Patent Description:
Waste from garbage dumps is strongly heterogeneous in its composition and comprises many unpredictable components. As a result of this, polyolefins and also other raw materials can presently not be recycled from garbage dumps.

In industrialized countries heterogeneous polyolefin-rich waste streams are either recycled mechanically to give lower-quality products, e.g. polyolefin recycling from Green dot collections of packaging waste in Germany employed as substitute fuel or incinerated with or without energy recovery.

The commercial recycling process of PO-containing waste uses a mechanical recycling, i.e. recompounding. In recompounding, PE and PP waste are usually separated by automated near-infrared (NIR) spectroscopy. The sorted materials are compounded after various grinding, floating, washing and drying steps.

The disadvantage of this technique is that recompounding can only be applied for mono-material. Modern plastic packages are, however, often made from many different materials.

For flexible film packaging applications the majority of used plastics are mixtures by themselves. These mixtures are multilayers of compatible and incompatible polymers and cannot be re-compounded without the use of expensive modifiers. In addition to that, the products obtained by recompounding such materials exhibit worse mechanical properties than pure polymers and their compatible polymer blends.

Thus, with the increasing use of multilayer packaging the recycling of PO has become more difficult. Common separation techniques like spectroscopic or density sorting are not successful due to the complexity of these materials. Optical means only scan the material at the surface layer (ignoring deeper materials within a multilayer composite) and the effective density of a particle depends on the ratio and the types of polymer used for a multilayer. Thus, mixed polymers from multilayers are only recovered by downcycling and can only be used in low-value markets, e.g. thick plastic parts as substitute for cement bricks or profiles.

In contrast to these mechanical recovery approaches solvent-based recycling is selective for polyolefins and generates pure and high quality recovered polymers from mixed post-consumer waste.

Dissolution-based processes are mentioned in a variety of patents for polyolefin-containing waste streams. However, no process is currently available that recovers high-quality polyolefin products from post-use flexible multilayer waste of garbage dumps in a quality that is comparable to virgin polyolefin material and can replace the latter in the typical subsequent processing steps.

It is known from <CIT> and <CIT>) to separate commingled post-consumer plastics with aromatic solvents (xylene, toluene) by selective dissolution. At first polystyrenic and second polyolefinic polymers are dissolved. In order to separate PVC Mizumoto used THF for post-extraction of the residue and Naumann proposed to use THF first (dissolution already at room temperature, incl. PS-extraction). All solvents mentioned therein are either aromatic or flammable low boiling (bp < <NUM>) and do not show very high electrical conductivities which is hazardous due to the risk of electrostatic charging and/or explosion. Thus these techniques require strict and expensive safety measurements to protect human health and environment. Another disadvantage is the low selectivity of the disclosed solvents for the target polyolefins which makes a pre-extraction necessary. Alternatively, Naumann proposed microdispersing the incompatible coextracted polymer (<CIT> and <CIT>). Both approaches result in additional costs for the process and are only able to provide a limited product quality.

A further disadvantage is that the residual solvent traces which are foreign substances for virgin PO-qualities have a negative impact on the applicability of the recovered polymer.

Though there are efforts to pre-extract foreign polymers or to use more selective solvents or solvent mixtures, there are still traces of co-dissolved foreign polymers which will be concentrated (together with the target polymer) during the drying process in which the filtered polymers are separated from the solvent. At locally higher concentrations the foreign polymers are incompatible with the target polymer and result in undesired impurities, like stickies, crusts or gel-particles, in the recovered polymer in particular during melt drying and extrusion with high temperature and friction.

Such a melt filtration of target polymer gel after a first solvent separation is known from <CIT>.

<CIT> discloses a process for the treatment or recycling of polyolefins and polyolefin-containing composite materials for complete material recycling of the individual components containing one or more further synthetic polymers and/or metal and/or natural polymers, wherein the process comprises treating the composite materials with a solvent selected from the group consisting of cycloalkanes, n-alkanes, isoalkanes and mixtures thereof, dispersing the polyolefin solution and an aqueous surfactant solution in one another after insoluble components have been separated off, and separating the obtained dispersion (which comprises precipitated polyolefin, an aqueous phase and an organic phase) into its constituents.

It was therefore an object of the present invention to provide the recycling process with an increased selectivity for the polyolefin.

This problem is solved by the method with the features of claim <NUM>.

According to the invention, a method for recycling of a polyolefin containing waste having the following steps is provided:.

The Hansen parameter δH is an acknowledged parameter which characterizes the solubility of a compound. For a variety of compounds the value of the Hansen parameter δH can be looked up in standard chemical books. The Hansen parameters δH mentioned in this patent application refer to the values tabulated in the following handbook: <NPL>.

It is preferred that the polyolefin is selected from the group consisting of PE, PP, LDPE, HDPE, LLDPE and mixtures of those.

