Patent Grant
12168715
This application is a national-stage application under 35 U.S.C. § 371 of International Application No. PCT/IN2020/050230, filed Mar. 13, 2020, which international application claims the benefit of priority to Indian Patent Application No. 201911010930, filed Mar. 20, 2019.
The present invention relates generally to biodegradable PET polymeric raw material. In particular, the present invention relates to a process of manufacturing biodegradable polyethylene terephthalate or PET chips for use in making biodegradable polyester package such as film/laminate pouches, bottles, trays or any other product.
Plastics are typically organic polymers of high molecular mass. They are usually synthetic and made by polymerisation, most commonly derived from petrochemicals. Plastics are inexpensive, durable and easy to process substances compared to the other options, which are employed to manufacture a variety of components that find usage in a wide range of applications. As a consequence, the production of plastics has increased dramatically over the last few decades. For example, polyethylene terephthalate, or PET, is a widely produced thermoplastic polymer for manufacturing polymeric products such as films, bottle etc. Because of the durability of the polymeric products having high resistance to degradation (due to high molecular mass values, hydrophobicity and crystallinity), despite being recyclable, due to poor collection, substantial quantities of disposable plastics are piling up in landfill sites and in natural habitats, generating increasing environmental problems worldwide.
To answer these problems, different physical, chemical and/or biochemical approaches have been developed to reduce the biodegradation resistance of polymeric products and to increase their biodegradation rate. For example, additives have been introduced to mix/blend with non-biodegradable polymeric resins during user end polymeric product manufacturing stage to make polymeric product biodegradable. However the mixing of additives during the end product manufacturing to make biodegradable polymeric product appears to be satisfactory, but mixing of additive during end product manufacturing, particularly for large scale production for packaging and other products made of polyester or PET chips having specific properties including a minimum intrinsic viscosity and uniform dispersion, requires additional complex observation, expertise, testing and quality control. This inhibits the adaptation of the process of mixing the additive at end product manufacturing stage to make biodegradable product.
Thus, there is a need of biodegradable PET chips for making biodegradable PET polymeric products, ready to use for making bio degradable polymeric products without mixing of such additive at the end product manufacturing stage.
The present invention describes a process of manufacturing biodegradable PET chips, comprising the steps of providing a purified terephthalic acid (PTA) in a predetermined quantity in a slurry tank; providing virgin and/or recycled Mono-Ethylene Glycol (MEG) in a predetermined quantity in the slurry tank; transferring the combination of the slurry tank to an esterification reactor for esterification of the combination in the reactor at above 250° C. temperature which releases monomers; transferring the monomers from the esterification reactor to a polymerisation reactor; providing poly-catalysts such as, but not limited, to Ti-based catalyst, Sb2O3 or any other suitable catalysts or combination thereof into the polymerisation reactor; and polymerization of the monomers in the polymerisation reactor at above 280° C. temperature, wherein an enzyme based composition is provided either at PTA/MEG stage or poly-catalyst stage or at other stages or combination thereof.
While the present invention has been described in connection with what are currently considered to be the most practical and preferred embodiments, it is to be understood that various arrangements and alternative embodiments are intended to be included within the scope of the appended claims.
The present invention generally describes a biodegradable PET polymeric raw material and more particularly a process of manufacturing film grade biodegradable polyethylene terephthalate or PET chips for use in making biodegradable polyester film/laminate package. The biodegradability in the PET chips is induced by an enzyme based composition, present either on the surface or in the entire thickness of the chips, provided at one of the steps or combination thereof, of the process.
The enzyme in the enzyme-based composition are natural protein molecules that act as highly efficient catalysts in biochemical reactions, that is, they help a chemical reaction take place quickly and efficiently. Studies show that the enzymes present in the enzyme-based composition attracts microbes over the polymeric product surface and colonize on the surface of the plastic forming a biofilm and thus accumulating the microbes on the polymeric product surface. Once the microbes have colonized on the product surface they secrete acids and/or enzymes that break down the polymeric chains. The microbes utilize biodegradable polymeric as the component in unavailability of microbial nutrients.
The formulation of the enzyme based composition may include, but not limited to, natural peptides/enzymes/proteins obtained from edible biological sources such as plant or vegetables etc.
