excellent source of energy recovery are, instead, precisely ease of combustion and high calorific value (comparable to that of coal).
For this reason, the most widely used application of this type of ELT disposal is that which produces fuel for cement works or furnaces for the production of steam.
The disadvantages of this operating solution for ELT disposal the same as those of the previously described solution which includes resorting to incinerators, because a waste-to-energy plant is nothing other than an implemented version of an incinerator, with the sole and exclusive advantage of energy recovery.
In relation to the pyrolysis thermal treatment, it is worth noting that the disposal of the ELTs by means of pyrolysis consists in a thermal decomposition in inert atmosphere, obtained by indirect heating, after which, for example, the tires undergo thermal cracking at temperatures of about 500/600° C., breaking down, as already pointed out above, into a solid component (char), a liquid part (tar or pyrolysis oils) and a gaseous, partially condensable one (syngas).
The pyrolysis products may be used, in turn, to feed plants which exploit combustion processes or can be used as raw materials for other processes.
Therefore, this type of process has the features to transform polymeric materials into products adapted for the production of energy or petrochemical raw materials. In pyrolysis plants, heating is performed in the total absence of oxygen, unlike incinerators, and the processed material thus undergoes the cracking of original chemical bonds with the formation of simpler molecules.
This points to a major advantage in the use of pyrolysis plants consisting in the absence of nanoparticles, unburned fumes, dioxins or whatever else is created in the plants described above, which must be accompanied by adequate (and expensive) technological plant abatement solutions.
The fundamental part of each pyrolysis apparatus currently available on the market resides in the reactor (or heating means) in which the produced heat is transferred from the source to the material.
Many types of pyrolysis apparatus reactors (or devices) are currently available. The main ones will list below, focusing on the disadvantages thereof.
First of all, the autoclave is available—notoriously, a vessel or appliance provided with a hermetic sealing system, in which the positive pressure difference between the inside and the outside of the vessel facilitates the sealing—the main drawback of which lies in the fact that heat transfer is not effective.
It is then mentioned rotary kiln (having a cylindrical shape and generally supported on rolling rollers) used in various industrial applications and in particular as a pyrolysis appliance reactor in the field of waste disposal; the main drawbacks or disadvantages of such an ELTs heating system consist in:
The prior art of interest herein also comprises pyrolysis devices with so-called static bed (or fixed) reactor, the most relevant disadvantages or drawbacks of which are:
Alternatively, in the background art, pyrolysis devices are available provided with so-called fluidized bed reactor, which however has the following drawbacks:
From that briefly outlined above, it can be inferred that that the only applications used so far on a large industrial scale provide that the pyrolysis process for ELT disposal is mostly performed by conventional heating and, in short, adversely require:
Additionally, ELTs recovery by reuse of its compounds, obtained from processes such as pyrolysis, continues to struggle to take off because it strongly suffers also from the high processing costs required by the heat treatment processes described above. Incidentally, patent application published under WO2012/220991 A1 describes an ELTs pyrolysis process which, by exploiting heating by microwaves of the material to be treated, appears potentially very interesting.
Therefore, the present invention suggests to remedy fully and effectively the aforesaid disadvantages suffered by the prior art considered hereto, the present invention suggests to effectively overcome such drawbacks.
In particular, it is a primary object of the present invention to provide an industrial pyrolysis device for the disposal of polymers and in particular of end-of-life tires, which with respect to the known pyrolysis devices used for the same function either eliminates or at least considerably reduces the difficulties in heat transfer to the material to be treated.
Within the scope of this object, it is the task of the invention to devise an industrial pyrolysis device (or apparatus) for the disposal of polymers and in particular of end-of-life tires, which has an efficiency, in the thermal treatment of the material, typically of the one or more end-of-life tires, higher than that of the devices of the prior art.
In other words, it is the object of the invention to provide an industrial pyrolysis device (or apparatus) for the disposal of polymers and in particular of end-of-life tires, which allows heating the material to be treated more efficiently than the devices of the prior art comparable thereto in some measure.
It is a further object of the present invention to suggest an industrial pyrolysis device (or apparatus) for the disposal of polymers and in particular of end-of-life tires, which includes shorter reaction times of the material to be treated than those which can be encountered in the devices of known type.
In the cognitive scope of such a second object, it is the task of the invention to provide an industrial pyrolysis device (or apparatus) for the disposal of polymers, and in particular of end-of-life tires, which, with respect to the closer prior art, allows reducing production cost, the factors involved in the calculation of such a cost, such as labor and the raw materials used for the construction thereof, being equal.
It is a last but not least object of the present invention to provide an industrial pyrolysis device (or apparatus), for use in particular for the disposal of end-of-life tires, which can be manufactured at sustainable costs and which has a competitive sales price.
Said objects are achieved by a pyrolysis device according to appended claim 1, to which reference is made for brevity.
Further detailed technical features of the pyrolysis device of the present invention are contained in the respective dependent claims.
The aforesaid claims, hereinafter specifically and concretely defined, are an integral part of the present description.
Advantageously, in light of the fact that the pyrolysis process is a promising solution in the perspective of disposal of polymers, and of ELTs in particular, and in the perspective of recovery of the materials which form such products, the innovative pyrolysis device of the present invention intends to overcome the criticalities of the conventional heating methods described above, by using one or more microwave sources as means for heating the material to be treated.
Experimentally, the pyrolysis process of polymers and of ELTs, in particular by means of microwave heating sources, has already been studied, highlighting considerable advantages with respect to conventional methods, such as:
The features and conformation of the industrial device designed and disclosed herein allow extending and applying the scientific study (underlying the aforementioned patent application WO2012/220991 A1) to a device (or apparatus) which can be manufactured and provided on large scale, while maintaining of the advantages described in the experiment but with the possibility of performing a pyrolysis process even on large amounts and on large-size parts of material to be processed (e.g., simultaneously even on multiple, whole end-of-life tires).