In a preferred embodiment the solvent is selected from the group consisting group consisting of hydrocarbon compounds, preferably aliphatic hydrocarbon compounds, more preferably cycloaliphatic, linear or branched hydrocarbon compounds, in particular cycloaliphatic, linear or branched hydrocarbons compounds with <NUM> to <NUM> carbon atoms and mixtures of those.

It is further preferred that the liquid filtration aid contains at least one fluid selected from the group consisting of mono-/poly-hydroxy hydrocarbons with <NUM> to <NUM> carbon atoms, preferably with <NUM> to <NUM> carbon atoms, more preferably at least one fluid selected from the group consisting of <NUM>-propanol, <NUM>-propanol, <NUM>-butanol, <NUM>-butanol, <NUM>-pentanol, <NUM>-pentanol, <NUM>-pentanol, <NUM>,<NUM>-propanediol, <NUM>,<NUM>-propanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-pentanediol, <NUM>,<NUM>-pentanediol, <NUM>,<NUM>-pentanediol, <NUM>,<NUM>-pentanediol, <NUM>,<NUM>,<NUM>-propanetriol, <NUM>,<NUM>,<NUM>-butanetriol, <NUM>,<NUM>,<NUM>-butanetriol, <NUM>-(hydroxymethyl)-<NUM>,<NUM>-propanediol, <NUM>,<NUM>,<NUM>-pentanetriol, <NUM>,<NUM>,<NUM>-pentanetriol, <NUM>-(hydroxymethyl)-<NUM>-methyl-propanediol, <NUM>-propene-<NUM>-ol, propene-<NUM>-ol, <NUM>-butene-<NUM>-ol, <NUM>-buten-<NUM>-ol, <NUM>-buten-<NUM>-ol, <NUM>-butene-<NUM>-ol, (E)-<NUM>-Buten-<NUM>-ol, (Z)- <NUM>-Buten-<NUM>-ol, <NUM>-methyl-<NUM>-propen-<NUM>-ol, <NUM>-methyl-prop-<NUM>-en-<NUM>-ol, cyclopropylcarbinol, cyclobutanol, <NUM>-penten-<NUM>-ol, <NUM>-methyl-<NUM>-buten-<NUM>-ol, (Z)-<NUM>-penten-<NUM>-ol, <NUM>-methyl-<NUM>-buten-<NUM>-ol, <NUM>-methyl-<NUM>-buten-<NUM>-ol, (E)-<NUM>-penten-<NUM>-ol, <NUM>-methyl-<NUM>-buten-<NUM>-ol, <NUM>-penten-<NUM>-ol, <NUM>-penten-<NUM>-ol, <NUM>-penten-<NUM>-ol, <NUM>-penten-<NUM>-ol, (Z)-<NUM>-penten-<NUM>-ol, (Z)-<NUM>-Penten-<NUM>-ol, <NUM>-methyl-<NUM>-buten-<NUM>-ol, <NUM>-penten-<NUM>-ol, (E)-<NUM>-penten-<NUM>-ol, (E)- <NUM>-penten-<NUM>-ol, <NUM>-methyl-<NUM>-buten-<NUM>-ol, <NUM>-penten-<NUM>-ol, pent-<NUM>-en-<NUM>-ol, <NUM>-methyl-(E)-<NUM>-butenol, trans-<NUM>-penten-<NUM>-ol, <NUM>-penten-<NUM>-ol, (Z)-pent-<NUM>-en-<NUM>-ol, (E)-pent-<NUM>-en-<NUM>-ol, prop-<NUM>-en-<NUM>,<NUM>-dimethyl-<NUM>-ol, <NUM>-ethylcyclopropanol, <NUM>-methylcyclopropanemethanol, cyclopentanol, cyclobutanemethanol, cyclopropylmethylcarbinol, <NUM>,<NUM>-cyclopentanediol, and mixtures of those.

The at least one fluid contained in the liquid filtration aid can either show miscibility gaps with the solvent or is completely immiscible with the solvent. Complete immiscibility in the context of this patent application means that the fluid is only miscible with the solvent in a weight ratio of a maximum of <NUM> wt.

Preferably, the polyolefin containing waste is selected from the group consisting of green dot collection waste, industrial waste, post-consumer waste, household-waste, bulky waste, packaging waste, rigid plastic waste and mixtures thereof and comprises or consists of multilayered plastic material and contaminant, wherein the multilayered plastic material contains at least one layer with at least <NUM> wt. -% of a polyolefin and at least another layer with at least <NUM> wt. -% of an other polymer or polymer blend and, optionally, a further layer comprising more than <NUM> wt. -% metal and/or paper.

