AU668724B2 - Method for processing residue-containing packages - Google Patents

Abstract

A method is disclosed for processing residue-containing packages so as to recover valuable materials, in particular pressure containers for dispensing polyurethane foams with propellant gases. For that purpose, extraction with a solvent is carried out essentially in atmosphere of propellant gas and/or solvent vapours.

Description

OPT DATE 29/11/9$3 AQIP DATE 10/02/94 Aii LN. ID 40293/9311111111Jl PCT NUMBER PCT/EP93/00988 AU9340293 (21) Internationales Aktenzeichen: PCT/EP93/00988 (74) Anwijlte: H ERRMANN-TRENTE POH L, WVerner uswv.

SchaeferstraRe 18, D-4690 Herne I (DE).

(22) Internationales Anmeldedatumn: 23, April 1993 (23.04.93) (81) Bestimrnungsstaaten: AT, AU, BB, BG, BR. CA. CH. DE.

Priori tltsdaten: DK. ES, Fl, GB. HU, JP, KP, KR, LK, ILU, MG,'MN.

PCT/EP92/00893 23. April 1992 (23.04.92) WO MW, NL. NO, PL, RO. RU, SD, SE, US, europ~tisches (34) Ldnderlir die die regionale ode, Patent (AT, BE, CH, DE, DK, ES, FR, GB, GR. IE. IT, internationaic Anielduing eingereicht LU, MC, NL, PT, SE), GAPI Patent (BF, BJ, CF. CG, 1vardenl ist.' DE usw. CI, CM, GA, GN, ML, MR, NE, SN, TD, TG).

P 43 03 168.4 4, Februar 1993 (04.02.93) DE Ver~iffentlicht (71) Annmelder (Air alIc Besdtnmnungsstcaten ausser US): RAT- Mit internationaleni Recherchenbericht.

NOR AG [CH/CH]: Rtitistrage, CH-9050 Appenzell Var Ablaiif derflir 4inderungen der Anspridchc zugelasse- (C nen Frist. Vleriifehntichung ivird wiiederhali fialls 4nderungell eintrqffll.

(72) Erfinder; und Erfinder/Anmnelder (nurfiir LIS) PAULS, Mathias [DE! Mooshaldenstrage. CH-9050 Appenzell (CH), KEL'LNER, Torsten [CHI'CHI: Rinkenbachstrage. CH- 9050 Appenzell Wen 6 (54)Title: METHOD FOR PROCESSING RESIDUE-CONTAINING PACKAGES (54) Bezeichnung: VERFAHREN ZUR AUFBEREITUNG VON RCJCKSTANDSHALTIGEN EMBALLAGEN (57) Abstract A method is disclosed for processing residue-containing packages so as to recover valuable materials, in particular pressure containers for dispensing polyurethane foams with propellant gases. For that purpose, extraction with a solvent is carried out essentially in atmosphere of propellant gas and/or szo;'ent vapours.

(57) Zusammenfassung Die Erfindung betrifft emn Verfahren zur Aufbereitung von rockstandshaltigen Emballagen unter Gewinnung der Wertstoffe, insbesondere von Druckbehtfiltern zur Ausbringung von Polyurethanschilumen mit Treibgasen, durch Extraktion mit einem Lisungsmittel, das im wesentlichen in einer Atmosphire aus Treibgas und/oder 1_6sungsmitteldflimpfen durchgefohrt wird.

W093/22077 PCT/EP93/00988 -1- "Method for processing residue-containing packages" Description This invention concerns a method for processing used or damaged, residue-containing packages and recovering the valuable materials, in particular from pressurized cans (aerosol cans) for dispensing polyurethane foam with propellant gases, by extracting them with a solvent, as well as a plant for using this method.

Residue-containing packages such as partially or completely emptied aerosol cans, which occur in great quantities, aze an increasing problem for waste disposal. They cannot be dumped in waste disposal sites for environmental reasons because the residues still contained in the cans can escape to the atmosphere, the ground, or the ground water where they can cause considerable damage. The same applies to incineration which is frequently not complete, particularly for chemical-technical products, and which produces great quantities of harmful substances which can only be bonded, if at all, through very expensive measures. Insofar, incineration will greatly reduce the waste volume, but does not lead to a solution of the effects on the environment.

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li REPLACEMENT PAGE L V i_ -I; 41 WO 93/22077 PCT/EP93/00988 -2- In the following, we will discuss this problem in detail by referring to the disposal of prepolymer-containing aerosol cans for producing the polyurethane foams.