This is possible by virtue of the ideation of an innovative launch system of the heating microwaves inside the reactor, of a pyrolysis chamber structure designed to maintain radiation homogeneity inside, by closing (or compartmenting) systems of the process zones designed to maintain both the features required by the process itself and safety as regards the environment created inside the reactor.
Equally advantageously, due to the constructional features generally outlined here, the pyrolysis device of the invention optimizes the heat transfer from the specific heating sources of the microwave-type included to the polymeric material to be treated and conveyed inside the pyrolysis treatment chamber, thus substantially eliminating or at least reducing the difficulties encountered in this sense in the prior art.
Equally advantageously, the pyrolysis device of the invention promotes shorter reaction times of the polymeric material to be treated than those encountered in the known devices to the advantage of production costs.
Advantageously and briefly, the pyrolysis device of the invention has a significantly better yield than that offered by the devices of the however remotely comparable prior art.
Said objects and advantages will become more apparent from the description which follows, relating to preferred embodiments of the pyrolysis device of the invention given by way of indicative and illustrative but non-limiting example, with reference to the accompanying drawings, in which:
The pyrolysis device of the invention, used for the disposal of polymeric materials, especially at end of life, such as typically and preferably ELTs, is disclosed in the minimal variant thereof in
It is worth noting that, in accordance with the invention, the pyrolysis device 1 comprises an elongated tubular structure, designated as a whole by reference numeral 2, which extends along a longitudinal axis X and includes as essential components:
Hereinafter, for the purposes of the present invention, the expression “pyrolysis treatment” (or “pyrolysis thermal treatment”) means the specific step of the process implemented by the pyrolysis device 1 of the invention which occurs inside the pyrolysis chamber 13 of the second tubular body 11, while with the expression “pyrolysis process” (or “pyrolysis cycle”) means the entire process implemented by the pyrolysis device 1 of the invention, thus involving all its component members which will be disclosed in detail.
In an appropriate but non-binding manner, in essence and at least from a functional point of view, the pyrolysis device 1 of the invention also includes a third tubular body (not designated with a specific reference numeral in the figures which follow, for the reason that will be soon clarified), normally closed at a first head and placed functionally downstream of the second tubular body 11 from which it is physically separated and with which it temporarily communicates; the third tubular body has an end cooling chamber which receives the shaped carriage 5 coming from the pyrolysis chamber 13 and containing the residues of polymeric material just subjected to the pyrolysis treatment by exploiting the microwave sources 14.
In particular, since the elongated tubular structure 2 of pyrolysis device 1 of the invention extends along a longitudinal axis X, the first tubular body 3 and the second tubular body 11 are mutually coaxial and axially aligned, the third tubular body is also formally coaxial and aligned with both the first tubular body 3 and with the second tubular body 11.
Actually, in this specific variant of the invention, the third tubular body coincides with the first tubular body 3 and is closed, at a first head 3a, by the aforesaid movable center shutter 15 itself when the latter takes said closing position and, at a second head 3b, opposed to the first head 3a, by the movable front shutter 8 when the latter takes the first position, so that when the front shutter 8 takes the second position, the third tubular body is open and puts the final cooling chamber (coinciding with the initial washing or drainage chamber 4 but functionally distinct therefrom), into communication with the external environment for releasing the shaped carriage 5, at the end of the pyrolysis cycle (or process), according to an exit direction (given by arrow F in
The shaped carriage 5 is thus provided, after appropriate washing and cleaning cycle, for a successive pyrolysis treatment cycle of other polymeric material to be subjected to pyrolysis.
In practice, by means of the variant of pyrolysis device 1 of the invention shown in
This is possible because, in the philosophy of the invention, the initial washing or drainage chamber (indicated by reference numeral 4 in
Preferably but not necessarily, the closing means 12 comprise, in this case, a fixed laminar plate 17 provided with an annular flange 18 fixed to the outer annular edge of the second tubular body 11 at the first end 11a thereof opposite to the second end 11b coupled to the movable center shutter 15.
As far as the interface chimneys 6, 7 (intended respectively for extracting air from the initial chamber 4 and thus creating a vacuum therein, and for introducing an inert gas, such as nitrogen, in such an initial chamber 4) are concerned, they communicate with the initial chamber 4 of the first tubular body 3 on which they are arranged, preferably laterally with respect to aforesaid longitudinal axis X: such a position of the interface chimneys 6, 7, shown in greater detail in
Indeed, the safety chimneys 19 allow the evacuation of fumes, gases, dust, chips and/or small-size fragments in case of dangerous and unexpected explosions which could occur inside the pyrolysis chamber 13 during the pyrolysis treatment which, as known, may create, at least in theory, explosive environment conditions.
Further worth noting in
Furthermore, the first tubular body 3 has a pair of second connectors 40, almost symmetrically opposite to the interface chimney 6, for connecting cooling fluid passage ducts of the thermal exchange battery under the shaped carriage 5, as well as a third connector 41 for the power electrodes and for the electric battery reading sensors.
Thus,
As shown in particular in
By way of illustrative and preferred example only, the first moving means 23 comprise two transmission assemblies 25, 26, which are mutually and equally spaced apart and evenly distributed on the bottom 3d of the first tubular body 3 so as to ensure a balanced and stable conveying of the shaped carriage 5.
Each of such transmission assemblies 25, 26 (e.g. formed by two toothed wheels spaced connected by a chain) substantially extends over the entire length of the first tubular body 3 along the longitudinal axis X and is rotated by a transverse shaft 27 integral with the transmission assemblies 25, 26, which are thus synchronized by such a transverse shaft 27, and keyed onto the first driving means 24 adapted to rotate the transverse shaft 27 about a linear axis Y orthogonal to the aforesaid longitudinal axis X.
