Patent Application
20240287280
The invention relates to a method of depolymerizing a terephthalate polymer into reusable raw material, such as terephthalate monomer and oligomers. The invention further relates to a reactor system for depolymerizing a terephthalate polymer into the reusable raw material. The invention finally relates to a solid composition, being polymerizable raw material obtainable from the method of depolymerization.
Terephthalate polymers are a group of polyesters comprising terephthalate in the backbone. The most common example of a terephthalate polymer is polyethylene terephthalate, also known as PET. Alternative examples include polybutylene terephthalate, polypropylene terephthalate, poly pentaerythrityl terephthalate and copolymers thereof, such as copolymers of ethylene terephthalate and polyglycols, for instance polyoxyethylene glycol and poly(tetramethylene glycol) copolymers. PET is one of the most common polymers and it is highly desired to recycle PET by depolymerization thereof into reusable raw material.
One preferred way of depolymerization is glycolysis, which is preferably catalyzed. Typically, as a result of the use of ethylene glycol, a reaction mixture comprising at least one monomer comprising bis (2-hydroxyethyl) terephthalate (BHET) may be formed. One example of a suitable depolymerization by glycolysis is known from WO2016/105200 in the name of the present applicant. According to this process, the terephthalate polymer is depolymerized by glycolysis in the presence of a catalyst. At the end of the depolymerization process, water is added and a phase separation occurs. This enables to separate a first phase comprising the BHET monomer from a second phase comprising catalyst, oligomers and additives. The first phase may comprise impurities in dissolved form and as dispersed particles. The BHET monomer can be obtained by means of crystallization.
A high purity is required for reuse of the depolymerized raw material. As is well-known, any contaminant may have an impact on the subsequent polymerization reaction from the raw materials. Moreover, since terephthalate polymers are used for food and also medical applications, strict rules apply so as to prevent health issues.
While applicant's process according to WO2016/105200 leads to a very high conversion of the terephthalate polymer and also facilitates separation of various additives from the BHET monomer, the inventors identified by-products of the depolymerization reaction, in particular 2-hydroxyethyl[2-(2-hydroxyethoxy)ethyl]terephthalate (BHEET) and diethylene glycol (DEG) that both may have an effect on the quality of the crystallized BHET monomer.
There is a need therefore for providing a process of depolymerizing a terephthalate polymer into reusable raw material having a high purity, so as to be suitable for preparation of fresh terephthalate polymer. Such process may not always yield a very high conversion of the terephthalate polymer, but acceptable conversion (rates) may be achieved. There is also a need for providing a reactor system in which such depolymerization process may be implemented.
According to a first aspect of the invention there is provided a method of depolymerizing a polymer comprising terephthalate repeating units into reusable raw material, the method comprising the steps of:
According to a second aspect of the invention, a reactor system is provided for performing the method of the invention, as will be discussed in more detail below.
According to a third aspect of the invention, the invention relates to a solid composition, being polymerizable raw material obtained from depolymerization and comprising at least 90.0 wt. % BHET in crystalline form, wherein the solid composition comprises less than 5 wt. % BHEET relative to BHET.
It has been understood by the inventors in the investigations leading to the present invention that contamination of the BHET recovered from the depolymerized product stream, preferably recovered by crystallization, was at least in part due to the potential formation during depolymerization of 2-hydroxyethyl[2-(2-hydroxyethoxy)ethyl]terephthalate (BHEET) and also of other soluble non-volatile impurities containing ethylene glycol (EG), such as diethylene glycol (DEG), mono-2-hydroxyethyl terephthalate (MHET) and bis-2-hydroxyethyl isophthalate (iso-BHET). The presence of BHEET and/or the other impurities named in the product stream exiting the reactor and in the solution from which the BHET is recovered, preferably by crystallization, may lead to a BHET product of lesser quality in terms of crystal and other properties. It has been found that BHEET in particular is important in this respect. The present invention recognizes the importance of BHEET in particular on BHET product properties, and thus proposes to monitor the BHEET mass fraction in the depolymerized product stream exiting the reactor and optionally adjust a mass fraction of BHEET in the depolymerized product stream to below a predetermined limit value, such that the mass fraction of BHEET in the depolymerized product stream is below the predetermined limit value when the depolymerized product stream enters the recovery step e). As a consequence, a recovered crystalline BHET monomer product may be obtained that better meets the requirements of purity for subsequent polymerisation. It has also been established that the amount of the other soluble non-volatile impurities in the BHET monomer end product, such as DEG, MHET and iso-BHET, may also be reduced due to reduction of the amount of BHEET.