The polyurethane foams have found a wide use in many areas. In the construction industry, in particular, they are used for sealing and insulating, but also in technical areas. As a rule, polyurethane foams are dispensed from aerosol cans containing a polyurethane prepolymer together with the necessary propellant and, if necessary, some additives. These aerosol cans are pressurized, cannot be reused and must therefore be disposed of.

On the other hand, they represent a problem which cannot be solved through normal waste disposal. In addition, aerosol cans, particularly older ones, regularly contain fluoridated hydrocarbons, which are considered damaging to the ozone layer and should therefore not reach the atmosphere.

Within the framework of the efforts to contain residential and commercial waste, increasingly measures are discussed and regulations passed, which force manufacturers to take back these products after use and take measures for their reuse or disposal.

These measures have made it necessary t6 search for ways to treat such waste products in an economic way.

;I When processing these returned aerosol cans for polyurethane foams, a number of problems arise which, until now, have been REPLACEMENT PAGE ff 42 WO 93/22077 PCT/EP93/00988 -3an obstacle to an economic recycling and recovery. Some of the returned cans, for example, are still under considerable pressure because of the remaining propellant gas, which causes problems when shredding them or incinerating them. Furthermore, these cans are at different levels of filling, ranging from outdated cans with practically full prepolymer content, which cannot be dispensed because of a blocked valve, to the practically emptied cans with prepolymer residues sticking to the edges, either in interlaced or non-interlaced condition. Until now, these varied conditions str;d in the way of a unified method for recovering the residues.

Until now, aerosol cans were processed in plants filled with traditional inert gases because of the assumed danger of explosion during the process. The term "inert" here means noncombustible. Such inert gases include nitrogen and argon.

However, experiments showed that the use of nitrogen inflates the gas balaice enormously and has a negative influence on the efficient separation of propellant gas residues. In particular, the presence of large amounts of nitrogen requires very powerful and thus also very expensive condensing plants to achieve a sufficient separation. On the other hand, using inert gases to avoid an explosion in the plant is necessary.

Thus, the invention is based on the task of producing a method for processing packaging materials, containing polyurethane prepolymers for the foam production, but also for adhesives REPLACEMENT PAGE 4 so that the valuable materials contained therein can be recovered without releasing content materials that damage health and environment and without stressing the processing cycle with large amounts of fed-in nitrogen. At the same time, the method is intended to meet the requirements for protection against the danger of explosion.

Disclosure of the Invention According to the present invention there is provided a method of processing residuecontaining packaging materials to recover valuable materials, especially from pressurised containers for spraying polyurethane foams with propellants, and extracting with solvents, with the following steps, performed in an atmosphere consisting essentially of propellants lo and/or solvents vapours: feeding the packaging materials into a work container while simultaneously opening them and extracting the residue with a solvent, transferring the residue from the work container into a distillation container, concentrating the residue-containing solution in the distillation container by distilling out the solvent, condensing the processed solvent and returning it to the work container, and removing the packaging material residue from the work container and, after adequate enrichment, recovering of the residue in concentrated form from the distillation container.

The invention solves this problem with a method as described in the beginning which is carried out essentially in an atmosphere of propellant gas and/or solvent vapors.

Preferably, this is a method which includes the following parallel steps: feeding the packaging materials into a working container while, at the same time, shredding them and then extracting the residues with a solvent, .transferring the residue-containing solution from the working container to a distillation container, concentrating the residue-containing solution in this distillation container by distilling out the solvent, condensing the distilled solvent, returning the solvent to the working container as well as removing the packaging residues from the working container and, following sufficient enrichment, recovery of these residues in concentrated form from the distillation container.

The term "protective gas" or "propellant gas" ii the invention refers to gases used as propellants and foaming agent in traditional pressurised cans (aerosol cans), particularly those for producing polyurethane foam as propellant and foaming agent. In particular, this includes propane, butane, dimethylether, fluorocarbons, as well as fluoromethane and fluoroethane (approximately R 134a and R 152 a) as well as i, [N:\Iibuu]0041.KEH L i (213 4. C 44 WO 93/22077 PCT/EP93/00988 fluoridated chlorinated hydrocarbons, as far as these are still in use and licensed for use, C0 2

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2 0 etc. Nitrogen and argon are included only in that they are released from pressurized cans were they form a component of the propellant mixture contents.