It is worth noting that in other embodiments of the pyrolysis device of the present invention, not disclosed in the following, the first moving means may have a different constructional concept from that one just described and shown in the accompanying figures, as well as in further embodiments of the pyrolysis device of the invention, not yet disclosed, the first moving means may include a number of transmission assemblies different from two, since this number may vary according to requirements, starting from one.
It is worth noting that the first actuating means 10 which move the movable front shutter 8 preferably but not necessarily, comprise a linear actuating member 28, selected from the group consisting of pneumatic actuators, hydraulic actuators (preferred solution) and the like, which is rigidly coupled to a first end 29a of an articulation lever 29 provided with a second end 29b connected to the side edge 8a of the movable front shutter 8, so that, as shown in greater detail in
Advantageously but not exclusively, the pyrolysis device 1 of the invention also includes second moving means, indicated as a whole by reference numeral 31, which:
In particular, the second moving means 31 conveniently have the same constructional composition described above in detail, of the first moving means 23 with which they cooperate in this variant both in the passage of the shaped carriage 5 from the initial chamber 4 into the pyrolysis chamber 13 and in the reverse passage.
Preferably but not restrictively, the first tubular body 3 is made integral with the movable center shutter 15 by means of a first peripheral flange 33 which, as can be seen in
The combination in
In an advantageous and preferred manner, the second tubular body 11 also has:
Additionally, the second tubular body 11 (which generally has an axial length of about 1.5 meters) comprises, on the upper part of the outer lateral wall 11c, a plurality of auxiliary safety chimneys 42 communicating with the pyrolysis chamber 13, at least one of which comprising at least one burst disc which is activated to avoid dangerous damage of the second tubular body 11 due to an abrupt and sudden increase of the pressure difference between the pyrolysis chamber 13 of the second tubular body 11 and the environment outside the second tubular body 11. Each of such auxiliary safety chimneys 42 is provided with a terminal connector, not shown, to which a conveying duct (not shown) is connected adapted to convey outwards the fumes which may have damaged the burst disc.
Further constructional solutions of the pyrolysis device of the invention, not shown in the accompanying drawings, may provide that the first tubular body and/or the second tubular body comprise a number of interface chimneys and a number of safety chimneys different from that which can be derived from the accompanying figures, because each of such numbers may vary according to design choices, starting from one.
According to the preferred embodiment of the invention described herein, the microwave heating sources 14 include a plurality of cartridge feeders 44 communicating with the pyrolysis chamber 13 and uniformly distributed on the outer wall 11c of the second tubular body 11 to which they are coupled by fixing means of a type known per se to those skilled in the art (e.g. flanges), as shown in greater detail
In particular, the microwave sources 14 comprise a first plurality of cartridge feeders 44, mutually aligned along a first longitudinal direction X′ parallel to the longitudinal axis X, and a second plurality of cartridge feeders 44 mutually aligned along a second longitudinal direction X″, also parallel to the longitudinal axis X and symmetrical with respect to the first direction X′.
As clearly shown in
Each of the aforesaid cartridge feeders 44 internally contains a plurality of microwaves generation devices 45, shown in greater detail in
Preferably but not exclusively, the second tubular body 11 also includes shielding means, generally designated by reference numeral 46, transparent to electromagnetic waves, interposed between the microwave heating sources 14 and the pyrolysis chamber 13 that they directly face, adapted to protect the microwave sources 14 against the high temperatures and against the corrosive and/or aggressive gases which develop in the pyrolysis chamber 13 during the respective pyrolysis treatment.
The detail in
More precisely, each main laminar plate 47, 48 extends over the entire axial length of the second tubular body 11, to the inner wall 11e of which it is removably and slidingly coupled by means of the aforementioned supporting means 49 which act as guiding means during the insertion into position (or installation) and/or the extraction of each main laminar plate 47, 48.
In accordance with the arrangement of the first and of the second plurality of cartridge feeders 44 described above and shown in
It is understood that in other embodiments of the pyrolysis device of the invention, not shown in the accompanying drawings, the shielding means may comprise a number of main laminar plates made of refractory material different from that indicated above, because such a number may be varied at will by the manufacturer or according to requirements in relation to the positioning of the second tubular body.
Likewise, also the number of secondary laminar plates for each of the cartridge feeders can be different from that described above in other executive solutions of pyrolysis device of the invention: In this case, again, such a number of secondary laminar plates may vary according to design choices starting from one, and therefore to the actual shielding level of the electromagnetic waves which must be obtained.
The supporting means 49 are arranged in the upper portion of the inner wall 11e of the second tubular body 11 and define two mutually opposite longitudinal seats 53, 54, in which two longitudinal peripheral portions which are mutually opposite to the respective main laminar plates 47, 48 slide and remain housed, as shown in greater detail in
In preferred but non-binding manner, the supporting means 49 comprise a plurality of laminar tongues 55, 56 mutually spaced apart and uniformly distributed along the longitudinal axis X, on a pair of mutually opposite laminar plates 57, 58 facing each other and projecting from the inner wall 11e of the second tubular body 11 towards the pyrolysis chamber 13.
Of course, the laminar plates 57, 58 and the respective laminar tongues 55, 56 are defined both in front of the first plurality of cartridge feeders 44 to support the main laminar plate 47 and in front of the second plurality of cartridge feeders 44 to support the main laminar plate 48.
In the example of embodiment of pyrolysis device 1 of the invention described here, each of the two secondary laminar plates 50, 51 is stably sealed (e.g. by means of appropriate adhesives substances 59 foamed into position) to the inner surface 52a which delimits the through hole 52 of the second tubular body 11 and which is interposed between the microwave generation devices 45 and the respective main plate laminar 47 or 48.
It is stated precisely that, purely by way of preferred example, the transparent material of which each secondary laminar plate (or layer) 50, 51 is made is quartz glass: such a material effectively allows the passage of the microwaves E produced by the cartridge feeders 44 through each laminar plate 50, 51 but not of the gases which are developed during the pyrolysis treatment in the pyrolysis chamber 13.