The invention thus provides a method of depolymerizing a polymer comprising terephthalate repeating units into reusable raw material, the method comprising the steps of:
It is important to avoid producing too much BHEET in the reactor during depolymerization. It has turned out that the claimed catalyst, i.e. the reusable catalyst complex being capable of degrading the polymer into oligomers and/or monomers, wherein the catalyst complex comprises a catalyst entity, a metal containing particle, and a bridging moiety for connecting the catalyst entity to the magnetic particle, produces a decreased amount of BHEET for the same BHET yield, when compared to other catalysts. This means that the step of adjusting the mass fraction of BHEET in the product stream to below the predetermined limit value may not be necessary at all, or may only be necessary intermittently, and/or to a lesser extent than with other catalysts.
The depolymerized product stream exiting the reactor comprises at least the formed BHET, BHEET, DEG and the solvent used in depolymerization. According to an embodiment of the invention, a method is provided wherein the predetermined limit value of the BHEET-mass fraction in the depolymerized product stream defined relative to the BHET-mass fraction in the depolymerized product stream ranges from 1 wt. % to 10 wt. %, more preferably from 2 wt. % to 9 wt. %, and most preferably from 3 wt. % to 8 wt. %.
In another embodiment of the invention, a method is provided wherein the BHEET-mass fraction in the depolymerized product stream defined relative to the BHET-mass fraction in the depolymerized product stream is lower than 10 wt. %, or, in other preferred embodiments, ranges from 0.3 wt. % to 10 wt. %, more preferably from 1 wt. % to 9 wt. %, and most preferably from 2 wt. % to 8 wt. %. The use of the claimed catalyst complex allows producing such low relative amounts of BHEET in the depolymerization reaction.
Monitoring the mass fraction of BHEET in the product stream may be achieved by any means known in the art. For instance, the mass fraction may be measured by HPLC, either in-line or performed intermittently. Samples may be taken from the product stream, for instance just after exiting the reactor, to determine the mass fraction of BHEET. The samples may also be taken from other positions in the product stream, such as just before the recovery stage of BHET. In the claimed circular method, wherein the product stream is stripped from the BHET monomer and the remaining solvent is then re-fed to the reactor, it may be necessary to measure BHEET mass fraction during some cycles only. In other embodiments, the BHEET mass fraction is only measured a number of times and then assumed for future reaction runs. Although monitoring of BHEET is performed in accordance with the invention, the invention does not exclude that monitoring of at least one of the other by-products, such as DEG, MHET and iso-BHET, is executed as well.
It is observed, for the sake of completeness, that the optional adjustment of the mass fraction of BHEET in the depolymerized product stream in some embodiments may be achieved in a number of ways. For instance, it is not excluded that the mass fraction of BHEET in the depolymerized product stream exiting the reactor is reduced by dilution with solvent and/or BHET coming from another source. The depolymerized product stream in other words may be mixed with another stream so as to arrive at conditions suitable for the recovering of BHET, preferably by crystallization and the separation of formed crystals.
In an embodiment of the method as claimed, the mass fraction of BHEET in the depolymerized product stream and/or in the BHET-depleted stream may be adjusted by removing BHEET from at least one of the named product streams to a mass fraction below the predetermined limit value in the depolymerized product stream. Removal may be performed at any stage of the method, such as from the reactor itself, between the reactor and the BHET recovery, but, preferably, downstream from the BHET recovery when a circular product stream is created in a circular process such that recovered solvent (and some BHEET) is re-fed to the reactor. The essential feature is that the mass fraction of BHEET in the depolymerized product stream is lower than a predetermined limit value before entering the BHET-recovery step e). As already noted above, the claimed catalyst complex may not need an actual removal of BHEET from the depolymerized product stream, and preferably from the BHET-depleted stream, or only intermittently, and/or to a lesser extent than with other catalysts.
According to the invention a method is provided wherein the recovering step e) comprises separating BHET from the depolymerized product stream and recovering a BHET-depleted stream, and wherein the method further comprises the step of f) reusing the BHET-depleted stream as at least a part of the solvent in step a). It is not excluded that a part of the BHEET is recovered, and further processed so as to serve as a raw material for fresh polymerization for instance. Other uses may also be possible.
A further improved embodiment then adjusts the mass fraction of BHEET in the depolymerized product stream to below the predetermined limit value by purging a part of the BHET-depleted stream before refeeding it to the reactor in step g) and preferably after having recovered the BHET-depleted stream after the separation of BHET in step f). As already elucidated above, the claimed catalyst complex produces a relatively low amount of BHEET per process cycle. This means that none or a relatively low amount of BHEET has to be removed or purged in comparison with other catalysts. A lower purge is beneficial since the purge may also contain minor amounts of raw materials used in the depolymerization, and/or may contain minor amounts of the produced BHET, such as 1-2 wt. % of the purge amount.