In a preferred embodiment the other polymer or polymer blend is selected from the group consisting of polyesters, polyethers, polyvinylacetate, polyvinylalcohols, ethylenevinylalcohols, polyamides, polyacrylates, polycarbonates, polyurethanes, aromatic polymers, preferably polystyrene, polyvinylchloride, polyvinylbutyrate, polybutadiene and its blends or copolymers.

The contaminant is preferably selected from the group consisting of glass, fillers, flame retardants, papers, colourants, printing inks, whiteners, such as titanium dioxide, bonding agents (e.g. tie layers), coatings, inert contaminants, foams, adhesives, metals, heavy metals, volatile organic substances, aromatic substances, halogenated aromatic substances, halogenated hydrocarbons, biologically degradable dirt, residual foodstuff, wood, textile fibres, natural fibres and its mixtures.

A mixture of step a) comprises preferably from <NUM> to <NUM>, more preferably <NUM> to <NUM> wt. -% polymer.

It is preferred that a temperature of <NUM> to <NUM>, preferably a temperature of <NUM> to <NUM>, is applied in steps a) to b). The temperature is selected carefully not to have a sudden evaporation of water but to achieve preferably low viscosities in order to keep the process safe, technically as simple as possible and adaptable to variations in polyolefin content.

It is preferred that a temperature of <NUM> to <NUM> is applied in step c).

Preferably, method according to one of the preceding claims, characterized in that the contacting time with the liquid filtration aid in step b) is at least <NUM>, preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM>, in particular <NUM> to <NUM>. The contact time is adaptable to variations in polyolefin content, degree of contamination, operation mode (continuous or batch wise) and service life of optional downstream police filter unit and/or fine filter unit in order to optimize the maintenance work (reduced downtime and/or manual handling) and to maximize the process efficiency.

It is preferred that the volume of the liquid filtration aid in step b) is from <NUM> to <NUM> wt. -%, preferably from <NUM> to <NUM> wt. -%, in relation to the mixture of waste and solvent coming from step a). Furthermore, apart from the purification ability, the high heat conductivity of the liquid filtration aid reduces the safety risk of the process.

It is preferred that the mixture is subjected to a separation process prior to step c), preferably a multi-step separation process, more preferably selected from the group consisting of a filtration process, in particular a filtration process using a sieve or a gap-filter with gaps from <NUM> to <NUM>, a sedimentation, a centrifugation and a decantation process and/or combinations thereof.

Following a possible additivation, the separation in step c) is preferably effected by evaporation of the solvent or by addition of a precipitant followed by precipitation and mechanical separation of the polyolefin. The additivation can be done in order to influence colour, surface properties, thermal/mechanical stability of the polymer (e.g. by adding pigments, masterbatches, non-organic particles, stabilizers etc.).

In a preferred embodiment the separated polyolefin is directly fed into an extruder and processed to a polyolefin granulate compound or masterbatch or film or the polyolefin is dried in a drying process and cooled to room temperature.

The present invention is described in more detail with respect to the following examples. These are examples according to the invention (A3 and B5) and examples according to the state of the art (A1, A2 and B1-<NUM>). The examples should contribute to the general understanding of the invention. The invention should, however, not be limited to the examples.

Multilayer packaging films have been cut into pieces of approximately <NUM>-<NUM><NUM> and used as input samples. All input samples have been dissolved by a multifold polyolefin-extraction in several <NUM> and <NUM> batches. The temperature that has been applied in this extraction step in order to dissolve PE is <NUM>-<NUM>. The residence time which was found sufficient for a complete extraction of PE was <NUM>-<NUM>.

After extraction of the waste material the extract solution has been filtered coarsely by means of simple tea strainers with two different sieve sizes, <NUM> and <NUM>, respectively).

From the TiO<NUM>-pigmented multilayer film, the achieved filtered PE-solutions were white coloured. These solutions were dried. The resulting PE-powders were molten with a melt-flow-index-equipment (MFl-equipment). X-ray fluorescence (XRF) measurements were performed to check the content of TiO<NUM>-pigments. A titanium content of <NUM> wt. -% Ti has been found.

As an effect of the different colour of some input samples the extracted PE-dispersion (solution with impurities) was coloured light yellow or pink from dissolved parts of the colouring ink.

In order to achieve a white or even natural non-coloured PE, the yellow/pink hot extract solution has been filtered by means of a <NUM>-L heated pressurized (cake) filtration (Temp. <NUM>; <NUM>-<NUM> bar; Seitz® depth filter sheet T1500, <NUM><NUM> filter area). The filter showed a pore size of less than <NUM> and was successful in removing some of the TiO<NUM>-pigments. Solutions with a weight ratio of <NUM> to <NUM> % PE could be filtered easily with a fresh filter device, but repeatedly after filtration of <NUM>-<NUM> of white-pigmented PE (depending on concentration this number correlates to from <NUM> to <NUM> of PE-dispersion) the filter was blocked.

