Process for recycling mixed polymer containing polyethylene terephthalate

• US 5,554,657 A
• Filed: 05/08/1995
• Issued: 09/10/1996
• Est. Priority Date: 05/08/1995
• Status: Expired due to Fees

• Current Assignee: Corpus Christi Polymers LLC
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Rollick, Kevin L., Chuah, Hoe H., Tompkin, Mark R., June, Raymond L., Diaz, Zaida, Brownscombe, Thomas F., Fong, Howard L., Semple, Thomas C.
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): Asinovsky, Olga
• Application Number:
  US08/436,078
• Time in Patent Office: 491 Days
• Field of Search: 521/48, 521/46.5, 521/46, 528/308.1, 528/502, 209/166
• US Class Current: 521/48
• CPC Class Codes: B29B 17/0026 by agglomeration or compacting
• CPC Class Codes: B29B 17/02 Separating plastics from other materials
• CPC Class Codes: B29B 2017/0015 Washing, rinsing
• CPC Class Codes: B29B 2017/0203 Separating plastics from plastics
• CPC Class Codes: B29B 2017/0293 Dissolving the materials in gases or liquids
• CPC Class Codes: B29K 2067/00 Use of polyesters or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2067/003 PET, i.e. poylethylene terephthalate
• CPC Class Codes: C08J 11/08 using selective solvents for polymer components
• CPC Class Codes: C08J 2367/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds; C08J2367/06 takes precedence
• CPC Class Codes: Y02W 30/62 Plastics recycling; Rubber recycling

Abstract

The invention described herein provides a process for recycling a mixed polymer recycle stream containing polyester polymers, particularly polyethylene terephthalate (PET) typically in the form of carbonated soft drink or other containers. This novel process includes the steps of: (1) contacting the mixed polymer recycle stream with a solvent which selectively dissolves the PET. (2) separating the selective solvent containing PET from the residual mixed polymer, (3) cooling the selective solvent to precipitate the PET, and (4) removing the selective solvent from the precipitated PET. It is preferable that the mixed polymer recycle stream be prepared for recycling by conventional steps, such as water washing. In a preferred embodiment, the mixed polymer recycle stream is chemically washed subsequent to water washing and prior to contact with the selective solvent. The PET recovered is preferably combined with "virgin" PET and further processed to increase its molecular weight.

Claims

1. A process for recovering a polyester polymer from a mixed polymer recycle stream, while maintaining the polyester polymer in polymer form, comprising:

contacting a mixed polymer recycle stream comprising at least 50 weight percent polyester polymer, lesser portions of other polymers, including one or more polyolefins, and impurities, with a chemical wash solvent that dissolves at least a portion of the impurities present in the mixed polymer recycle stream and substantially rejects dissolution of the polyester polymer present in the mixed polymer recycle stream, to form a chemical wash solution containing impurities dissolved in the chemical wash solvent, and a residual mixed polymer recycle stream;

separating the chemical wash solution from the residual mixed polymer recycle stream;

contacting, at an elevated temperature, the residual mixed polymer recycle stream with a selective solvent that selectively dissolves the polyester polymer and substantially rejects dissolution of any other polymer present in the mixed polymer recycle stream, to form a residual waste stream, a separate polyolefin phase, and a selective solvent solution comprising the polyester polymer dissolved in the selective solvent;

separating the selective solvent solution from the separate polyolefin phase, and from the residual waste stream; and

precipitating the polyester polymer from the selective solvent solution, to form a precipitated polyester polymer and a spent selective solvent solution; and

separating the spent selective solvent from the precipitated polyester polymer, to obtain a recovered polyester polymer product having an intrinsic viscosity of from about 0.2 dl/g to about 0.8 dl/g.

2. The process of claim 1 wherein the recovered polyester polymer is combined, in a melt processing operation, with a virgin polyester polymer stream having a comparable molecular weight to produce a recycle-content polyester polymer product containing at least 15 weight percent of the polyester polymer recovered from the mixed polymer recycle stream.

3. The process of claim 2 wherein the recycle-content polyester polymer product is further polymerized to increase its molecular weight.

4. The process of claim 2 wherein the chemical wash solvent is selected from the group consisting of methyl ethyl ketone, tetrahydrofuran, hexanones, 1,4-dioxane, diethoxymethane, and mixtures thereof.