"Propellant gases" in the narrow sense that they used in the invention refer to the propellant gases released from pressurized cans that are processed. It must be understood here that in the starting phase for the method, "propellant gases" from other sources must be used to make the plant inert. R 134a and R152a are particularly suited for this. The extraction solvent, which is present in the atmosphere based on its vapor pressure, also plays a more or less significant role in rendering the plant inert. Up to 50% of C0 2 can be added to this mixture to protect against the danger of explosion.

We have to point out here that the operational saety of the method depends on the fact that the process takes place in a closed system and above the explosion limit of all component materials that are combustible and explosive. Insofar, it does not rest on the complete replacement of oxygen by a noncombustible gas.

The packaging to be processed is preferably transferred via conduit into the working container. This can be done with a traditional conduit, which ensures that the container remains sealed against the environment.

If the packaging material has not been opened, it is useful to do this during the feed-in and preferably along with REPLACEMENT PAGE I 0 ff i i. WO 93/22077 PCT/EP93/00988 -6the shredding, e.g. in a shredder especially designed for this purpose. In the following, this is called shredding.

It is particularly advantageous to open or shred the packaging materials by spraying them with solvents. On the one hand, this prevents foaming and, on the other, possibly entered water is absorbed by the solvent and distributed before it causes uncontrolled reactions with the content materials. This is very important particularly with materials that are sensitive to moisture, especially moisture-based interlacing of polyurethane prepolymers.

The shredded packaging material is subsequently placed onto a conveyor in the work area, preferably a worm conveyor, which is suited for separating the solid materials from fluids and solvents. A magnetic conveyor system must be considered if these packaging materials are ferromagnetic. A combination of both conveying methods may also be useful, particularly if the packaging materials consist of tinplate with plastic components, which is often the case with aerosol cans.

Extraction of the residues from the opened and/or shredded packaging material takes place in the w6rking container with a solvent that is specifically designed for the respective residue.

In any case, suitable solvents are those used to produce the packaging content originally and/or those still contained in the packaging materials.

REPLACEMENT PAGE 4> 6L r- ?Jti p~C j 46 WO 93/22077 PCT/EP93/00988 -7- On the one hand, extraction may take place by dropping the opened and/or shredded packaging materials into a working container filled with solvent and leaving them there for a period before they are moved along. The parallel alternative is to spray the packaging materials during the shredding and/or the conveying process with fresh solvent and then washing them. It is useful to bring the packaging materials in all three stages in contact with the solvent, that is to spray them during the shredding and conveying as well as subjecting them to solvent in the working container, for example in a catch funnel for the worm conveyor.

Subsequent to removing them, the solid residues are then dried in any optional sequence, are brought out on the conveyor and then sorted and moved toward the recycling area.

The traditional esters, ketones, aliphatic and aromatic hydrocarbons and their derivatives are particularly well suited as solvents, especially those with a boiling point of about 200 C. If containers with polyurethane prepolymers are processed, then acetone and toluol are particularly well suited as solvents.

Large amounts of propellant gases are released during the processing of residue-containing spray, pressurized and aerosol cans. It is not desirable that these gases escape to the atmosphere. If these propellant gases are not needed as inert gases, they are collected and condensed with suitable means.

Such a condensation on the one hand may take place through REPLACEMENT PAGE ,i C AT 0 47 WO 93/22077 PCT/EP93/00988 -8compression until the gas liquefies and on the other by condensing out under low temperatures. These measures are useful, particularly for propellant gases that can be liquefied such as low boiling point fluorocarbons or even combustible hydrocarbons such as propane or butane.

The invention method transfers the residue-containing solution in the working container to a distillation container with, for example, a pump. In the distillation container, the solution is further condensed. To do this, the solution is heated up and the solvent distilled out of the liquid phase. It may be useful to work with reduced pressure to reduce the boiling temperature and avoid displacements in the residues. The distilled out solvents are condensed and, following this cleaning through distillation, are returned to the processing cycle if necessary. The residues in the distillation container liquid are drawn off after they are sufficiently condensed and removed for further processing.

In case the method in this invention is used to process aerosol cans with polyurethane prepolymers, it is useful to add a known thinner to increase the flow capacity of the prepolymers that collect in the distillation container. Such a thinner should have a higher boiling point than the respectively used solvent.

Particularly suited for this is triethylphosphate or fresh raw material such as the raw materials used originally to fill the packaging materials.