Typical enzyme-based compositions are described in Indian patent Appl. Nos. 3104/MUM/2015 and 201611028054, and U.S. Pat. No. 9,925,707/EP3162841, however any other similar/modified composition can also be used without deviating from the scope of the present invention.
With reference to
The process (100) of manufacturing biodegradable PET chips includes step (102) of providing a purified terephthalic acid (PTA) in a predetermined quantity in a slurry tank (302). The predetermined quantity of the PTA may be 68% by weight; however other suitable quantity of the PTA may be provided based on requirement without deviating from the scope of the present invention. The process (100) further includes the step (104) of providing virgin or recycled Mono-Ethylene Glycol (MEG) in a predetermined quantity in the slurry tank (302). The predetermined quantity of the MEG is typically 31% by weight; however other suitable quantity of the MEG may be provided based on requirement without deviating from the scope of the present invention. The process (100) further includes the step (106) of transferring the combination of the slurry tank (302) to an esterification reactor (304) for esterification of the combination in the reactor (304) which releases monomer. The esterification happens in the esterification reactor (304) at temperature range of above 250° C. under 2.5 bar pressure releasing the monomers and water vapours. At step (106), the esterification success is confirmed if 95% by weight measured quantity of distilled water, obtained from the water vapour, is extracted from the esterification reactor (304).
The process (100) further includes the step (108) of transferring the monomers from the esterification reactor (304) to a polymerisation reactor (306). The polymerization reactor (306) may have a capacity of 20 m3; however reactor (306) of other capacity may also be used without deviating from the scope of the present invention. The process (100) further includes the step (110) of providing poly-catalysts into the polymerisation reactor (306) to induce desired properties in the polymer to be produced. The poly-catalysts may be, but not limited to, Ti-based catalyst, Sb2O3 or any other suitable catalysts known in the art or combination thereof. The process (100) further includes the step (112) of polymerization of the monomers in the polymerisation reactor (306). The polymerization of the monomers occur by retaining the monomers in the reactor (306) for a period of 1.5-3 hours having vacuum environment at the temperature range of above 280° C.
At step (112) of the process (100), the polymerization of the monomers take place in the polymerization reactor (306) at the above mentioned predetermined temperature range producing PET polymers. The produced PET polymers (polymerized monomers) are pushed by a pressure of inert gases such as Nitrogen (N2) from top of the polymerisation reactor (306) to push through strands die (308), of a suitable specification, configured to the polymerization reactor (306). In an example, specification of the strands die (308) includes a plurality of holes, such as but not limited to 95 number of holes, each having diameter of size approx. 8 mm, however strands die (308) of different specification may also be used without departing from the scope of the present invention. The strands coming out of the die (308) are stretched up to a predetermined length, such as but not limited to 1.5 meters. The stretched strands are cooled inline by spraying chilled demineralization (DM) water over the stretched strands or by other suitable cooling mechanism such as but not limited to automatic strand in-feed underwater. The cooled PET polymer strands are thereafter pelletized in chips of a predetermined shape, such as but not limited to 4×4×3 mm inline using roller pelletizer or other suitable pelletizer.
The enzyme based composition, as discussed heretofore above, is provided either with PTA at (102) or with MEG at (104) or poly-catalyst stage (110) or at other stages or combination thereof in order to induce biodegradability in the polymeric chips to be produced by using the process (100).
The biodegradable PET chips may also be produced by providing the enzyme based composition at any of the steps or combination thereof, of the above described process (100) of manufacturing the PET chips if the composition is water insoluble. In other case, the composition can be provided only at the stages/steps or combination thereof, except the step of esterification, for producing biodegradable PET chips.
The biodegradable PET chips may also be produced by providing the aqueous enzyme-based composition in the cooling water of the underwater palletizer and then cutting the strands to chips. The dried chips have a coating of the enzyme-based composition on the surface of chips.
The biodegradable PET chips may also be produced by placing an additional mixing zone to the process (100) for feeding and mixing the enzyme-based composition before pushing the molten phase PET polymer into the strands die (308) and then cooling and cutting the strands to chips having dispersed enzyme-based composition.