Some of the accompanying figures hereto used for the present description show that the second tubular body 11 preferably also comprises a plurality of terminal ducts 60 projecting from the upper portion of the outer wall 11c of the second tubular body 11 and communicating with the pyrolysis chamber 13 to cool the electric part and electronics of microwaves sources 14.
Other embodiments of the pyrolysis device of the invention may evidently exist, not shown in hereinafter, in which the second tubular body includes a number of terminal ducts different from that shown in the figures mentioned hereto, because this number may vary according to operating requirements, starting from one.
Yet in
It follows that the microwave sources 14 are arranged, in this case, at two upper sides 61, 62 of the at least partially polygonal profile of the pyrolysis chamber 13, so that the magnetic field generated by the microwave sources 14 focuses mainly, if not almost integrally, towards the central zone of the pyrolysis chamber 13, i.e. that in which the shaped carriage 5 loaded with the polymeric material to be treated is positioned.
It is worth noting that, for the purposes of clarification only, the two upper sides 61, 62 of the at least partially polygonal profile of the pyrolysis chamber 13 are those which, in this case, are connected to each other by a curved portion 63.
Therefore, thanks to this constructional concept of the pyrolysis chamber 13, and of the consequent arrangement of the microwave sources 14, the magnetic field produced by the latter is almost entirely directed towards the center of the pyrolysis chamber 13 and therefore towards the polymeric material to be treated contained in the shaped carriage 5, without causing an excessive dispersion of such a magnetic field inside the pyrolysis chamber 13 itself, in the points in which there is no material to be treated (e.g., under the shaped carriage 5) or in which having the magnetic field itself is not required.
Indeed, the polygonal shape of the profile of the pyrolysis chamber 13 allows an effective play of reflections of the electromagnetic waves E generated by the cartridge feeders 44, accentuated by the shape of the shaped carriage 5 itself, which will be described below and which is characterized by squared stretches.
In essence, the at least partially polygonal profile of the pyrolysis chamber 13 allows maximizing the energy (or, in other words, increasing the density of the microwaves E) absorbed by the polymeric material to be treated present in the shaped carriage 5 and produced by the microwave sources 14, to the advantage of efficiency of the pyrolysis treatment and of the pyrolysis cycle as a whole.
On the other hand, the at least partially polygonal profile of the pyrolysis chamber 13 allows achieving a saving of material for manufacturing the second tubular body 11, which can be quantified in a reduction of the volume of the pyrolysis chamber 13 equal to about ⅓ with respect to a traditional type tubular body which typically has a circular profile.
The aforesaid reduction of size of the second tubular body 11 and thus of the volume of the pyrolysis chamber 13—without being at the detriment of the pyrolysis device 1 and in particular of the pyrolysis treatment performed in this pyrolysis chamber 13, quite the opposite, in light of its advantageous profile as mentioned—also advantageously reflects, for example, in a smaller amount of inert gas (typically nitrogen) to obtain the effective cleaning of the pyrolysis chamber 13.
To compensate for the inevitable structural strains generated by the profile of the pyrolysis chamber 13, the second tubular body 11 conveniently comprises a finned outer structure 64, formed by a plurality of laminar fins 65, which are equally spaced apart from one another, projecting in uniform manner from the outer wall 11c of the second tubular body 11.
In preferred but non-exclusive and non-limiting manner, the pyrolysis device 1 of the invention also comprises auxiliary heating means, not shown in the accompanying figures for simplicity, and comprising, for example, at least one electrical resistance of known type to those skilled in the art.
Such auxiliary heating means, such as, for example, electrical resistances of the traditional type, are arranged on the bottom 11d of the second tubular body 11 and inside the pyrolysis chamber 13, so as to be under the shaped carriage 5 when it is in the pyrolysis chamber 13 itself, and perform the function of preheating from ambient temperature the polymeric material to be subjected to pyrolysis treatment, present in the shaped carriage 5.
Basically, therefore, if present, the auxiliary heating means are activated before the microwave heating means 14, thus raising the temperature of the pyrolysis chamber 13, and thus of the polymeric material present in the shaped carriage 5, to a desired value (starting from the ambient temperature value): this allows optimizing the next amount of thermal energy which is supplied to the polymeric material by the microwave sources 14 for the pyrolysis thereof, the operational efficiency of which has been proven to be better when the polymeric material to be treated is already partially heated.
As shown in
Indeed,
The second tubular body 11 of pyrolysis device 1 of the invention preferably and advantageously further comprises fractionation means, not shown for convenience and consisting for example of a dephlegmator, of the vapors produced in the pyrolysis chamber 13 during the heat treatment and provided just above the furnace, connected to the auxiliary safety chimneys 42 from which the formed vapors exit.
In a preferred but not limiting manner, the second tubular body 11 also comprises means for modulating, also not shown for simplicity, of the microwave power E operatively connected to the microwave heating sources 14: they may be able to modulate the microwave power E by modulating the supply of electrical power of the microwave heating sources 14 and by activating the operation of only part of the microwave heating sources 14.
In this case, the auxiliary heating means may appropriately comprise one or more electrical resistors of traditional type or infrared rays, either instead or in combination therewith.
The movable center shutter 15, shown in detail in
Appropriately, in terms of safety and wear, the second actuating means 16 are contained inside the fixed outer bearing casing 70 of the movable center shutter 15, as shown in the sections in
It is worth noting that the main guiding means 72 are preferably arranged in the inner longitudinal surface 75a, 76a of two mutually opposite side walls 75, 76 of the fixed outer bearing casing 70 and cooperate with a transverse rod 77 belonging to the movable inner assembly 71 of the movable center shutter 15 and operatively connected to the second actuating means 16.
