Light olefin recovery from plastic waste pyrolysis

Patent metadata

Field	Value
Publication number	US-12065616-B2
Application number	US-202017595344-A
Country	US
Kind code	B2
Filing date	Jun 12, 2020
Priority date	Jun 13, 2019
Publication date	Aug 20, 2024
Grant date	Aug 20, 2024

Abstract

Systems and methods are provided for integration of a reactor for polyolefin pyrolysis with the effluent processing train for a steam cracker. The polyolefins can correspond to, for example, polyolefins in plastic waste. Integrating a process for polyolefin pyrolysis with a steam cracker processing train can allow a mixture of polymers to be converted to monomer units while reducing or minimizing costs and/or equipment footprint. This can allow for direct conversion of polyolefins to the light olefin monomers in high yield while significantly lowering capital and energy usage due to integration with a steam cracking process train. The integration can be enabled in part by selecting feeds with appropriate mixtures of various polymer types and/or by limiting the volume of the plastic waste pyrolysis product relative to the volume from the steam cracker(s) in the steam cracking process train. By selecting plastic waste and/or other polyolefin sources with an appropriate mixture of polyolefins as the feedstock, the resulting polyolefin pyrolysis product can be separated in a steam cracking process train to produce separate fractions for various polymer grade small olefin products.

First claim

The invention claimed is:

1. A method for pyrolyzing a mixed polyolefin feed, comprising:
exposing a feedstock comprising a mixture of polyolefins comprising two or more types of monomers to polyolefin pyrolysis conditions to form a pyrolysis effluent, the polyolefin pyrolysis conditions comprising:
heating the feedstock at a rate of 100° C. per second or more to form a heated reaction mixture having a temperature of 500° C. to 900° C., and
cooling the heated reaction mixture to a temperature of less than 500° C. to form the pyrolysis effluent, the heated reaction mixture being at a temperature of 500° C. or more for 0.1 seconds to 5.0 seconds;

performing an initial separation on the pyrolysis effluent to form at least a pyrolysis product fraction and a fraction comprising solid particles;
performing steam cracking on a steam cracker feed to form a steam cracker reactor effluent;
passing at least a portion of the steam cracker reactor effluent into a primary fractionator to form at least a first fractionator product and one or more additional fractionator products having a higher boiling range than the first fractionator product;
passing at least a portion of the first fractionator product and at least a portion of the pyrolysis product fraction into a process gas compressor to form a compressed olefin product fraction, a volume of the pyrolysis product fraction comprising 0.1 vol % to 20 vol % of a combined volume of the at least a portion of the first fractionator product and the pyrolysis product fraction; and
separating at least a first product stream comprising ethylene and a second product stream comprising propylene from the compressed olefin product fraction.

2. The method of claim 1 , wherein the feedstock comprises 0.1 wt % or more of polyvinyl chloride, polyvinylidene chloride, polyamide, polystyrene, polyethylene terephthalate, ethylene vinyl acetate, or a combination thereof.

3. The method of claim 1 , wherein the feedstock comprises 0.1 wt % to 35 wt % polystyrene.

4. The method of claim 1 , i) wherein the feedstock comprises 0.1 wt % to 10 wt % polyvinyl chloride, polyvinylidine chloride, or a combination thereof; ii) wherein the feedstock comprises 0.1 wt % to 1.0 wt % polyamide; or iii) a combination of i) and ii).

5. The method of claim 4 , the method further comprising:
separating the pyrolysis product fraction to form a lower boiling fraction and a higher boiling fraction; and
passing the lower boiling fraction into a contaminant removal stage to form the at least a portion of the pyrolysis product fraction, the at least a portion of the pyrolysis product fraction comprising a lower chlorine content than the lower boiling fraction.

6. The method of claim 1 , wherein the feedstock comprises 0.1 wt % to 10 wt % ethylene vinyl acetate, or wherein the feedstock comprises 0.1 wt % to 10 wt % polyethylene terephthalate, or a combination thereof.