A further embodiment offers a method wherein the purging is performed in each cycle of steps a) to g), or after each plurality of cycles of steps a) to g). The plurality of cycles may be chosen dependent on the need, and may be at least 2, more preferably at least 3, even more preferably at least 4, and at most 20, more preferably at most 15, even more preferably at most 10.
In yet another embodiment of the invention, a method is provided wherein the purging before refeeding the BHET-depleted stream to the reactor in step g) and preferably after having recovered the BHET-depleted stream after the separation of BHET in step f) is performed when a mass fraction of BHEET in the BHET-depleted stream is above a purge percentage of the predetermined limit value. The purge percentage may for instance be chosen such that it conforms to the amount of BHEET formed in one process cycle in some embodiments. This prevents the mass fraction of BHEET from accumulating in each process cycle. In such preferred embodiment, the purging is carried out until the mass fraction of BHEET in the BHET-depleted stream is about equal to the purge percentage of the predetermined limit value.
It has turned out that the purge percentage ranges from 0-50 wt % of the predetermined limit value in some embodiments. The predetermined limit value itself preferably ranges from 0-1 wt. % of the depolymerized product stream, but is more suitably defined in terms of a mass fraction relative to the mass fraction of BHET in the depolymerized product stream. The purge percentage when using the claimed catalyst may range from 0-20 wt % of the predetermined limit value in some embodiments.
The purging of the BHEET is preferably carried out in a distillation unit, which separates part of the BHEET from the reused solvent and optionally from water. In this process according to some embodiments, BHEET is separated from other components in the BHET-depleted stream, such as mother liquor originating from the recovery of BHET by crystallization.
The depolymerization step involves glycolysis, in which the ethylene glycol solvent is also a reactant to obtain BHET, and eventually the other by-products apart from BHEET, rather than for instance terephtalic acid that would be generated in hydrolysis. A polymer concentration in the reaction mixture or dispersion is typically from 1-30 wt. % of the total weight of the reaction mixture, although concentrations outside this range may also be possible.
The amount of ethylene glycol (EG) in the reaction mixture may be chosen within wide ranges. It has however been established that the ratio of the amount of polymer comprising terephthalate repeating units (in short PET) to the amount of EG is instrumental in influencing the BHEET mass fraction in the reaction mixture. In particular, it has been established that the BHEET mass fraction in the reaction mixture decreases with the PET:EG weight ratio. In a useful embodiment, the weight ratio of EG to the polymer is in the range of from 20:10 to 100:10, more preferably from 40:10 to 90:10, and most preferably from 60:10 to 80:10.
The reaction mixture is heated in step d) to a suitable temperature which is preferably maintained during depolymerization. The temperature may be selected in the range of from 160° C. to 250° C. It has turned out that a higher temperature in conjunction with the claimed catalyst complex yields a relatively low amount of BHEET in the reaction mixture and the ensuing product stream. In preferred embodiments therefore, the degrading step d) may comprise forming the monomer at a temperature in the range of from 185° C. to 225° C. Suitable pressures in the reactor are from 1-5 bar, wherein a pressure higher than 1.0 bar is preferred, and more preferably lower than 3.0 bar.
An average residence time of the BHET monomer during the degrading step d) may range from 30 sec-3 hours, and longer. In order to stop the depolymerization reaction and/or deactivate the catalyst complex, the temperature may be reduced to a temperature below 160° C. or lower, but preferably not lower than 85° C.
The BHET in the product stream may be recovered according to a number of methods. In a useful embodiment, the recovering step e) of BHET comprises a crystallization step wherein the depolymerized product stream is cooled, by passing through a heat exchanger for instance or, preferably, by adding water to the depolymerized product stream. In this way, a decrease of the temperature from the temperature of the degrading step d) to a crystallization temperature is achieved. Thereby BHET crystals are produced in the depolymerized product stream, thereby obtaining a mixture of BHET crystals and a mother liquor as BHET-depleted stream comprising at least ethylene glycol and BHEET. The crystallization temperature is preferably selected below 85° C., and may comprise a temperature between ambient and 85° C.
In an advantageous implementation, the crystallization temperature of the BHET crystallization is in the range of 10° C.-70° C., such as around 55° C., although lower temperatures may also be chosen, preferably in the range of 15° C.-40° C., more preferably about 18-25° C. The crystallization temperature is herein defined as the temperature defined at the start of the crystallization step, thus typically at which the nucleation occurs. It is not excluded that the temperature changes or is actively modified during the crystallization.
Yet another embodiment provides a method further comprising the step of:
In another embodiment of the method, the method further comprises separating the BHET crystals from the mother liquor stream in a solid/liquid separator arranged downstream of a unit for the crystallization of BHET and upstream of a unit for purging said part of the mother liquor stream. It is also possible to use two or more units for the crystallization of BHET.