REPLACEMENT PAGE V 0.P f 48 WO 93/22077 PCT/EP93/00988 -9- The invention method is carried out with protective gas.

Protective gases are the previously listed "propellant gases" and C0 2 C0 2 -containing combustion gases and others like it, whereby the displacement of oxygen in the processing range is particularly important to avoid an explosive mixture. If a stored propellant gas admixture such as C0 2 R 134a and R 152a is used, it is useful to circulate it, whereby at suitable stages, propellants that are released from pressurized cans and evaporated solvents are separated out.

One special advantage of the inventive method that it can be run continuously and, with slight modifications, can be adapted to a multitude of pressurized can/aerosol cans now on the market.

Thus, the inventive method makes is possible, for example, to process residues-containing polyurethane prepolymers from aerosol cans and other containers and recover these so that they can be reused while, at the same time, recovering the raw material for the containers in a relatively clean form so that they can be recycled or sent to a waste dump. The prepolymer, which is enriched and concentrated during the process in the distillation container can be used for many purposes. For instance, it can be used as adhesive, dissolved in toluol or another solvent, or as bonding agent for composite materials or as coupling agent for the production of molded parts made from recycled products such a vinyl tiles made of granulated old tires.

1 REPLACEMENT PAGE 49 WO 93/22077 PCT/EP93/00988 In the course of this method, the residues from aerosol cans or containers are moved to the working container and submerged in the solvent therein. As a result of the feeding in of residues into the working container and return of distilled solvent, the volume inside the container rises above the operating volume during which solvent is moved from the working container to the distillation container. On the whole, there is a constant volume of solvents and dissolved residues in the working container.

With a suitable medium, the distillation container is heated until the solution inside is boiling and a continuous solvent is distilled out. This solvent is then condensed with a cooling agent and returned directly or indirectly to the working container so that this container always has fresh solvent for dissolving the residues that are conveyed in. In this way, the residues that enter the working container are extracted continuously with solvent. The extracts become concentrated in the distillation container because the solvent there is removed continuously and will be recovered from there once they are concentrated enough. Insoluble residues that remain in the working container are drawn off from there at certain intervals.

The use of the inventive method is particularly advantageous for the recovery of prepolymers from aerosol cans for the production i of polyurethane foam. The aerosol can empties via an adapter into the working container. However, it is more advantageous to open the canE and extract the contents in the working container.

It is preferable to shred the aerosol can inside REPLACEMENT PAGE -i

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WO 93/22077 PCT/EP93/00988 -ll- -11the working container in a specially equipped device, such as a shredder. The shredding residues can be removed from the working container with a magnet because aerosol cans usually consist of tinplate, or with a worm conveyor, as mentioned above.

Ester, ketone, apliphatic or aromatic hydrocarbons or their derivatives with a boiling point of about 2000 C are particularly suited as solvent for the extraction. Alkyl ester of monocarboxylic acids and ketones with up to 8 carbon atoms, as well as alkyl benzene with up to 10 carbon atoms are especially suitable. Acetone, ketone, toluol and xylene are preferred. If the extracted prepolymer subsequently is to be used for adhesives, it is advisable to use toluol because adhesives based on polyurethane are frequently used in toluol solution. In addition, solvents of polyurethane prepolymers in toluol have a comparably low viscosity.

A thinner may be added to the distillation container which ensures or improves the flowability of the transferred and concentrated prepolymer. If the thinner is added at the start of the extraction already, it must have a higher boiling point than the solvent so that it does not become depleted during the extraction. Generally used thinners for prepolymers are trialkylphosphate, particularly triethylphosphate, or other raw materials that correspond to the original material.

REPLACEMENT PAGE [N:\LIBU]19848:KEH 51 WO 93/22077 PCT/EP93/00988 -12- With the inventive method, the propellant still contained in the aerosol cans as a rule fluoridated chlorhydrocarbons, partially halogenated hydrocarbons, dimethylether, propane, butane, etc. is collected and recovered if it is not used to render the plant inert. For this purpose, the gas flow coming from the working container can be condensed so that the propellants in. it are liquefied. As an alternative, the propellants can be condensed by cooling them and collected in a cooling trap.

The inventive method is suited for batch quantities as well as S for a continuous process. However, a continuous operation is recommended because of the still high investment costs.