7. The method of claim 1 , a) wherein the first product stream comprises ethylene derived from exposing the feedstock comprising a mixture of polyolefins to the polyolefin pyrolysis conditions; b) wherein the second product stream comprises propylene derived from exposing the feedstock comprising a mixture of polyolefins to the polyolefin pyrolysis conditions; or c) a combination of a) and b).

8. The method of claim 1 , wherein the one or more additional fractionator products comprise a naphtha boiling range product, the method further comprising:
passing at least a portion of the naphtha boiling range product into a silicon removal stage to form a modified naphtha boiling range product.

9. The method of claim 1 , wherein the heated reaction mixture further comprises heat transfer particles, the polyolefin pyrolysis conditions further comprising exposing the feedstock to the heat transfer particles.

10. The method of claim 9 , wherein the heat transfer particles comprise calcium oxide, at least a portion of the calcium oxide being converted to calcium chloride under the polyolefin pyrolysis conditions.

11. The method of claim 10 , wherein the fraction comprising the solid particles comprises heat transfer particles and calcium chloride, the polyolefin pyrolysis conditions further comprising:
recycling a first portion of the fraction comprising the solid particles to the pyrolysis reactor; and
purging a second portion of the fraction comprising the solid particles.

12. The method of claim 1 , wherein the heated reaction mixture further comprises 10 wt % or more of steam.

13. The method of claim 1 , wherein the feedstock is heated at a rate of 200° C. per second or more.

14. The method of claim 1 , wherein the at least a portion of the first fractionator product and the pyrolysis product fraction are quenched in a quench tower prior to being passed into the product gas compressor, or wherein the at least a portion of the first fractionator product and the pyrolysis product fraction are quenched in separate quench towers prior to being passed into the product gas compressor.

15. The method of claim 1 , further comprising:
exposing the compressed olefin product fraction to a water wash, a caustic wash, an amine wash, or a combination thereof, to form a washed compressed olefin product fraction, and
passing the washed, compressed olefin product fraction into a contaminant removal stage to form a reduced-contaminant product fraction,
wherein separating at least a first product stream comprising ethylene and a second product stream comprising propylene from the compressed olefin product fraction comprises separating the at least a first product stream and a second product stream from the reduced-contaminant product fraction.

16. The method of claim 1 , wherein the one or more additional fractionator products comprise a bottoms fraction, a tar fraction, or a combination thereof.

17. The method of claim 1 , further comprising mixing at least one of the pyrolysis effluent and the pyrolysis product fraction with a quench oil.

18. The method of claim 17 , wherein the one or more additional fractionator products comprise a gas oil fraction, the quench oil comprising at least a portion of the gas oil fraction.

19. The method of claim 1 , wherein a second pyrolysis product fraction is separated from the pyrolysis effluent, the method further comprising passing the second pyrolysis product fraction into the primary fractionator.

20. The method of claim 1 , wherein the first product stream comprises 90 wt % or more ethylene, or wherein the second product stream comprises 90 wt % or more propylene, or a combination thereof.

21. The method of claim 1 , further comprising physically processing a polymer feed to form the feedstock, the mixture of polyolefins comprising particles having a median particle size of 3.0 mm or less.

22. The method of claim 1 , further comprising forming the feedstock by combining a polymer feed with a solvent, the mixture of polyolefins being at least partially solvated by the solvent.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Uppili Sundararajan
• Patel Bryan A
• Smiley Randolph J
• Gros Lawrence R
• Go Anthony
• Maduskar Saurabh S
• Foster Melissa D
• Laurent Philippe

Classifications

• C10G9/36

  with heated gases or vapours · CPC title

• C10B53/07 Primary

  {of solid raw materials consisting} of synthetic polymeric materials, e.g. tyres (recovery or working-up of waste materials of organic macromolecular compounds or compositions based thereon by dry-heat treatment for obtaining partially depolymerised materials C08J11/10; production of liquid hydrocarbon mixtures from rubber or rubber waste C10G1/10) · CPC title

• C10B49/22

  according to the "fluidised bed" technique · CPC title

• C10G2300/1003

  Waste materials · CPC title

• C10B57/06

  containing additives · CPC title