Preferably, the process conditions during the BHET crystallization are controlled. Feasible control parameters include a mass fraction of BHEET, as claimed, in the composition at the start of the step of forming the BHET crystals; and/or a volume ratio between water and ethylene glycol in the depolymerized product stream during the step of forming the BHET crystals; and/or duration of the crystallization, particularly by controlling the temperature within a predetermined range for a predefined residence time, such as 2 minutes to 120 minutes, preferably in the range of 5 minutes to 60 minutes.
Also, an anti-solvent may be added to the product stream, prior to forming BHET crystals. The anti-solvent is preferably water or an aqueous solution, such as an aqueous salt solution. The solubility of the BHET is reduced by the addition of the anti-solvent.
More generally, the process conditions may be controlled so as to control the depolymerized product stream prior to the crystallization step with respect to the mass fraction of BHEET, and also of the BHET to be crystallized, and further with respect to a volume ratio between water and ethylene glycol and the control of the temperature during a predefined period.
In accordance with other embodiments of the invention, the formation of BHET crystals precedes a solid/liquid separation step in which the corresponding mother liquor is removed and the solid BHET crystals separated therefrom. The separation step may be carried out with any method known in the art, such as by filtration.
It is not excluded that the crystallization reactor includes the separator, which is for instance activated after a predefined residence time. However, a separate separator is deemed preferable. In case that the crystals are to be recovered, a washing step is preferably carried out after the separation step. A band filter is deemed one practical arrangement for performing a separation step and a subsequent washing step. The characteristic size of the solid/liquid separation means can be chosen in dependence of the size of the generated crystals and a desired duration for the separation step. In an implementation, recovering the BHET crystals comprises separating the BHET crystals from the mother liquor by means of filtration using a filter element.
The BHET monomer is preferably recovered in solid form. It is deemed appropriate that the recovery is followed by a washing step and a drying step. Preferably, the BHET monomer crystals essentially consist of BHET, such as at least 95 wt %, more preferably at least 96 wt. % or even at least 97 wt. %. More preferably, said BHET monomer crystals comprise at most 5.0 wt % of BHEET, at most 4.0 wt % of BHEET, at most 3.0 wt % of BHEET, at most 2.0 wt % of BHEET, at most 1.5 wt % of BHEET or even at most 1.0 wt % of BHEET.
The depolymerization step is catalysed by means of a catalyst. In a depolymerization method according to an embodiment, the catalyst forms a dispersion in the reaction mixture during step c). The heterogeneous catalyst that is used in the invention is a catalyst complex comprising catalyst particles and a catalyst entity that is associated with the catalyst particles, for instance attached thereto via a linking group. The catalyst entity comprises an ionic liquid comprising a cationic moiety having a positive charge and an anionic moiety having a negative charge. The claimed catalyst complex yields a relatively low amount of BHEET during depolymerization by glycolysis. The catalyst particles are preferably nanoparticles, and more preferably magnetic particles and the latter are preferably used in a method wherein the recovering step of said catalyst is carried out using a magnetic force of attraction between a magnet and said particles. The catalyst particles in themselves may also exhibit catalytic activity.
The catalyst complex (ABC) comprises three distinguishable elements: a (nano) particle (A), a bridging moiety comprising a linking group (B) attached to the particle chemically, such as by a covalent bond, or physically, such as by adsorption, and a catalyst entity (C) that is associated with the particles (A), such as by being chemically bonded, for instance covalently bonded, to the linking group. The linking group preferably does not fully cover the nanoparticle surface, such as in a core-shell particle.
The particles of the claimed catalyst complex are preferably based on ferromagnetic and/or ferrimagnetic materials. Also anti-ferromagnetic materials, synthetic magnetic materials, paramagnetic materials, superparamagnetic materials, such as materials comprising at least one of Fe, Co, Ni, Gd, Dy, Mn, Nd, Sm, and preferably at least one of O, B, C, N, such as iron oxide, such as ferrite, such as hematite (Fe2O3), magnetite (Fe3O4), and maghemite (Fe2O3, γ-Fe2O3) may be used. In view of costs, even when fully or largely recovering the present catalyst complex, relatively cheap particles are preferred, such as particles comprising iron (Fe). A further advantage of particles of iron or iron oxides is that they have highest saturation magnetisation, making it easier to separate the particles via a magnetic separator. And even more importantly, the iron oxide (nano)particles have a positive impact on the degradation reaction. The iron oxide may further contain additional elements such as cobalt and/or manganese, for instance CoFe2O4.