5. The process of claim 4 wherein the selective solvent is selected from the group consisting of dialkyl terephthalates, dialkyl phthalates, dialkyl isophthalates, dialkyl naphthalates, alkylene carbonates, and mixtures thereof.

6. The process of claim 5 wherein the mixed polymer recycle stream includes polyvinyl chloride polymer, and the chemical wash solvent dissolves the polyvinyl chloride, in addition to impurities present in the mixed polymer recycle stream, to form a chemical wash solution containing impurities and polyvinyl chloride dissolved in the chemical wash solvent.

7. The process of claim 2 wherein the recovered polyester polymer is combined with the virgin polyester in a polymerization reactor in a melt processing operation.

8. The process of claim 2 wherein the recovered polyester polymer is combined with the virgin polyester in an extrusion step in a melt processing operation.

9. The process of claim 2 wherein the recovered polyester polymer is combined with the virgin polyester in a spinning step in a melt processing operation.

10. The process of claim 2 wherein the selective solvent is selected from the group consisting of dimethyl terephthalate, dimethyl phthalate, dimethyl isophthalate, dimethyl naphthalate, ethylene carbonate, propylene carbonate, and mixtures thereof.

11. The process of claim 10 wherein the chemical wash solvent is selected from the group consisting of methyl ethyl ketone, tetrahydrofuran, and mixtures thereof.

12. The process of claim 2 wherein the mixed polymer recycle stream comprises at least 65 weight percent polyethylene terephthalate.

13. A process for recovering a polyester polymer from a mixed polymer recycle stream, while maintaining the polyester polymer in polymer form, comprising:

contacting a mixed polymer recycle stream comprising at least 65 weight percent polyester polymer, lesser portions of other polymers, including one or more polyolefins, and impurities, with a chemical wash solvent selected from the group consisting of methyl ethyl ketone, tetrahydrofuran, and mixtures thereof, to form a chemical wash solution containing impurities dissolved in the chemical wash solvent, and a residual mixed polymer recycle stream;

separating the chemical wash solution from the residual mixed polymer recycle stream;

contacting, at an elevated temperature, the residual mixed polymer recycle stream with a selective solvent selected from the group consisting of dimethyl terephthalate, dimethyl phthalate, dimethyl isophthalate, dimethyl naphthalate, ethylene carbonate, propylene carbonate, and mixtures thereof, to form a residual waste stream, a separate polyolefin phase, and a selective solvent solution comprising the polyester polymer dissolved in the selective solvent;

separating the selective solvent solution from the separate polyolefin phase, and from the residual waste stream; and

precipitating the polyester polymer from the selective solvent solution, to form a precipitated polyester polymer and a spent selective solvent solution;

separating the spent selective solvent from the precipitated polyester polymer, to obtain a recovered polyester polymer product having an intrinsic viscosity of from about 0.2 dl/g to about 0.8 dl/g; and

combining the recovered polyester polymer, in a melt processing operation, with a virgin polyester polymer stream having a comparable molecular weight to produce a recycle-content polyester polymer product containing from about 15 weight percent to about 55 weight percent of the polyester polymer recovered from the mixed polymer recycle stream.

14. The process of claim 13 wherein the chemical wash solvent is contacted with the mixed polymer recycle stream at a temperature in the range of from about 25°

C. to about 100°

C.

15. The process of claim 14 wherein the selective solvent is contacted with the mixed polymer recycle stream at a temperature in the range of from about 140°

C. to about 285°

C.

16. The process of claim 15 wherein the polyester polymer is present in the selective solvent solution at a concentration of from about 10 weight percent to about 40 weight percent.

17. The process of claim 16 wherein the polyester polymer is precipitated from the selective solvent solution by cooling the selective solution to a temperature in the range of from about 60°

C. to about 170°

C.

18. The process of claim 17 wherein the chemical wash solvent is methyl ethyl ketone, and the selective solvent is selected from the group consisting of dimethyl terephthalate, dimethyl phthalate, dimethyl isophthalate, and mixtures thereof.

19. The process of claim 17 wherein the chemical wash solvent is methyl ethyl ketone, and the selective solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, and mixtures thereof.

20. The process of claim 19 wherein the level of impurities present in the selective solvent is used to control the intrinsic viscosity of the recovered polyester polymer product.