Furthermore, the invention concerns a plant for use with the inventive method. Such a plant includes an incoming conduit, a device for opening the fed-in packaging materials, a collection container for the opened materials, at least one each feed-line for fresh solvent and protective gas, one discharge for solvent containing soluble packaging residues, one conveyor for solid packaging residues as well as at least one solvent spraying nozzle that is directed toward the device for opening the packaging materials. Peripheral equipment for recovering the solid and uissolved packaging residues, recovering the solvent as well as a trap for propellant gases released from the packaging S materials are also connected.

REPLACEMENT PAGE I v 52 WO 93/22077 PCT/EP93/00988 -13- The device for opening the fed-in packaging materials, which is used in the plant, consists of a traditional shredder with two counter-rotating drums equipped with cutting blades. It is essential that such a shredder or any other device for opening the packaging materials is sprayed with solvent during the process of opening so that all released residues are absorbed directly in by the solvent. This avoids a foaming up of the contents if it contains propellants, but also the sticking together. At the same time, any water adhering to or which has entered the packaging material is distributed by the spraying so that an uncontrolled reaction between the water and any released packaging content is avoided. This is particularly important during the processing of packaging materials containing polyurethane prepolymer, which interlaces uncontrollably if there is water present and can gum up the opening device. In the presence of sufficient amounts of solvent, the concentration of water that has entered can be reduced to a level where an uncontrolled reaction is impossible. Any interlacing that might still occur will stay in the tolerable range.

It is useful to have at least one spraying nozzle above the shredder. It is particularly advantageous if during the process of opening the containers, the opener is sprayed with solvent from top and bottom with at least one spray nozzle. Following the shredding, the packaging materials, together with the sprayed-on solvent, are transferred to a collection and extraction container from which the dissolved and/or liquid components are discharged REPLACEMENT PAGE B"

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53 WO 93/22077 PCT/EP93/00988 -14via a line and the solid residues are removed by conveyor.

It is useful if the conveyor is a worm conveyor which projects into the lower part of the collection container filled with solvent and removes the solid components from there. This worm conveyor is preferably sprayed with fresh solvent from one or more spray nozzles to wash off any packaging residue solution still clinging to the solid packaging residue that is removed.

The washed conveyor materials is then moved through a drying plant and removed via an outgoing conduit from the plant.

Subsequently it is moved to another place for further sorting and reuse.

The solvent used in the inventive method is effectively recirculated. This requires a continuous removal of the solvent from the extraction and collection container, distilling out of the dissolved content materials and, following condensation, feeding the solvent back into the plant via a pipe system and the spray nozzles or, if necessary, the washing device.

In accordance with the inventive method, the plant is run with protective gas, as described above. If'the protective gas is not released from the packaging materials themselves, it is piped in near the opening device and is drawn off again from the extraction and working container and/or the drying plant. In order to avoid additional costs, the protective gas can be recirculated. It is useful in that case to equip the protective REPLACEMENT PAGE

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2 54 WO 93/22077 PCT/EP93/00988 gas circulation with a device to separate out aerosols, moisture, propellant gases that were carried along and absorbed solvents.

It is useful to load the conduits with inert gases via separate lines. This is the only time it makes sense to use nitrogen, argon or C0 2 to prevent unwanted gases from escaping to the environment.

The invention is explained in more detail in the enclosed drawings (preferred form), which show as follows: Fig. 1 A laboratory-type recycling plant for illustration.

Fig. 2 A technical plant according to the invention.

Fig. 3 A detailed representation of the plant in Fig. 1.

Figure 1 shows a laboratory-scale recycling plant for polyurethane foaming agent. Inside a three-necked flask 1 with feed-in 2 and an overflow 4, as well as a vertical tube which ends in a reflux condenser 3, is the extraction solvent, to which the contents of not completely empty aerosol cans for the PU foam production is added via a feed-in 2 and an adapter that is not shown. A hollow magnet 10, which is moved with r magnetic stirrer 9, ensures continuous mixijag.

The solution from flask 10 is transferred to liquid flask 6 via overflow 4 in the same amounts at which material is added via feed-in 2 to the three-necked flask. A shut-off valve 5 ensures REPLACEMENT PAGE L t it V A WO 93/22077 PCT/EP93/00988 -16that there is a continuous supply of solution. The liquid flask 6 is heated with a heated bath 7 until the solution inside is boiling and evaporated solvent is distilled out via a tube 8 which connects to the reflux cooler 3. The solvent without extract that condenses at reflux cooler 3 drips back into operating flask 1, where it again participates in the extraction and, at the same time, effects a transfer of solution to the liquid flask 6.