The catalyst particles that are used in the catalyst complex according to the invention may be coated at least partly with a protective coating. The coating may further serve to stabilize the catalyst in that the particles remain in suspension. Thus, at least a part of the surface of the catalyst particles may be coated with materials such as polyethyleneimine (PEI), polyethylene glycol (PEG), silicon oil, fatty acids like oleic acid or stearic acid, silane, a mineral oil, an amino acid, or polyacrylic acid or, polyvinylpyrrolidone (PVP). Carbon is also possible as coating material. The coating may be removed before or during the catalytic reaction. Ways to remove the coating may for instance comprise using a solvent wash step separately before using it in the reactor, or by burning in air. Removal of the coating however is not essential.
Preferably, the catalyst particles are selected so as to be substantially insoluble in the (alcoholic) reactive solvent, also at higher temperatures of more than 100° C. Oxides that readily tend to dissolve at higher temperatures in an alcohol such as ethylene glycol, such as for instance amorphous SiO2, are less suited.
It has been found that the catalyst particles preferably are sufficiently small for the catalyst complex to function as a catalyst, therewith degrading the terephthalate polymer into smaller units, wherein the yield of these smaller units and specifically the monomers thereof, is high enough for commercial reasons. It has further been found that the nanoparticles preferably are sufficiently large in order to be able to reuse the present complex by recovering the present catalyst complex. Suitable catalyst particles have an average diameter of larger than 1 μm up to 3 μm and larger. Suitable nanoparticles have an average diameter of from 2-500 nm, and even larger up to 1 μm.
In an example of the present catalyst complex the magnetic particles have an average diameter of 2 nm-500 nm, preferably from 3 nm-100 nm, more preferably from 4 nm-50 nm, such as from 5-nm. It has been found that e.g. in terms of yield and recovery of catalyst complex a rather small size of particles of 5-10 nm is optimal. It is noted that the term “size” relates to an average diameter of the particles, wherein an actual diameter of a particle may vary somewhat due to characteristics thereof. In addition aggregates may be formed e.g. in the solution. These aggregates typically have sizes in a range of 50-200 nm, such as 80-150 nm, e.g. around 100 nm.
Particle sizes and a distribution thereof can be measured by light scattering, for instance using a Malvern Dynamic light Scattering apparatus, such as a NS500 series. In a more laborious way, typically applied for smaller particle sizes and equally well applicable to large sizes, representative electron microscopy pictures are taken and the sizes of individual particles are measured on the picture. For an average particle size, a number average may be taken. In an approximation the average may be taken as the size with the highest number of particles or as a median size.
Non-porous particles according to embodiments of the invention have a surface area suitably less than 10 m2/g, more preferably at most 5 m2/g, even more preferably at most 1 m2/g. In an embodiment, the surface area of the catalyst particles is preferably more than 3 m2/g. The porosity is suitably less than 10−2 cm3/g or even at most 10−3 cm3/g. Porous particles are also possible, generally having a higher surface area.
The present catalyst entity comprises at least two moieties. A first moiety relates to a moiety having a positive charge (cation). A second moiety relates to a moiety, typically a salt complex moiety, having a negative charge (anion). The negative and positive charges typically balance one another. It has been found that the positively and negatively charged moieties have a synergistic and enhancing effect on the degradation process of waste terephthalate polymer in terms of conversion and selectivity.
The positively charged moiety (cation) may be aromatic or aliphatic, and/or heterocyclic. The cationic moiety may be aliphatic and is preferably selected from guanidinium (carbamimidoylazanium), ammonium, phosphonium and sulphonium. A non-aromatic or aromatic heterocyclic moiety preferably comprises a heterocycle, having at least one, preferably at least two hetero-atoms. The heterocycle may have 5 or 6 atoms, preferably 5 atoms. The positively charged moiety may be an aromatic moiety, which preferably stabilizes a positive charge. Typically the cationic moiety carries a delocalized positive charge. The hetero-atom may be nitrogen N, phosphor P or sulphur S for instance. Suitable aromatic heterocycles are pyrimidines, imidazoles, piperidines, pyrrolidine, pyridine, pyrazol, oxazol, triazol, thiazol, methimazol, benzotriazol, isoquinol and viologen-type compounds (having f.i. two coupled pyridine-ring structures). Particularly preferred is an imidazole structure, which results in an imidazolium ion. Particularly suitable cationic moieties having N as hetero-atom comprise imidazolium, (5-membered ring with two N), piperidinium (6-membered ring with one N), pyrrolidinium (5-membered ring having one N), and pyridinium (6-membered ring with one N). Preferred imidazolium cationic moieties comprise butylmethylimidazolium (bmim+), and dialkylimidazoliums. Other suitable cationic moieties include but are not limited to triazolium (5-membered ring with 3 N), thiazolidium (5-membered ring with N and S), and (iso)quiloninium (two 6-membered rings (naphthalene) with N).
In a preferred method, the cationic moiety of the catalyst entity is selected from at least one of an imidazolium group, a piperidinium group, a pyridinium group, a pyrrolidinium group, a sulfonium group, an ammonium group, and a phosphonium group.
