IP Library Granted Patent US 12,590,252
Granted Patent B2
US 12,590,252 · App. 17/755,322 · Granted Mar 31, 2026

Pyrolysis method and system for recycled waste

Inventors: Xianchun Wu (Longview, TX); Daryl Bitting (Longview, TX); Kenny Randolph Parker (Afton, TN); Michael Gary Polasek (Longview, TX); David Eugene Slivensky (Tatum, TX); Damon Ray Billodeaux (Longview, TX)
Assignee: ExxonMobil Product Solutions Company
C10G1/10B01D53/685C10G1/002C10G1/02B01D2251/404B01D2251/604B01D2251/606B01D2257/2025B01D2258/02C10G2300/1003C10G2300/201C10G2300/308C10G2300/4006
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Quick Facts
Patent No.
US 12,590,252
App. No.
17/755,322
Granted
Mar 31, 2026
Kind
B2
Abstract

A pyrolysis method and system are provided that utilizes a multistage dehalogenation method to effectively remove halogen-containing compounds that are present in an initial recycled plastic feedstock. More particularly, the multistage dehalogenation system and process may involve physical sorting the plastic feedstock, melting and separating the feedstock, and subjecting the feedstock a two-stage pyrolysis with intermediate HCl removal.

Claims (36)

1 . A method of making a pyrolysis oil, said method comprising:

a) providing a plastic-containing feed comprising at least one halogen-containing waste plastic;

b) dehalogenating at least a portion of said plastic-containing feed in a pretreatment unit to thereby form a halogen waste stream and a dehalogenated feed, wherein the dehalogenating comprises physically separating solid halogen-containing waste plastic from at least one other type of waste plastic upstream of a pyrolysis unit; and

c) pyrolyzing at least a portion of said dehalogenated feed to thereby form a pyrolysis effluent comprising a pyrolysis oil, wherein said pyrolysis oil:

i.) comprises an aromatic content of less than 25 weight percent,

ii.) comprises an alkane content of at least 25 weight percent,

iii.) comprises a 90% boiling point of at least 350° C.; and

iv.) exhibits a density at 15° C. of less than 0.9 g/cm 3 ,

wherein said dehalogenating of step (b) comprises pretreating said plastic-containing feed by heating to a temperature in a range from at least 150° C. and not more than 325° C. for a time sufficient to remove at least 5 percent of the halogen originally present in the plastic-containing feed and thereby release a halogen-containing waste stream and form a dehalogenated feed having a halogen content of not more than 1000 ppm,

wherein said pyrolyzing of step (c) occurs at a temperature of at least 450° C. and not more than 1100° C., and

wherein the pyrolysis oil is not hydrotreated.

2 . The method according to claim 1 , wherein said dehalogenating comprises:

(i) melting and physically separating a melted halogen-containing waste plastic from at least one other type of melted waste plastic,

(ii) heating the halogen-containing waste plastic to a temperature in a range from at least 150° C. and not more than 250° C. for a time sufficient to crack at least a portion of said halogen-containing waste plastic to remove at least 5 percent of the halogen originally present in the plastic-containing feed and thereby release a halogen-containing gas and then venting off said halogen-containing gas and form a dehalogenated feed having a halogen content of not more than 1000 ppm, and absorbing said halogen-containing gas into a halogen scavenger.

3 . The method according to claim 1 , wherein said dehalogenating comprises melting and physically separating a melted halogen-containing waste plastic from at least one other type of melted waste plastic.

4 . The method according to claim 2 , wherein said dehalogenating comprises venting off said halogen-containing gas.

5 . The method according to claim 2 , wherein said dehalogenating comprises absorbing said halogen containing gas into a halogen scavenger.

6 . The method according to claim 5 , wherein said halogen scavenger comprises a metal oxide, a metal hydroxide, a carbon composite, or a combination thereof.

7 . The method according to claim 5 , wherein said halogen scavenger comprises slaked lime, calcium carbonate, or a combination thereof.

8 . The method according to claim 1 , wherein said dehalogenating removes at least 50 percent of the halogen originally present in said plastic-containing feed.

9 . The method according to claim 1 , wherein said plastic-containing feed comprises at least 5 weight percent of at least one halogen-containing waste plastic.

10 . The method according to claim 1 , wherein said dehalogenated feed comprises a halogen content of less than 1,000 ppm.

11 . The method according to claim 1 , wherein said pyrolysis oil comprises an aromatic content of less than 5 weight percent.

12 . The method according to claim 1 , wherein said pyrolysis oil exhibits a density at 15° C. of at least 0.65 g/cm 3 and less than 0.1 g/com 3 .

13 . The method according to claim 1 , wherein said pyrolysis oil comprises a combined paraffin and olefin content of at least 55 weight percent and not more than 99 weight percent.

14 . The method according to claim 1 , wherein said pyrolysis oil comprises a C6-C12 hydrocarbon content of at least 10 weight percent and less than 95 weight percent.

15 . The method according to claim 1 , wherein said pyrolysis oil comprises a C13-C23 hydrocarbon content of at least 1 weight percent and not more than 80 weight percent; and wherein said pyrolysis oil comprises a C24+ hydrocarbon content of at least 1 weight percent and less than 15 weight percent.

16 . The method according to claim 1 , wherein said pyrolyzing occurs at a temperature of at least 775° C. and not more than 1,100° C.

17 . The method according to claim 1 , wherein said pyrolyzing occurs in the presence of a pyrolysis catalyst.

18 . The method according to claim 1 , wherein said pyrolyzing occurs in the absence of a pyrolysis catalyst.