In particular, the main guiding means 72 preferentially comprise:
In more detail, the two vertical plates 78, 79 are arranged in the upper middle line of each of the two mutually opposite lateral sides 75, 76 of the fixed outer bearing casing 70: this constructional detail is emphasized because it is of some relevance in relation to a further constructional assembly belonging to the movable inner assembly 71 of the movable center shutter 15, which will be described in greater detail below.
In a preferred but not exclusive way, the aforesaid second actuating means 16 comprise a pair of vertically actuated hydraulic actuators 83, 84, which are mutually parallel and spaced apart, each of which is provided with:
On the basis of this, the maximum allowable output of the force piston 87 by the supporting cylinder 85 is achieved when the movable inner assembly 71 of the movable center shutter 15 takes the raised position and forms the vertical stop point of the movable inner assembly 71 when passing from the lowered position to the raised position, while the maximum admitted return of the piston force 87 in the supporting cylinder 85 is achieved when the movable inner assembly 71 takes the lowered position and forms the vertical stop point of the movable inner assembly 71 when passing from the raised position to the lowered position.
By way of preferred but not limiting example, the movable inner assembly 71 comprises:
According to the preferred embodiment described herein of the invention, the driving means 92, in this case, comprise a pair of separate, opposed and mutually facing rise wedges 96, 97, coupled to a base plate 98 operatively connected to the transverse rod 77.
Each of such rise wedges 96, 97 is provided with a sloping surface 96a, 97a, which cooperates by sliding, respectively, with the side wall 93a, 94a of the idle rollers 93, 94 during the passage of the movable inner assembly 71 from the lowered position to the raised position and vice versa to arrange the idle rollers 93, 94:
More specifically, in the example described here, the flat contrast surface 99 belongs to a center zone of the base plate 98 (for the idle roller 94), while the flat contrast surface 100 belongs to a laminar fin 101, projecting from the sloping surface 96a of one of the rise wedges 96, 97 laterally and towards the main development axis of a base plate 98 from which it is separated (for the idle roller 93).
Also for the feeding means, it is understood that in other embodiments of the invention, not shown in the accompanying drawings, they may comprise a different number of rise wedges from two, since such a number may vary according to design choices, starting from one; it is apparent that in these circumstances, also the number of idle rollers and flat contrast surfaces will vary in accordance, remaining equal to that of the rise wedges.
In particular, if a single idle roller is included in the presence of a single rise wedge, the idle roller itself will be coupled only to one of the compartmenting shutters of the movable inner assembly, provided that the two shutters are mutually integral also in the raising and lowering motion to open and close the through apertures which are presented thereto, respectively.
In appropriate but not limiting manner, the compartmenting bulkheads 88, 89 and the through apertures 90, 91 have in cross section at least partially polygonal profile substantially equal to and mating with that of the shaped carriage 5 and of the profile of the pyrolysis chamber 13, so as to allow the precise sliding passage along the longitudinal axis X of the shaped carriage 5 through the movable center shutter 15. Particularly,
Preferably but not necessarily, the movable inner assembly 71 also comprises:
The shaped closure wedges 102 and 103 cooperate respectively with the first pair of shaped pressing wedges 106, 107 and with the second pair of pressing wedges 108, 109 to ensure a tight closing of the through apertures 90, 91, as well as of the axial outlet mouth 73 of the first tubular body 3 and of the axial inlet mouth 74 of the second tubular body 11 facing such through apertures 90, 91.
As shown in particular in
In more detail, the compartmenting bulkhead 88 supports the shaped pressing wedges 106 and 108, while the compartmenting bulkhead 89 supports the shaped pressing wedges 107 and 109.
Furthermore, the three-dimensional reticular body 111 preferably comprises refractory material, such as poured concrete (not shown for simplicity), adapted to protect each of the compartmenting bulkheads 88, 89 against the high temperatures which develop inside the pyrolysis chamber 13 during the pyrolysis treatment.
Advantageously, each of the shaped closure wedges 102, 103 has in cross section a composite polygonal profile, tapered from the top downwards, comprising at least:
In particular, the first linear stretches 112 of each shaped closure wedge 102, 103:
For their part, instead, the second linear portions 114 of each of the shaped closure wedge 102, 103:
More particularly, it is worth noting that the first distance is greater than the second distance so that the lateral thrust applied on the respective shaped pressing wedges 106, 107, 108, 109 by the first linear portions 112 of the shaped closure wedges 102, 103 is greater than that of the second linear portions 114 of the shaped closure wedges 102, 103.
As a function of the appropriate although not essential presence of the shaped closure wedges 102, 103, it is apparent that the feeding means 92 are coupled to an upper wall 103c of the wedge-shaped closure 103, that between the two more smaller according to a vertical direction and that which, to all effects, operatively connects the feeding means 92 to the transverse rod 77.
Preferably, each of the supporting uprights 116, 117 has an open-profile linear recess to 118, passing through the thickness of the supporting uprights 116, 117 at the upper end 116a, 117a: the transverse rod 77 fits inside the through recess linear 118 for a respective section when the movable inner assembly 71 takes the lowered position and protrudes from the through linear recess 118 during the passage of the movable inner assembly 71 from the lowered position to the raised position described above.
In the figures mentioned hereto, it is also worth noting that the auxiliary guiding means 115 are arranged below the main guiding means 72 and receive two vertical edges 88b, 88c, 89b, 89c mutually opposed to each compartmenting bulkhead 88, 89 when the movable inner assembly 71 takes the lowered position.
Preferentially but not necessarily, the auxiliary guiding means 115 comprise, for each of the supporting uprights 116, 117, a pair of longitudinal grooves 120, 121, mutually parallel and placed side-by-side and communicating with the outside frontally and superiorly, in which the vertical edges 88b, 88c and 89b, 89c of the compartmenting bulkheads 88, 89 are engaged.