Said cationic moiety may have one ore more substituents, which one ore more substituents is preferably selected an alkyl moiety. In particular examples, said alkyl moiety has a length of C1-C6, such as C2-C4. In specific examples, said imidazolium group has two substituents R1, R2 attached to one of the two nitrogen atoms, respectively, said piperidinium group has two substituents R1, R2 attached to its nitrogen atom, said pyridinium group has two substituents R1, R2 wherein one of the two substituents R1, R2 is attached to its nitrogen atom, said pyrrolidinium group has two substituents R1, R2 attached to its nitrogen atom, said sulphonium group has three substituents R1, R2, R3 attached to its sulphur atom, said ammonium group has four substituents R1, R2, R3, R4 attached to its nitrogen atom, and said phosphonium group has four substituents R1, R2, R3, R4 attached to its phosphor atom, respectively.
The negatively charged moiety (anion) may relate to an anionic complex, but alternatively to a simple ion, such as a halide. It may relate to a salt complex moiety, preferably a metal salt complex moiety, having a two- or three-plus charged metal ion, such as Fe3+, Al3+, Ca2+, Zn2+ and Cu2+, and negatively charged counter-ions, such as halogenides, e.g. Cl−, F−, and Br−. In an example the salt is a Fe3+ comprising salt complex moiety, such as an halogenide, e.g. FeCl4−. Alternatively, use can be made of counter-ions without a metal salt complex, such as halides as known per se.
The linking group may comprise a bridging moiety for attaching the catalyst entity to the catalyst particle. The present catalyst entity and particle are combined by the bridging moiety by attaching the catalyst entity to the catalyst particle. The attachment typically involves a physical or chemical bonding between a combination of the bridging moiety and the catalyst entity on the one hand and the catalyst particle on the other hand. Particularly, a plurality of bridging moieties is attached or bonded to a surface area of the present catalyst particle. Suitable bridging moieties comprise a weak organic acid, silyl comprising groups, and silanol. More particularly, therefore, the bridging moiety comprises a functional group for bonding to the oxide of the particle and a second linking group for bonding to the catalyst entity. The functional group is for instance a carboxylic acid, an alcohol, a silicic acid group, or combinations thereof. Other acids such as organic sulphonic acids are not excluded. The linking group comprises for instance an end alkyl chain attached to the cationic moiety, with the alkyl chain typically between C1 and C6, for instance propyl and ethyl. The linking group may be attached to the cationic moieties such as the preferred imidazolium moiety. In the attached state, a BC complex then for instance comprises imidazolium having two alkyl groups, such as butylmethylimidazolium (bmim+) or ethylmethylimidazolium as an example.
The bridging moiety is suitably provided as a reactant, in which the linking group is functionalized for chemical reaction with the catalyst entity. For instance, a suitable functionalization of the linking group is the provision as a substituted alkyl halide. Suitable reactants for instance include 3-chloropropyltrialkoxysilane and 3-bromopropyltrialkoxysilane. The alkoxy-group is preferably ethoxy, although methoxy or propoxy groups are not excluded. It is preferred to use trialkoxysilanes, although dialkyldialkoxysilanes and trialkyl-monoalkoxysilanes are not excluded. In the latter cases, the alkyl groups are preferably lower alkyl, such as C1-C4 alkyl. At least one of the alkyl groups is then functionalized, for instance with a halide, as specified above.
The said reactant is then reacted with the catalyst entity. Preferably, this reaction generates the positive charge on the cationic moiety, more particularly on a hetero-atom but mostly delocalized, in the, preferably heterocyclic, cationic moiety. The reaction is for instance a reaction of a (substituted) alkyl halide with a hetero-atom, such as nitrogen, containing cationic moiety, resulting in a bond between the hetero-atom and the alkyl-group. The hetero-atom is therewith charged positively, and the halide negatively. The negatively charged halide may thereafter be strengthened by addition of a Lewis acid to form a metal salt complex. One example is the conversion of chloride to FeCl4−.
According to the present invention, the bridging moiety and the catalyst entity bonded thereto are provided in an amount of (mole bridging moiety/gr magnetic particle) 5*10−6-0.1, preferably 1*10−5-0.01, more preferably 2*10−5-10−3, such as 4*10−5-10−4. It is preferred to have a relatively large amount available in terms of an effective optional recovery of the catalyst complex, whereas, in terms of amount of catalyst and costs thereof, a somewhat smaller amount may be more preferred.
The catalyst is in preferred embodiments used in a weight ratio of the catalyst complex to the polymer ranging from 0.001:10 to 1.0:10, preferably 0.005:10 to 0.5:10.
According to another aspect of the invention there is provided a reactor system for depolymerizing a terephthalate polymer into reusable raw material, said reactor system comprising:
This reactor system is configured for performance of the process of the invention.