The working of the inventive method in the above-described apparatus starts with the preparation of operating flask 1 which is filled, for example, with acetone as solvent. Parallel to that, a small amount of thinner such a triethylphosphate is filled into liquid flask 6 along with another solvent so that the collecting prepolymer in it remains free-flowing.

Subsequently, the cycle is started. The liquid flask 6 is heated to about 900 C and the reflux cooler and magnetic stirrer are activated. After about 15 mln., a system cycle has balanced out, meaning as much solvent as evaporates from liquid flask 6 via the distillation bridge 8 into reflux cooler 3, condensates there and drips into operating flask 1. From there, the solvent circulates via overflow 4 and shut-off valve 5 back to liquid flask 6. The cycle is closed.

As soon as a balance has been established, PU foam is fed into operating flask 1 via the feed-in tube 2 and an adapter which is not depicted. There, the foam dissolves immediately, the REPLACEMENT PAGE 4 3 11 56 WO 93/22077 PCT/EP93/00988 -17prepolymer dissolves and the propellant escapes through cooler 3 and is deposited in a cooling trap (not shown) at its upper end.

The fed-in prepolymer volume flows as a thinned solution via the overflow 4 into liquid flask 6. There, the prepolymer is enriched to the same degree that PU foam is sprayed via feed-in tube 2 into the operating flask 1 and is then transferred wo the liquid flask as a thinned solution. The free-flowing solvent, on the other hand, is in the cycle and is returned again and again from the liquid flask to the operating flask.

At the end of the operating cycle, a prepolymer solvent mixture rich in prepolymer forms in liquid flask 6. Closing the shut-off valve will prevent new solution from flowing into the liquid flask so that the prepolymer can be condensed further through distillation. The prepolymer is drawn from the liquid flask once it has reached the desired concentration and/or enrichment.

It is natural that not only the prepolymer component from the aerosol cans will be enriched in the liquid flask, but also the inherent additives and catalysts. As far as the product is again used to form polyurethane, these substances do not cause any problems. If it is used for other purposes, these substances can be removed at least partially through distillation under normal pressure or in a vacuum through extraction with solvents, which do not dissolve the polymer and do not react with it.

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57 WO 93/22077 PCT/EP93/00988 -18- Figure 2 shows a diagram of the processing sequence inside a plant for prepolymer recovery from packaging containing prepolymers, particularly aerosol cans, which is operated according to the inventive method. This method can be used to process other packaging materials as well, without modifications apparent to the expert.

The plant as shown in Figure 2 consists of three stages, the mechanical processing, the prepolymer recovery and the propellant recovery. In the mechanical processing stage, the delivered packaging materials first pass through an initial storage area and then reach a charging station where the packaging is freed of foreign materials and plastic components and is also pre-dried.

They are then fed into a shredder 12 via a metered addition with a scale and an input conduit 11. In the shredder, they are shredded while being sprayed with solvent and transferred to working container 13. In this working container, the shredded packaging materials are washed with solvent and separated from any soluble components. The solid components are removed via a conveyor 14 while being sprayed continuously with solvent and are then fed into a drying plant 15 and subsequently removed from the operating cycle via a conduit 16. The solvent evaporated in the drying plant 15 is condensed and returned to the process. After being removed, the shredded solid materials are sorted according to material type and moved to a recycling facility.

The solvent collected in working container 13 and all residues dissolved therein is conducted through line 17 to a receiving REPLACEMENT PAGE la 58 WO 93/22077 PCT/EP93/00988 -19container 18 from which the solution is then piped to the distillation plant. There, the solution is distilled out, if necessary under low pressure. The distillation residue is then drawn off, adjusted and conditioned for further use and returned to the economic cycle. Residues which cannot be reused can either be burned or deposited as concentrate on a disposal site.

The solvent distilled out of distillation plant 19 is condensed in a condensation plant 20 and returned to the cycle via a storage tank 21 and line 22. Solvent losses are balanced by fresh solvent. The condensed solvent travels from storage tank 21 via spray nozzles (see Fig. 3) to shredder 12 and conveyor 14 back into working container 13.