More in detail,
In a particularly advantageous way, each of the longitudinal grooves 120, 121 ends at the respective lower end with a curved portion 126 which is closed by the aforesaid limit stop partition 124 and in which each of the vertical edges 88b, 88c and 89b, 89c of the compartmenting bulkheads 88, 89 is forced by the shaped closure wedges 102, 103 in order to further increase the tightness and sealing of the closure of the through apertures 90, 92 present in the compartmenting bulkheads 88, 89.
By virtue of the latter constructional arrangement, together with the fact that the movable center shutter 15 has an extremely compact box-like structure, the movable shutter 15 itself is also configured as a sort of pressure chamber, in which the nitrogen (introduced at a pressure higher than that of the nitrogen contained in the initial chamber 4 and of the gases in the pyrolysis chamber 13):
Therefore, the movable center shutter 15 is a physical structural barrier, resistant to the corrosive agents which are inevitably developed during the pyrolysis process, which is maintained stably in position, for which the movable inner assembly 71 takes the lowered position, when the pyrolysis treatment of the polymeric material is in progress inside the pyrolysis chamber 13, which ensures high safety conditions for operators, personnel and the environment.
Further constructional embodiments of pyrolysis device of the invention, not shown in the accompanying drawings, may include that the movable center shutter comprises a number of interface ducts different from that shown in the accompanying figures, because this number may vary according to the requirements starting from one.
Advantageously but not limitedly, the outer fixed bearing casing 70 of the movable center shutter 15 has in an upper lamina 128, a through slot 129 which promotes the extraction, for any reason, of the movable inner assembly 71 of the movable shutter 15 and/or the inspection, maintenance, repair and/or replacement of the inner volume of the outer fixed bearing casing 70 or of the components of the movable inner assembly 71.
Equally advantageously but not necessarily, the outer fixed bearing casing 70 of the movable center shutter 15 has in the side surface 70d one or more revolving service doors 130 to allow the access, inspection, maintenance, repair and/or replacement of the components of the movable inner assembly 71 or the simple cleaning of the inside of the outer fixed bearing casing 70.
In other embodiments of the pyrolysis device of the invention, not shown in the accompanying figures, the fixed outer bearing casing of the movable center shutter may have a different number of service through holes from that shown in accompanying figures because this number may vary according to design choices and/or operating requirements, starting from one.
In preferred but not essential manner, the movable center shutter 15 also comprises, within its box-like structure, a sealing gasket 131 made of soft (e.g. elastomeric) material of inflatable type, interposed between the movable inner assembly 71 and the fixed outer bearing casing 70, as shown in the enlarged detail in
Still advantageously, the pyrolysis device 1 of the invention also comprises a metal sealing gasket 132, also shown in the enlarged detail in
More than one sealing gasket made of soft material and one metal sealing gasket may be present in alternative embodiments, not shown, of the pyrolysis device of the present invention.
Another substantial difference between the pyrolysis device 1 described above and the pyrolysis device 200 disclosed in this step of the description of the invention is related to the fact that, in an appropriate but non-binding manner, the pyrolysis device also comprises two third tubular bodies 216, 217 arranged in series and coaxial with each other and with the second tubular body 210 and the first tubular body 202, along the longitudinal axis X.
Both the third tubular bodies (or tubular extension bodies, in the specific case) 216, 217 are arranged in mutually axial and consecutive manner downstream of the second tubular body 210 from which are physically separated and with which only the third tubular body 216 directly and temporarily communicates.
The third tubular bodies 216, 217 are also physically separated and made independent from one another by the closure means, indicated as a whole by reference numeral 211, which, in given operating conditions, are put temporarily in communication: in essence, therefore, these closure means 211, which, as will be explained shortly, comprise compartmenting doors, perform the function of hermetically separating, for a given interval of time, the interior of the process chambers (or cells) of the pyrolysis device 200 from one another, while inside them, in particular inside the pyrolysis chamber 212, the respective treatment provided by the process itself is performed.
Thereby, the closure means 211 isolate and make the process chambers of the pyrolysis device 200 mutually independent in relation to the environmental conditions which are generated inside them, such as developed aggressive gases, pressures, temperatures and anything else.
Furthermore, the third extension tubular body 216 has a final cooling chamber 218 which receives the shaped carriage 204 containing the residues of the newly treated polymeric material exiting from the pyrolysis chamber 212 of the second tubular body 210, while the third extension tubular body 217 (in series and successive to the third tubular body 216) has a final cooling chamber 219 which also receives the shaped carriage 204 coming from the final cooling chamber 218 of the third tubular body 216.
Thus, in brief, in this solution of embodiment of the invention, the shaped carriage 204 continues always forwards along the longitudinal axis X, during the cycle of pyrolysis, without ever traveling backwards, as occurs for the shaped carriage 5 of the pyrolysis device 1.
It follows that the third tubular extension body 216 (and thus the third tubular extension body 217 successive to and distinct from it) is arranged downstream of the second tubular body 210 from a constructional, not only from a functional, point of view, always advancing in any case following a single direction, given by the arrow H in
To summarize, the third tubular body 216 is thus a distinct and separate mechanical piece from the first tubular body 202 (unlike the third tubular body of the pyrolysis device 1 which could be defined as such by semantic artifice only which is perfectly valid and verified from the functional point of view, as mentioned) and from the second tubular body 210 with respect to which it is:
Therefore, on the basis of the technical features described above, the pyrolysis device 200 of the invention has a high productive capacity, certainly greater than that of the pyrolysis device 1 of the invention described before, because it allows continuously loading the initial chamber 203 with a shaped carriage 204 filled with polymeric material to be treated, while at the same time, the next pyrolysis chamber 212 is processing the polymeric material contained in another shaped carriage 204 and the next final cooling chambers 218, 219 are finishing the complete pyrolysis cycle on the polymeric material already treated (or subjected to pyrolysis) and contained in the other shaped carriages 204, thus eliminating the operation downtimes which are encountered, instead, in the pyrolysis device 1 of the invention when the shaped carriage 5, with the polymeric material already been treated, returns into initial chamber 4 from the pyrolysis chamber 13.