The pelletized biodegradable PET chips is transferred to a dryer (310) to evaporate the water from the PET chips before packing up for further usage, such as making polymeric films.
As used herein, PET polymer of textile or fiber grade, film grade, and bottle grade intend to describe PET, which can be described as having an intrinsic viscosity within the range of 0.64-0.75, 0.6-0.66, and 0.57-0.64, respectively. In order to suit the use of the PET polymer of the different grades, it is desirable that the PET have specifications according to following.
The above described process (100) produces film grade biodegradable PET chips having IV of 0.6 to 0.66 which can used to make PET polymeric film laminate for various suitable packaging applications. The injection moulding and bottle grade biodegradable PET chips are manufactured using a process (200) as depicted in
The process (200) includes the step (202) of transferring a predetermined quantity of the biodegradable PET chips at a predetermined frequency through at least one pre-crystallizer or crystallizer fluidized bed chambers (402, 404). In an example, the predetermined quantity of the biodegradable chips may be transferred at the rate of 1.5 T/hr., however any other quantity or frequency may also be used without deviating from the scope of the present invention. In the fluidized bed chambers (402, 404), air or Nitrogen gas at 150° C.-170° C. is used to heat the PET chips before transferring to the SSP reactor (406), as described in the next step (204).
The process (200) further includes the step (204) of transferring the chips from the fluidized bed chamber(s) (402, 404) to a SSP reactor (406) of a predetermined capacity for a predetermined residence time in batches.
In an example, the capacity of the SSP reactor (406) is 30 Tons however SSP reactor (406) of other suitable capacity may also be used. In an example, the residence time of the SSP reactor (406) may be in the range of 10-20 hours however the residence time may vary according to the desired IV of the PET chips to be produced.
During the residence in the SSP reactor (406), one or more bi-products such as but not limited to aldehyde, MEG etc. are released which needs to be extracted during the residence time, out of the SSP reactor (406). Inert gas such as Nitrogen (N2) from the bottom of the SSP reactor (406) at 180° C.-200° C. is passed into the SSP reactor (406) in order to extract the bi-products leaving only the biodegradable injection mounding and bottle grade PET chips having the desired IV.
The process (200) further includes the step (206) of cooling the chips, drawn periodically in a calculated quantity and frequency from the bottom of the SSP reactor (406), using a suitable cooler (408) ensuring desired residence time for each batch drawn from the SSP reactor (406).
The biodegradable injection moulding and bottle grade PET chips produced are thereafter ready to be packed up for further usage, such as making polymeric bottle or other suitable products.
For only bottle grade biodegradable PET chips, at step (102) of the process (100) of manufacturing film grade biodegradable PET chips, a predetermined quantity of Purified Isophthalic Acid (IPA) is provided along with PTA making combined weight of IPA and PTA about 68%. The predetermined quantity of the IPA may be 2% by weight and PTA may be 66% by weight making combined quantity 68% by weight; however other suitable quantity of the IPA and PTA may be provided based on requirement without deviating from the scope of the present invention.
In various other embodiments besides or without having addition of enzyme-based composition in afore described stages, the ingredients such as but not limited to PTA, MEG, Polycatalyst etc. may be premixed with at least one of the ingredients in predetermined quantity of enzyme-based composition.
While the present invention has been described in connection with what are currently considered to be the most practical and preferred embodiments, it is to be understood that various arrangements and alternative embodiments are intended to be included within the scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201911010930 | Mar 2019 | IN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IN2020/050230 | 3/13/2020 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2020/188594 | 9/24/2020 | WO | A |
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|---|---|---|---|
| 9925707 | Iyer | Mar 2018 | B2 |
| 20060173154 | Charbonneau | Aug 2006 | A1 |
| 20080194771 | Kong | Aug 2008 | A1 |
| 20090131627 | Colhoun | May 2009 | A1 |
| 20120136132 | Schulz Van Endert | May 2012 | A1 |
| 20140197580 | Poulat | Jul 2014 | A1 |
| Number | Date | Country |
|---|---|---|
| H06322263 | Nov 1994 | JP |
| 2013034743 | Mar 2013 | WO |
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| Number | Date | Country | |
|---|---|---|---|
| 20220153926 A1 | May 2022 | US |