19 . The method according to claim 1 , wherein said pyrolysis oil comprises a C8+ hydrocarbon content of at least 35 weight percent, based on the total weight of said pyrolysis oil.

20 . The method of claim 1 , further comprising:

cracking a cracker feedstock composition comprising:

a) the pyoil of claim 1 , and

b) a non-recycle cracker feed stream chosen from a predominantly C2-C4 hydrocarbon containing composition, wherein the pyoil is present in an amount of at least 1 weight percent, and wherein said non-recycle cracker feed stream is present in an amount of at least 55 weight percent, based on the total weight of the cracker feedstock composition, to thereby provide olefins.

21 . The method of claim 20 , wherein the predominantly C2-C4 hydrocarbon containing composition contains at least 90 weight percent of C2-C4 hydrocarbon and wherein said C2-C4 hydrocarbon are chosen from ethane and propane.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 20, 2025
From: EASTMAN CHEMICAL COMPANY
To: EXXONMOBIL PRODUCT SOLUTIONS COMPANY
Reel/Frame 073142/0954 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 28, 2022
From: WU, XIANCHUN; BITTING, DARYL; PARKER, KENNY RANDOLPH; POLASEK, MICHAEL GARY; SLIVENSKY, DAVID EUGENE; BILLODEAUX, DAMON RAY
To: EASTMAN CHEMICAL COMPANY
Reel/Frame 060330/0472 →
Continuity (2)
Provisional Application 62928512 · Oct 31, 2019
Related Publication 20220396735A1 · Dec 15, 2022
References Cited (45)
US 5368723A · Takahashi · 1994 [cited by examiner]
US 5731483A · Stabel · 1998 [cited by examiner]
US 5841011A · Hashimoto · 1998 [cited by examiner]
US 6011187A · Horizoe · 2000 [cited by examiner]
US 6172275B1 · Tadauchi · 2001 [cited by examiner]
US 20100121097A1 · Sasaki · 2010 [cited by examiner]
US 20120125813A1 · Bridges et al. · 2012 [cited by applicant]
US 20120160659A1 · Koukios · 2012 [cited by examiner]
US 20120184787A1 · Miller · 2012 [cited by applicant]
US 20130296619A1 · Iaccino et al. · 2013 [cited by applicant]
US 20140155661A1 · Frediani · 2014 [cited by examiner]
US 20150001061A1 · Bordynuik · 2015 [cited by examiner]
US 20150284645A1 · Schmidt et al. · 2015 [cited by applicant]
US 20160024390A1 · Ullom · 2016 [cited by applicant]
US 20160045841A1 · Kaplan et al. · 2016 [cited by applicant]
US 20160264883A1 · Narayanaswamy et al. · 2016 [cited by applicant]
US 20160264885A1 · Narayanaswamy · 2016 [cited by examiner]
US 20180002609A1 · Narayanaswamy et al. · 2018 [cited by applicant]
US 20190002664A1 · Streiff et al. · 2019 [cited by applicant]
US 20190055483A1 · Bafna et al. · 2019 [cited by applicant]
US 20190256781A1 · Baker · 2019 [cited by applicant]
US 20200234679A1 · Nam et al. · 2020 [cited by applicant]
US 20210009907A1 · Frecon et al. · 2021 [cited by applicant]
CN 101875847A · 2010 [cited by applicant]
JP 06210263A · 1994 [cited by applicant]
JP 2002212571A · 2002 [cited by applicant]
JP 2007099827A · 2007 [cited by applicant]
KR 1020040062793A · 2004 [cited by applicant]
KR 1020090028173A · 2009 [cited by applicant]
WO WO2009065271A1 · 2009 [cited by applicant]
WO WO2009152667A1 · 2009 [cited by applicant]
WO WO2015000840A1 · 2015 [cited by applicant]
WO WO2018069794A1 · 2018 [cited by applicant]
N. Miskolczi et al., Pyrolysis of Polyvinyl Chloride (PVC)-Containing Mixed Plastic Wastes for Recovery of Hydrocarbons, 23 Energy & Fuels 2743-2749 (2009). [cited by examiner]
Co-pending U.S. Appl. No. 17/755,323, filed Apr. 27, 2022; Wu et al. [cited by applicant]
ASTMD2887; “Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography”; Published Jan. 2020. [cited by applicant]
ASTMD5399; “Standard Test Method for Boiling Point Distribution of Hydrocarbon Solvents by Gas Chromatography”; Published Dec. 2017. [cited by applicant]
Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority with Date of Mailing Feb. 18, 2021 for International Application No. PCT/US2020/057871. [cited by applicant]
Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority with Date of Mailing Feb. 23, 2021 for International Application No. PCT/US2020/057878. [cited by applicant]
USPTO Office Action dated Aug. 31, 2023 received in U.S. co-pending U.S. Appl. No. 17/755,323. [cited by applicant]
European Search Report dated Dec. 14, 2023 for Application No. 20881239.6. [cited by applicant]
European Search Report dated Nov. 24, 2023 for Application No. 20880502.8. [cited by applicant]
USPTO Office Action dated Mar. 21, 2024 received in U.S. co-pending U.S. Appl. No. 17/755,323. [cited by applicant]
USPTO Office Action dated Mar. 6, 2025 received in U.S. co-pending U.S. Appl. No. 17/755,323. [cited by applicant]
USPTO Office Action dated Aug. 28, 2024 received in U.S. co-pending U.S. Appl. No. 17/155,323. [cited by applicant]