The MFI-strand which has been produced after drying was still white. The XRF-measurement which was performed to check the content of TiO<NUM>-pigments revealed a titanium content of <NUM> wt.

After extraction of the waste material a filtration aid has been added to the extract solution. The mixture of extract solution and filtration aid has been separated by sedimentation and filtered by means of a <NUM>-L heated pressurized (cake) filtration (Temp. <NUM>; <NUM>-<NUM> bar; <NUM><NUM> filter area). An MFI-strand of the filtered material has been produced and examined by XRF-measurements. The titanium content was <NUM> wt.

Thus, a very high purification efficiency of <NUM>% with respect to the TiO<NUM>-pigments could be achieved.

For extract solutions of the same PE-concentration an increase in the service life of the filter by a factor of <NUM> could be achieved by using a filtration aid whilst also maintaining the purification performance.

Post-consumer flexible waste material has been extracted and filtered in the same way as described in example A.

Subsequently, the extract solution has been filtered by means of a coarse filter such as in example A1. The resulting coarsely filtered PE-solution has a green-brown (olive) colour and showed many fine dispersed dark-grey impurities. A microscopic analysis (frame size: <NUM><NUM>) of a film blown from the finely filtered material has revealed that the filtration has not been effective. The sample contained <NUM> particles formed by impurities. Their size can be derived from the particle size distribution diagram in <FIG>. The biggest particles show a considerable size of up to <NUM>.

The impurities caused blocking of the applied fine filter after filtration of <NUM> PE only.

The use of a massive excess of a solid filter aid (<NUM> % related to dissolved PE), e.g. celite™, could increase the throughput up to <NUM> PE (dissolved in hot solutions of <NUM>% to <NUM>% concentration).

To the same extent as in example B3 the fine-filtration throughput was increased by using the supernatant after <NUM> to <NUM> sedimentation of the coarse-filtered PE-solution.

Thus (even with applied accelerated sedimentation of the hot PE-solution in centrifugal field) there were no means to achieve a robust (long-lasting) fine filtration of the PE-solution by non-expensive methods (affordable by the low commercial price of the recovered PE). the cost of single-use dead end filters and/or consumption of filter aids including their later disposal are much too high for achieving a profitable application.

And from a technical view the throughput of the fine-filter is too low in relation to the necessary cleaning/CIP-expenses, filter media and used solvent amounts for rinsing. Additionally, the very small flows would require an expensive large filter device: A post-consumer-PE-dispersion of <NUM>% concentration could be filtered at a rate of <NUM> PE/(bar · cm<NUM> · s) only.

A liquid filtration aid was added to the already coarsely filtered PE-solution. The liquid filtration aid was a second polar solvent, e.g. an alcohol, which accelerated the sedimentation of the impurities. As a result either a) a homogeneous liquid phase with a solid precipitate consisting in insoluble impurities or b) a second liquid phase was obtained. The settled impurities were separated mechanically from the PE-containing phase without any loss of PE.

Blocking of the fine filter only occurs at PE-amounts as high as <NUM> - <NUM> when solutions of <NUM> wt. -% to <NUM> wt. -% PE are used. In comparison to the filter blocking observed in example B1) this is an improvement factor of almost <NUM> orders of magnitude.

A pc-PE-dispersion of <NUM> wt. -% concentration could be filtered at a rate of <NUM> PE/(bar · cm<NUM> · s). Necessary filter devices can be much smaller (cheaper) than in comparative example B4.

The microscopic analysis (frame size: <NUM><NUM>) of a film which has been blown from the PE recyclate confirmed that also the amount of impurities could be reduced considerably. The sample contained only <NUM> particles formed by impurities. This corresponds to reduction of impurities (fines) by means of liquid filtration aid of <NUM> %. Additionally, it can be concluded from the particle size distribution diagram in <FIG> that the impurities in the recyclate are smaller (only up to <NUM>) than in the case of a filtration without a liquid filter aid (compare to <FIG>).

Moreover, after the process, the filtration aid fluid showed enrichments of bonding agents and other polymeric materials, such as adhesives and/or polystyrene based polymers. <FIG> provide evidence for that.

Claim 1:
Method for recycling a polyolefin containing waste with the following steps:
a) mixing the polyolefin containing waste with a solvent having a Hansen parameter δH from <NUM> to <NUM> MPa<NUM>/<NUM>;
b) contacting this mixture with a liquid filtration aid having a Hansen parameter δH > <NUM> MPa<NUM>/<NUM>, wherein the liquid filtration aid contains at least one fluid with a Hansen-parameter δH from <NUM> to <NUM> MPa<NUM>/<NUM> that forms a miscibility gap with the solvent; and
c) separating the polyolefin from the mixture.