Preferably, both the third tubular body 216 and the third tubular body 217 of pyrolysis device 200 of the invention have a constructional structure substantially equal to that of the first tubular body 202, in which the final chamber cooling of 218 and 219 is subjected to the action of cooling devices (not shown for simplicity) adapted to cool the residues deriving from the thermal pyrolysis treatment performed on the polymeric material.
In this case, in accordance with the elongated structure 201 which distinguishes the pyrolysis device 200 of the invention, the closure means 211 physically separate also the third tubular extension body 216 from the third tubular extension body 217, with the latter normally closed at a first head 217a.
In preferred but not exclusive manner, the closure means 211 firstly comprise a first auxiliary movable center shutter 221 interposed between the second tubular body 202 and the third tubular body 216, opposite to and facing the movable center shutter 214 and cooperating with third actuating means (not shown in the accompanying figures but of the same type as the second actuating means 16 provided on the movable shutter 15 of the pyrolysis device 1).
The third actuating means move the first auxiliary movable shutter 221 alternately between a closed position, in which the first auxiliary movable shutter 221 keeps the pyrolysis chamber 212 and the final cooling chamber 218 mutually insulated (and hermetically closes the third tubular body 216 at least at the height of the second head 216b), and an open position in which the first auxiliary movable shutter 221 connects the pyrolysis chamber 212 to the chamber cooling end 218 (which in
In greater detail, the first rear movable shutter 221 is arranged at the inlet mouth of the third tubular body 216 and the outlet mouth 220 of the second tubular body 210 from which the shaped carriage 204 exits at the end of the pyrolysis treatment in the pyrolysis chamber 212.
Similarly, the closure means 211 firstly also comprise, in this case, a second auxiliary movable center shutter 222 interposed between the third tubular body 216 and the third tubular body 217, opposite to and facing the first movable center shutter 221 and cooperating with fourth actuating means (not shown in the accompanying figures but of the same type as the second actuating means 16 provided on the movable shutter 15 of the pyrolysis device 1).
Also the third actuating means move the second auxiliary movable shutter 222 alternately between a closing position, in which the first auxiliary movable shutter 221 keeps the pyrolysis chamber 218 and the final cooling chamber 219 mutually insulated and hermetically closes the third tubular body 217 at least at the height of the second head 217b, and an opening position, in which the second auxiliary movable shutter 221 puts the final chamber 218 into communication with the final chamber 219.
Advantageously but not necessarily, the first auxiliary movable center shutter 221 and the second auxiliary movable center shutter 222 have the same construction as the movable center shutter 214 (which is the possible subject of separate patenting, and therefore protection, as already pointed out above and assumed) thus promoting the creation of economies of scale in their manufacture.
In a preferred but not limiting manner, the third tubular body 217 (the last one of the pyrolysis device 200, following the direction given by arrow H) is provided at the first head 217a of a rear movable shutter 223 operatively connected to third actuating means, not shown, which alternately move between a first position, in which the rear shutter 223 closes from an outer side 219a the final cooling chamber 219, and a second position in which the rear flap 223 opens the final cooling chamber 219 from such an outer side 219a, by putting it into communication with the outside environment for extracting the shaped carriage 204 at the end of the pyrolysis cycle. As regards the second moving means (not shown in
It is understood that in further embodiments of the invention, not accompanied by reference drawings, the pyrolysis device may comprise a number of tubular extension bodies, normally closed at a first head and arranged functionally and constructionally downstream of the second tubular body, which is different from two, since this number may vary according to production requirements (and obviously the spaces available at the processing plant), starting from one.
Operatively, we will primarily describe the most congenial operation of the pyrolysis device 200 of the invention primarily, which is substantially as follows.
When it is started for the first time, it is necessary replace the air with the inert gas (which is preferably nitrogen) in the process chambers 203, 212, 218 and 219 of pyrolysis device 200 of the invention.
To start this procedure, it is firstly necessary to close the front movable shutter 207 and the rear movable shutter 223 of the device 200 (already in the startup phase, it is possible to introduce the shaped carriage 204, loaded with polymeric material to be subjected to pyrolysis, e.g. thirty end-of-life tires in the initial washing or drainage chamber 203), while the movable center shutters 214, 221 and 222—inside the elongated structure 201 of the pyrolysis device 200—arranged between the various process chambers 203, 212, 218 and 219 may be left in the respective opening position during this first step of the start-up phase.
By means of the appropriate flanged interface chimneys (in
Once the air has been replaced with the inert gas in the entire pyrolysis device 200, the movable center shutters 214, 221 and 222 are closed (of course, if they have been left open during the preliminary start-up phase), the last air is extracted from the pyrolysis chamber 212 and the cycle procedure continues.
At the beginning of a complete pyrolysis cycle, after performing the start-up procedure, both the movable front shutter 207 and the movable rear shutter 223 take the previously defined first position and all the movable center shutters 214, 221 and 222 of the pyrolysis device 200 take the closing position.
To start the cycle, the movable front shutter 207 for entering the initial washing or drainage chamber 203 and the shaped carriage 204 is introduced inside loaded with the polymeric material to be subjected to pyrolysis, accommodated for the treatment.
Once having closed and compartmented the initial room 203 by activating the first actuating means 209, the air is extracted and the inert gas is introduced (such as nitrogen, as mentioned), again in this case, advantageously but not necessarily repeating the process several times to replace all the air present in the pyrolysis device 200 with the inert gas, with the appropriate but not absolute arrangement of including a final extraction of the air and of the introduced nitrogen.