The reactor system according to an embodiment is provided such that the optional means for adjusting the mass fraction of BHEET in the depolymerized product stream are configured to purge a part of the BHET-depleted stream before refeeding it to the reactor via the feedback loop.
Yet another embodiment provides a reactor system, comprising at least one controller unit configured to control the purging such that the mass fraction of BHEET in the BHET-depleted stream is about equal to a purge percentage of the predetermined limit value.
In another practical embodiment, a reactor system is provided wherein the BHET recovering stage comprises a crystallization unit for crystallization of BHET monomer from said product stream, wherein a remaining BHET-depleted stream constitutes a mother liquor comprising ethylene glycol and BHEET.
A preferred reactor system according to an embodiment further comprises a feedback loop to the reactor for reusing the recovered mother liquor stream as at least a part of the solvent in the reactor, and a unit for purging the mother liquor stream arranged upstream of the feedback loop when a mass fraction of BHEET in the recovered mother liquor stream is above a purge percentage of the predetermined limit value.
In such embodiment, the reactor system preferably further comprises a solid/liquid separator for separating the BHET crystals from the mother liquor stream arranged downstream of the crystallization unit for crystallization of BHET and upstream of a purging unit for purging said part of the mother liquor stream.
Another preferred embodiment relates to a reactor system, wherein the purging unit comprises a distillation unit for separating part of the BHEET from the reused solvent and optionally from water.
It may also have advantages to provide a reactor system according to yet another embodiment further comprising a separator unit for separating and recovering the catalyst complex from the product stream, and, optionally, a feedback loop to the reactor for reusing the recovered catalyst complex. A suitable separator unit may comprise one or more of a filtration unit, a centrifugation unit, or a magnetic attraction unit, or combinations of these.
Typically the BHET recovering stage comprises a crystallization unit, embodied as at least one vessel with an inlet and an outlet. Preferably a controller is present for controlling process conditions in each of said vessels. Sensors may be available thereto, as known to those skilled in the art. The crystallization unit, and the separator may be configured for batch operation or for continuous operation. Alternatively, the system is semi-continuous, in that the crystallization unit is of a batch type but the streams from the further processing stage and beyond are continuous. In this implementation, a plurality of crystallization units may be arranged in parallel so as to load one crystallization unit while performing the crystallization treatment in another parallel arranged one. In another embodiment, a plurality of crystallization units may be arranged in series for more continuous operation.
An integrated reactor system has the advantage that heat loss is reduced to a minimum, which prevents unforeseen precipitation. It is a further advantage that the mother liquor remaining after crystallization of the BHET is recycled for use in the depolymerization stage, after a certain amount of BHEET has been purged therefrom. Thereto, it is preferably subjected to a distillation treatment so as to reduce BHEET and water content in the ethylene glycol.
In an embodiment, the monomer crystal recovering stage comprises a filtration unit configured to separate the BHET crystals from the mother liquor by means of filtration, and wherein the filtration unit is configured to carry out an optional washing of the separated BHET crystals inside the filtration unit.
It is to be understood that any of the embodiments discussed hereinabove and/or hereinafter with reference to the figures or in the context of the examples or as defined in the dependent claims with respect to one aspect of the invention is also applicable and deemed disclosed in relation to any other aspect of the invention, which aspects are further defined in the claims as filed.
The above and other advantages of the features and objects of the invention will become more apparent and the invention will be better understood from the following detailed description when read in conjunction with the accompanying drawings, in which:
The accompanying drawings are used to illustrate presently preferred non-limiting exemplary embodiments of devices of the present invention. The figures are not drawn to scale. The same reference numerals in different figures refer to equal or corresponding elements.
The reactor system 10 is provided with an input stream A comprising polymeric material. Preferably, this polymeric material has been pre-separated so that at least the bulk thereof is the terephthalate polymer for depolymerization, more particularly PET. The input stream A may be in solid form, such as in the form of flakes. However, it is not excluded that the input stream is in the form of a dispersion or even a solution.
The input stream A goes into the depolymerization reactor 1. Other streams entering this depolymerization reactor include a stream B of fresh solvent, such as ethylene glycol, and a stream of fresh catalyst C. The stream C may also comprise an optional recycled stream X of catalyst. A recycled stream Y of solvent, such as ethylene glycol, also enters the reactor 1. The input streams A, B, C, and the recycle streams X and Y may be arranged as individual inlets or may be combined into one or more inlets. The depolymerization reactor 1 may be of a batch type or a continuous type. While it is indicated as a single reactor, it is not excluded that a combination of reactor vessels is used, such as the combination of a tank reactor and a plurality of plug flow reactors as disclosed in WO2016/105200A1, incorporated herein by reference. Also a plurality of vessels may be arranged in parallel within one unit. While not indicated, it will be understood that the reactor system 10 is provided with a controller and that sensors may be present as well as valves for setting flow rates into the reactor and for setting residence times in the reactor. Furthermore, the reactor 1 and separation means 2, 3, 4 and 5 may be provided with heating means and/or other temperature regulation means so as to prevent deviations from predefined temperatures and other variables.