Like the extraction and distillation, the shredding inside shredder 12 is done in the presence of protective gas, piped in via line 24. Normally, the accumulating propellant gases are sufficient to cover the protective gas need during the plant operation. A feed-in via line 24 is needed, in particular, if mostly empty pressurized cans are processed or if the plant is started. The gas component released during shredding is led together with the protective gas flow via line 25 and, if applicable, an aerosol separation plant and drying plant 25a to a condensation facility 26. There, in a first stage 26a, adhering solvent is separated out and fed into a storage container 27 which is connected via line 28 with the solvent tank 21 for condensing plant 20. In a second stage 26b, the propellants REPLACEMENT PAGE ","AVT r are condensed, recovered and collected in a tank 29 if they are not used as protective gas for the plant. Propellant gases which are collecting in distillation plant 19 can also be fed into the propellant condensing plant. A portion of the propellant gases is returned from the condensing plant to the processing plant and, if necessary, replenished from storage tank 35 via line 24.

Conduits 11 and 16 each are supplied via lines 32 and 34 with nitrogen from liquid gas tank 30, which arrives either after passing through a distiller 31 or heat exchanger 26b.

It is useful to condensate the propellants from line 25 in condenser 26b with the aid of fresh and cold liquid nitrogen supplied via line 33 from liquid gas tank 30. This nitrogen is subsequently fed into conduits 11 and 16 via lines 34 and 23.

Propellant gas components which are not condensed and do not cause damage are released into the atmosphere near tank following condensation, if the protective gas need of the plant is met.

Figure 3 shows an inventive plant for mechanical processing of residue-containing packaging materials. This plant consists of a material feed and a conduit 11, which is filled with packaging materials ready for processing via a traveller 11a and which releases the fed-in packaging materials via a second traveller lib to the actual plant. Conduit 11 is filled with nitrogen via line 23.

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o WO 93/22077 PCT/EP93/00988 -21- Below conduit 11 is an opening and/or shredding device consisting of two motor-driven and counter-rotating drums, which shred the fed-in packaging materials with their attached cutting blades or similar cutters. Two spray nozzles 41a and 41b for spraying solvent onto the surface of the rotating drum are arranged above the shredder. Solvent is sprayed onto the shredded materials in the same way with spray nozzles installed at an angle below the shredder drums.

Spray nozzles 41a, 41b as well as 42a and 42b are supplied with fresh solvent via feed-in lines 22 and 22b, which is transported after spraying, together with the shredded materials to the extraction and working container 13 below the shredder 12.

Container 13 holds the extraction/solvent mixture together with the solid components of the packaging materials. A motorized stirrer 44 ensures that solid residues and solvent are in close contact and the extraction is effective. The extract is pumped from container 13 with a motorized pump 45, through a line 17 and into storage container 18 for prepolymer recovery, which is shown in Figure 2.

S A worm conveyor 14, the lower end of which is submerged in the j extract/solvent mixture, removes solid packaging residues from container 13. To remove extract from the solid packaging II material residues, these are moved with the worm conveyor through j washing segment which contains spraying nozzles 43 that are pointed toward the conveyor. Spraying nozzles 43 are supplied REPLACEMENT PAGE tit, i s y 61 WO 93/22077 PCT/EP93/00988 -22with fresh solvent via lines 22 and 22a. The solvent sprayed onto worm conveyor 14 travels to container 13.

The solid packaging residues moved along with worm conveyor 14 are fed via a batch funnel into a drying facility 15 where a conveyor 46 moves the solid residues along under a heater 47.

From there, the materials are moved to a discharge conduit 16.

This conduit 16 is sealed on the plant side with a slide 16a and on the solid material processing side with a slide 16b. Nitrogen can be fed into conduit 16 via a line 23a.

The processing plant consists of a motorized conveyor 48 which transports the material through a magnetic separator 49. With the aid of this magnetic separator, the material is separated according to its magnetic qualities.

The invention-based plant according to Fig. 3 with the exception of the conduits is operated with protective gas.

This protective gas is fed via line 24 into shredder 12 and distributed throughout the plant. Any protective gas leaving the plant, which contains solvents and small amounts of nitrogen from the conduits, is drawn off via line 25 from container 13 and/or via line 25a from the drying facility 15 for solid packaging residues. It may be useful to recirculate the protective gas if the amount of gas collecting from the pressurized cans it low.

It is useful to have motorized valves in all lines if it is necessary to regulate the flow of material in them.

REPLACEMENT PAGE Vi -LYr^ L I WO 93/22077 PCT/EP93/00988 -23- This is particularly true for the solvent feed-in lines to the spray nozzles and washing facilities, the operation of which can be stopped as soon as the material feeding and/or removal of solid residues is finished.