At the end of this phase, the pressure between the initial washing or drainage chamber 203 and the next pyrolysis chamber 212 is equalized.
When the pressures between the aforesaid two process chambers 203 and 212 are equalized by means of the second actuating means (not shown in
After completing the pyrolysis treatment, before the opening of the next auxiliary movable shutter 221 and the advancement of the shaped carriage 204 along the longitudinal axis X according to arrow H, the pressure is equalized again between the pyrolysis treatment chamber 212 and the cooling chamber 218 of the tubular extension body 216.
After completing such a new pressure equalization phase, it is possible to open the auxiliary movable center shutter 221 which puts the cooling chamber 218 into communication with the pyrolysis chamber 212 and by operating automatically by means of the second moving means transfer the shaped carriage 204 into the cooling chamber 218, closing the auxiliary movable shutter 221 again at the end of transfer along the longitudinal axis X, according to the arrow H.
The shaped carriage 204 is then left in the cooling chamber 218 for the time necessary to cool the process residues, while maintaining the vacuum inside it to extract of emanated gases.
After cooling, it is possible to open the auxiliary movable center shutter 222 and then exit the cooling chamber 218 the shaped carriage 204 containing the residual elements of the pyrolysis treatment.
In entirely identical way, the shaped carriage 204 is then transferred to the final cooling chamber 219, by virtue of the actuation of the third moving means and from here towards the outside after having completed the pyrolysis cycle.
Before removing the shaped carriage 204 from the pyrolysis device 200 with the treatment residues a washing cycle is performed with suction and introduction of nitrogen into the cooling chamber 218, then balancing the pressure with the outside environment and finally opening the rear shutter 223.
The operation of the pyrolysis device 1 of the present invention is substantially the same as that just described for the pyrolysis device 200, especially from the point of view of the operation of the single process cells (or chambers) 4 and 13 and of the movement therebetween of the shaped carriage 5 by means of the opening and closing cycles of the movable center shutter 14 which can be obtained by actuating the second actuating means 16.
It is worth noting that the shaped carriage 5 is smaller in size than the shaped carriage 204, because the initial chamber 4 is smaller than the initial room 203: therefore, the shaped carriage 5 may contain a smaller amount of ELTs than shaped carriage 204.
The only substantial difference between the operation of pyrolysis device 1 and that of the pyrolysis device 200 derives from the fact that, at the end of the treatment of the polymeric material in the pyrolysis chamber 13, the shaped carriage 5 is moved axially along the longitudinal axis X, by the second moving means 31, in cooperation with the first moving means 23, according to the direction given by the arrow G in
On the basis of this description, it is therefore understood that the pyrolysis device for disposal of polymeric materials, especially end-of-life tires (ELTs), which is the subject of the present invention achieves the aims and offers the advantages mentioned previously.
Upon execution, changes may be made to the concerned pyrolysis device of the present invention, consisting, for example, in a length of the initial washing or drainage chamber and/or the pyrolysis chamber of pyrolysis treatment different from which can be obtainable from the accompanying figures.
Particularly, each initial washing or drainage chamber and each final cooling chamber may have, in other embodiments of the pyrolysis device of the present invention not accompanied herein by reference to figures, a modular composition different from that shown in the accompanying figures, according to the amount of polymeric material that it is desired to process in the unit of time (in other words, according to production efficiency needs) and the consequent overall duration of the processing cycle.
Additionally, further embodiments of the invention, also not shown in the accompanying drawings, the pyrolysis device may comprise a number of microwave heating sources coupled to the second tubular body different from that shown in the figures of these drawings, because this number may vary according to production requirements, design choices and constructional concept, starting from one.
Furthermore, in other optional embodiments of the pyrolysis device of the present invention, not disclosed hereinafter, the first tubular body and/or the second tubular body may be provided with a number of interface chimneys different from that one previously described and shown in the accompanying drawings, since such a number also vary in this case according to requirements and design and operational choices, starting from one.
The variability of the number of such interface chimneys also depends on the fact that the use thereof could not be finalized only at replacing the air with an inert gas in the initial washing or drainage chamber, in the pyrolysis chamber (at least before performing the pyrolysis treatment therein) and/or in the at least one final cooling chamber but also to the installation of measuring instruments which may be deemed useful to the control of the process in progress.
Alternative and optional embodiments of the invention, again not shown, may provide that only the first body or only the second tubular body comprise one or more interface chimneys for extracting air from the respective process chambers or introducing nitrogen therein.
Yet further, in further applicative and operative embodiments of the pyrolysis device of the invention, not covered in the proceeding description, only the initial chamber or only the pyrolysis chamber may require the replacement of air with an inert gas through the interface chimneys.
In addition to this, other embodiments of the pyrolysis device which is exclusively disclosed herein, not shown below, in which the first actuating means and second actuating means are of a different type from that described above, without impairing the advantage provided by the present invention.
In particular, the pyrolysis device of the invention lends itself to exploit at least part of the process for the pyrolysis of end-of-life tires (ELTs) described in the patent document published under WO2012/220991 A1, the teachings of which are incorporated by reference in the present description.
Finally, it is apparent that many other variants may be made to the concerned pyrolysis device, without departing from the principles of novelty inherent in the inventive idea, just as it is apparent that in the practical implementation of the invention, the materials, shapes and sizes of the details shown may be any according to the requirements and may be replaced by other technically equivalent elements.
Where the constructional features and techniques mentioned in any one of the following claims are followed by references signs or numerals, such reference signs were introduced for the sole purpose of increasing intelligibility of the claims themselves and therefore such reference signs have no limiting effect on the interpretation of each element identified by way of example only by such reference signs.
Number | Date | Country | Kind |
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102018000003163 | Mar 2018 | IT | national |
102018000005441 | May 2018 | IT | national |
Filing Document | Filing Date | Country | Kind |
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PCT/IB2019/051611 | 2/28/2019 | WO | 00 |