Following the depolymerization in reactor 1, the depolymerized reaction mixture is pumped to a separation/filtration unit 2, which may be provided with an inlet for water D. The water D may alternatively be provided as an aqueous solution. It is not excluded that one or more further additives are added thereto, so as to facilitate the phase separation intended to occur in the separation/filtration unit 2. The separation/filtration unit 2 serves to cool down the depolymerized mixture from a depolymerization temperature, typically in the range of 160-200° C., to a processing temperature, for instance around 100° C. The optional water D may contribute to the cooling process, and also to the generation of a two-phase mixture in the separation/filtration unit 2. A first phase at least comprises monomer BHET and BHEET as solutes in a mixture of ethylene glycol and optionally water. A second phase comprises BHET oligomers, catalyst, additives. The two-phase mixture is separated in the separation/filtration unit 2 which thereto comprises a first separator, for instance a centrifuge. The second phase containing catalyst may thereafter be recycled to the depolymerization reactor 1 as stream X. While the separation/filtration unit 2 is shown as one unit, it is not excluded that this unit 2 comprises a number of separate units, such as a cooling vessel, the first separator, and a filtration unit. Alternatively, a cooling function may actually be incorporated in the depolymerization reactor 1 as a physically single unit, particularly in case of using a batch process. Also, in other embodiments, further purification units may be provided. Separating BHEET may also be carried out before BHET crystallisation by providing a suitable separation unit for BHEET stream upwards from a BHET crystallization stage 3.
The first phase leaving the separation/filtration unit 2 is also referred to as a solution S in the context of the present invention. Rather than a pure solution, the solution S may be a colloidal solution or a dispersion. The solution S is transferred to a BHET crystallization stage 3 in which BHET is crystallized and subsequently recovered in a separator 4 as solid BHET monomer product I. Rather than or in addition to lowering the temperature relative to the separation/filtration unit 2, an anti-solvent such as water E may be added to the solution S in the crystallization stage 3, as indicated in the figure by means of the line E. This will reduce the solubility of BHET and enable crystallization and a higher temperature. Upon the crystallization of the BHET, the solution S is transformed into a slurry M that comprises solid BHET, as well as BHEET. The slurry M enters a solid/liquid separation stage 4, in which the solid BHET monomer product I is separated from the slurry M. The remaining mother liquor MI that also contains BHEET is then led to a processing stage 5, which preferably includes at least one distillation column. In the processing stage 5, the mother liquor MI is processed to reduce its water content, as well as its BHEET content through a BHEET purge Z. The resulting upgraded ethylene glycol is returned to the depolymerization reactor 1 as stream Y. The dewatering process results in a water recycle stream
By means of the process of the invention, it has turned out feasible to arrive at a BHET monomer product I that is white and free of major contaminants.
Further variations may be envisaged by a skilled person. It is for instance feasible that the recycling of one or more of the streams X and Y comprises a (further) purification step, heating or cooling step. It is not excluded that the streams X and Y are merged prior to the entry into the depolymerization stage.
Depolymerization experiments were carried out using a 500 ml round bottom flask. An amount of 0.034 g of dry catalyst was used in combination with 33.4 g of polyethylene terephthalate (PET) flakes (pieces of 0.3×0.3 cm2) and 250 g of ethylene glycol. The tested heterogeneous catalysts of Examples 1-3 and Comparative Experiments A and B were chosen as indicated in Table 1. A homogeneous catalyst was used in Comparative Experiment C, as also shown in Table 1.
The round bottom flask was placed in a heating set up. The heating was started under stirring, and after 20 minutes, the reaction mixture had reached the reaction temperature of 197° C. under reflux. The reaction was followed in time by taking in-process-control samples to measure the mass fraction of monomer (bis(2-hydroxyethyl) terephthalate, or BHET) and by-products (such as 2-(2-hydroxyethoxy)ethyl (2-hydroxyethyl) terephthalate or BHEET) produced as a function of time (in minutes). The mass fraction of BHET and BHEET was determined with HPLC.
The results are shown in
The claimed catalyst complex not only performs well in depolymerization of PET but also produces the lowest amount of impurities, in particular BHEET. This means that, since the BHEET purge is active only when the predetermined limit value is exceeded, the BHEET purge for the claimed catalysts is much less active, or can even be omitted, which is advantageous from an energetic point of view.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2028499 | Jun 2021 | NL | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/NL2022/050348 | 6/20/2022 | WO |