21. The process of claim 17 wherein the recycle-content polyester polymer product is further polymerized to increase its molecular weight.

22. The process of claim 17 wherein the mixed polymer recycle stream comprises at least 80 weight percent polyethylene terephthalate.

23. The process of claim 17 wherein the mixed polymer recycle stream includes polyvinyl chloride polymer, and the chemical wash solvent dissolves the polyvinyl chloride, in addition to impurities present in the mixed polymer recycle stream, to form a chemical wash solution containing impurities and polyvinyl chloride dissolved in the chemical wash solvent.

24. A process for recovering a polyester polymer from a mixed polymer recycle stream, while maintaining the polyester polymer in polymer form, comprising:

contacting, at a first elevated temperature, a mixed polymer recycle stream comprising at least 50 weight percent polyester polymer, lesser portions of other polymers, including one or more polyolefins, and impurities, with a chemical wash solvent that dissolves any polyolefins present, and at least a portion of the impurities present in the mixed polymer recycle stream, and substantially rejects dissolution of the polyester polymer present in the mixed polymer recycle stream, to form a residual polymer recycle stream and a chemical wash solution comprising polyolefin polymer and impurities dissolved in the chemical wash solvent;

separating the chemical wash solution from the residual polymer recycle stream;

contacting, at a second elevated temperature, the residual polymer recycle stream with a selective solvent that selectively dissolves the polyester polymer and substantially rejects dissolution of other polymers present in the mixed polymer recycle stream, to form a selective solvent solution containing the polyester polymer dissolved in the selective solvent, and a residual waste stream;

separating the selective solvent solution from the residual waste stream;

precipitating the polyester polymer from the selective solvent solution, to form a precipitated polyester polymer and a spent selective solvent solution; and

separating the spent selective solvent from the precipitated polyester polymer, to obtain a recovered polyester polymer product having an intrinsic viscosity of from about 0.2 dl/g to about 0.8 dl/g.

25. The process of claim 24 wherein the recovered polyester polymer is combined, in a melt processing operation, with a virgin polyester polymer stream having a comparable molecular weight to produce a recycle-content polyester polymer product containing at least 15 weight percent of the polyester polymer recovered from the mixed polymer recycle stream.

26. The process of claim 25 wherein the recycle-content polyester polymer product is further polymerized to increase its molecular weight.

27. The process of claim 25 wherein the chemical wash solvent is selected from the group consisting of cyclohexanone, alkyl-substituted cyclohexanones, diol diacetates, dibutyl phthalate, and mixtures thereof.

28. The process of claim 27 wherein the selective solvent is selected from the group consisting of dialkyl terephthalates, dimethyl phthalate, dialkyl isophthalates, dialkyl naphthalates, alkylene carbonates, and mixtures thereof.

29. The process of claim 28 wherein the mixed polymer recycle stream includes polyvinyl chloride polymer, and the chemical wash solvent dissolves the polyvinyl chloride, in addition to impurities present in the mixed polymer recycle stream, to form a chemical wash solution containing impurities and polyvinyl chloride dissolved in the chemical wash solvent.

30. The process of claim 25 wherein the recovered polyester polymer is combined with the virgin polyester in a polymerization reactor in a melt processing operation.

31. The process of claim 25 wherein the recovered polyester polymer is combined with the virgin polyester in an extrusion step in a melt processing operation.

32. The process of claim 25 wherein the recovered polyester polymer is combined with the virgin polyester in a spinning step in a melt processing operation.

33. The process of claim 25 wherein the chemical wash solvent is cyclohexanone and the selective solvent is selected from the group consisting of dimethyl terephthalate, dimethyl phthalate, dimethyl isophthalate, dimethyl naphthalate, and mixtures thereof.

34. The process of claim 25 wherein the chemical wash solvent is cyclohexanone and the selective solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, and mixtures thereof.

35. The process of claim 25 wherein the mixed polymer recycle stream comprises at least 65 weight percent polyethylene terephthalate.