In the preceding description, the terms propellant, propellant gas, protective gas and inert gas are used interchangeably, insofar as the operation of the actual plant is concerned. With respect to the conduit arrangement, the protective and/or inert gases are understood to be traditional protective gases such as nitrogen and argon.

The facilities and plants used for the inventive method are commercially available or can be retrofitted by an expert to suit this purpose through simple modification or adaptation of known facilities and plants.

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REPLACEMENT PAGE

Claims (24)

1. A method of processing residue-containing packaging materials to recover valuable materials, especially from pressurised containers for spraying polyurethane foams with propellants, and extracting with solvents, with the following steps, performed in an atmosphere consisting essentially of propellants and/or solvents vapours: feeding the packaging materials into a work container while simultaneously opening them and extracting the residue with a solvent, transferring the residue from the work container into a distillation container, concentrating the residue-containing solution in the distillation container by distilling out the solvent, condensing the processed solvent and 1o returning it to the work container, and removing the packaging material residue from the work container and, after adequate enrichment, recovering of the residue in concentrated form from the distillation container.

2. The method according to claim 1, wherein the packaging materials are opened by shredding,

3. The method according to claim 2, wherein the packaging materials are shredded and, at the same time, sprayed with solvents.

4. The method according to any one of claims 1 to 3, wherein solid shredder residues are removed from the working container with the aid of a conveyor.

5. The method according to claim 4, wherein the conveyor is a worm conveyor.

6. The method according to any one of claims 2 to 5, wherein ferromagnetic shredder residues are removed magnetically from the work container,

7. The method according to any one of claims 2 to 6, wherein the shredder residues are sprayed with solvent while they are removed.

8. The method according to any one of claims 1 to 7, wherein ester, ketone, aliphatic and/or aromatic hydrocarbons with a boiling point of about 200 0 C are used as solvents,

9. The method according to claim 8, wherein acetone or toluol are used as solvents.

10, The method according to any one of claims 1 to 9, wherein the solvent is distilled from the distillation container under reduced pressure.

11. The method according to any one of claims 1 to 10, wherein the gases contained in the packaging material, in particular the propellants and, if applicable, the solvents, are separated and extracted,

12. The method according to claim 11, wher.in the gases are condensed.

13. The method according to any one of claims 1 to 12, carried out with a released propellant gas as protective gas which is propane, butane, dimethylether, fluoridated hydrocarbons and/or COz,

14. The method according to claim 13, wherein the protective gas is propane.

I *g I I rII I -'p [N:\libuu]00418:KEBl L MM Processing plant for applying the method according to one of claims 1 to 14 with an intake and an exit channel, a device for opening the fed-in packaging material, at least one each feed line for fresh solvent and the protective gas, one conduit for soluble packaging material residue-containing solvents, one conveyor for solid residue and at least one spray nozzle for spraying solvents, which is directed toward the device to open up the packaging materials, characterised by an extraction and collection container for the opened material, as distilling plant for distilling out the solvents, one condensing plant for the distilled solvents, one return pipe for condensed solvents as well as the equipment for recovering the dissolved packaging materials.

16. The plant according to claim 15, wherein the device for opening the packaging materials consists of two counter-rotating cutting drums, which form the shredder.

17. The plant according to claim 15 or claim 16, wherein at least one spray nozzle is attached above the device for opening the packaging materials and is pointed toward it.

18. The plant according to any one of claims 15 to 17, wherein at least one spray nozzle is installed below the device for opening the packaging materials and is pointed toward it.

19. The plant according to any one of claims 15 to 18, comprising a worm conveyor for removing the packaging material residues, which projects into the collection container.

20. The plant according to any one of claims 15 to 19, wherein nozzles for spraying solvents are installed above the conveyor for solid packaging material residues and are pointed toward it.

21. The plant according to any one of claims 15 to 20, comprising a drying rack which joins the conveyor.

22. The plant according to any one of claims 15 to 21, comprising separate protective gas lines in the area of the conduit.

23. A method of processing residue-containing packaging materials to recover valuable materials, substantially as hereinbefore described.

24. Material recovered by the method according to any one of claims 1 to 14 or eIIe 30 claim 23. A processing plant, substantially as hereinbefore described with reference to the accompanying drawings. Dated 5 January, 1996 Rathor AG Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON [N:\libuu]004 18:K3H1 ~rrrr~l~u