36. A process for recovering a polyester polymer from a mixed polymer recycle stream, while maintaining the polyester polymer in polymer form, comprising:

contacting, at a first elevated temperature, a mixed polymer recycle stream comprising at least 50 weight percent polyester polymer, lesser portions of other polymers, including one or more polyolefins, and impurities, with a chemical wash solvent selected from the group consisting of cyclohexanone, alkyl-substituted cyclohexanones, diol diacetates, dibutyl phthalate, and mixtures thereof, to form a residual polymer recycle stream and a chemical wash solution comprising polyolefin polymer and impurities dissolved in the chemical wash solvent;

separating the chemical wash solution from the residual polymer recycle stream;

contacting, at a second elevated temperature, the residual polymer recycle stream with a selective solvent selected from the group consisting of dialkyl terephthalates, dimethyl phthalate, dialkyl isophthalates, dialkyl naphthalates, alkylene carbonates, and mixtures thereof, to form a selective solvent solution containing the polyester polymer dissolved in the selective solvent, and a residual waste stream;

separating the selective solvent solution from the residual waste stream;

precipitating the polyester polymer from the selective solvent solution, to form a precipitated polyester polymer and a spent selective solvent solution;

separating the spent selective solvent from the precipitated polyester polymer, to obtain a recovered polyester polymer product having an intrinsic viscosity of from about 0.2 dl/g to about 0.8 dl/g; and

combining the recovered polyester polymer, in a melt processing operation, with a virgin polyester polymer stream having a comparable molecular weight to produce a recycle-content polyester polymer product containing from about 15 weight percent to about 55 weight percent of the polyester polymer recovered from the mixed polymer recycle stream.

37. The process of claim 36 wherein the chemical wash solvent is contacted with the mixed polymer recycle stream at a temperature in the range of from about 30°

C. to about 200°

C.

38. The process of claim 37 wherein the selective solvent is contacted with the mixed polymer recycle stream at a temperature in the range of from about 140°

C. to about 285°

C.

39. The process of claim 38 wherein the polyester polymer is present in the selective solvent solution at a concentration of from about 10 weight percent to about 40 weight percent.

40. The process of claim 39 wherein the polyester polymer is precipitated from the selective solvent solution by cooling the selective solution to a temperature in the range of from about 60°

C. to about 170°

C.

41. The process of claim 36 wherein the chemical wash solvent is cyclohexanone and the selective solvent is selected from the group consisting of dimethyl terephthalate, dimethyl phthalate, dimethyl isophthalate, dimethyl naphthalate, and mixtures thereof.

42. The process of claim 36 wherein the chemical wash solvent is cyclohexanone and the selective solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, and mixtures thereof.

43. The process of claim 42 wherein the level of impurities present in the selective solvent is used to control the intrinsic viscosity of the recovered polyester polymer product.

44. The process of claim 36 wherein the recycle-content polyester polymer product is further polymerized to increase its molecular weight.

45. The process of claim 36 wherein the mixed polymer recycle stream comprises at least 80 weight percent polyethylene terephthalate.

46. The process of claim 36 wherein the mixed polymer recycle stream includes polyvinyl chloride polymer, and the chemical wash solvent dissolves the polyvinyl chloride, in addition to impurities present in the mixed polymer recycle stream, to form a chemical wash solution containing impurities and polyvinyl chloride dissolved in the chemical wash solvent.

47. A process for recovering a polyester polymer from a mixed polymer recycle stream, while maintaining the polyester polymer in polymer form, comprising:

contacting, at an elevated temperature, a mixed polymer recycle stream comprising at least 50 weight percent polyester polymer, lesser portions of other polymers, including one or more polyolefins, and impurities, with a selective solvent that selectively dissolves the polyester polymer and substantially rejects dissolution of the other polymers and impurities present in the mixed polymer recycle stream, to form a residual waste stream, a separate polyolefin phase, and a selective solvent solution comprising the polyester polymer dissolved in the selective solvent;

separating the selective solvent solution from the separate polyolefin phase, and from the residual waste stream;

precipitating the polyester polymer from the selective solvent solution, to form a precipitated polyester polymer and a spent selective solvent solution;

separating the spent selective solvent and the precipitated polyester polymer, to obtain a recovered polyester polymer product having an intrinsic viscosity of from about 0.2 dl/g to about 0.6 dl/g; and

combining, in a melt processing operation, the recovered polyester polymer product with a virgin polyester polymer product having a comparable intrinsic viscosity, to produce a recycle-content polyester polymer product containing at least 15 weight percent of the polyester polymer recovered from the mixed polymer recycle stream.