WO2024057098A1 - Method to produce an oil from olefin-based resins by pyrolysis - Google Patents
Method to produce an oil from olefin-based resins by pyrolysis Download PDFInfo
- Publication number
- WO2024057098A1 WO2024057098A1 PCT/IB2023/020058 IB2023020058W WO2024057098A1 WO 2024057098 A1 WO2024057098 A1 WO 2024057098A1 IB 2023020058 W IB2023020058 W IB 2023020058W WO 2024057098 A1 WO2024057098 A1 WO 2024057098A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- olefin
- based resin
- lmw
- reactor
- oil
- Prior art date
Links
- 239000011347 resin Substances 0.000 title claims abstract description 73
- 229920005989 resin Polymers 0.000 title claims abstract description 73
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 63
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 40
- 238000005336 cracking Methods 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000013502 plastic waste Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000001993 wax Substances 0.000 description 30
- 229920000642 polymer Polymers 0.000 description 27
- -1 polyethylene Polymers 0.000 description 25
- 238000004064 recycling Methods 0.000 description 21
- 229920000092 linear low density polyethylene Polymers 0.000 description 16
- 239000004707 linear low-density polyethylene Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 238000002411 thermogravimetry Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 101150102573 PCR1 gene Proteins 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000008380 degradant Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- CMQYQYOEMPTEBC-UHFFFAOYSA-N (3-hydroxy-2-methylpentan-2-yl) 4,4-dimethylpentaneperoxoate Chemical compound CCC(O)C(C)(C)OOC(=O)CCC(C)(C)C CMQYQYOEMPTEBC-UHFFFAOYSA-N 0.000 description 1
- MVELOSYXCOVILT-UHFFFAOYSA-N (4-hydroxy-2-methylpentan-2-yl) 7,7-dimethyloctaneperoxoate Chemical compound CC(O)CC(C)(C)OOC(=O)CCCCCC(C)(C)C MVELOSYXCOVILT-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- IMYCVFRTNVMHAD-UHFFFAOYSA-N 1,1-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CCCCC1 IMYCVFRTNVMHAD-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- QJTVKOWKKWRAMT-UHFFFAOYSA-N 1,2,4,5,7,8-hexaoxonane Chemical compound C1OOCOOCOO1 QJTVKOWKKWRAMT-UHFFFAOYSA-N 0.000 description 1
- CITHEXJVPOWHKC-UUWRZZSWSA-N 1,2-di-O-myristoyl-sn-glycero-3-phosphocholine Chemical group CCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCCCCCCC CITHEXJVPOWHKC-UUWRZZSWSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 description 1
- BSAKKMQHOSYINC-UHFFFAOYSA-N 2-ethyl-2-(4-hydroxy-2-methylpentan-2-yl)peroxyhexanoic acid Chemical compound CCCCC(CC)(C(=O)O)OOC(C)(C)CC(C)O BSAKKMQHOSYINC-UHFFFAOYSA-N 0.000 description 1
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- PHIGUQOUWMSXFV-UHFFFAOYSA-N 2-methyl-2-[2-(2-methylbutan-2-ylperoxy)propan-2-ylperoxy]butane Chemical compound CCC(C)(C)OOC(C)(C)OOC(C)(C)CC PHIGUQOUWMSXFV-UHFFFAOYSA-N 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- ZIDNXYVJSYJXPE-UHFFFAOYSA-N 2-methylbutan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCC(C)(C)OOC(=O)CCCCCC(C)(C)C ZIDNXYVJSYJXPE-UHFFFAOYSA-N 0.000 description 1
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 description 1
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical compound CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 description 1
- WFAUFYAGXAXBEG-UHFFFAOYSA-N 2-phenylpropan-2-yl 4,4-dimethylpentaneperoxoate Chemical compound CC(C)(C)CCC(=O)OOC(C)(C)C1=CC=CC=C1 WFAUFYAGXAXBEG-UHFFFAOYSA-N 0.000 description 1
- NXVGUNGPINUNQN-UHFFFAOYSA-N 2-phenylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1=CC=CC=C1 NXVGUNGPINUNQN-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- XKXGWYAQJRXDPI-UHFFFAOYSA-N 7-methyloctanoyl 7-methyloctaneperoxoate Chemical compound CC(C)CCCCCC(=O)OOC(=O)CCCCCC(C)C XKXGWYAQJRXDPI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- SXPLGYBFGPYAHS-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(O)C(C)(C)C1 SXPLGYBFGPYAHS-UHFFFAOYSA-N 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- QZYRMODBFHTNHF-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OOC(C)(C)C QZYRMODBFHTNHF-UHFFFAOYSA-N 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NICWAKGKDIAMOD-UHFFFAOYSA-N ethyl 3,3-bis(2-methylbutan-2-ylperoxy)butanoate Chemical compound CCOC(=O)CC(C)(OOC(C)(C)CC)OOC(C)(C)CC NICWAKGKDIAMOD-UHFFFAOYSA-N 0.000 description 1
- HARQWLDROVMFJE-UHFFFAOYSA-N ethyl 3,3-bis(tert-butylperoxy)butanoate Chemical compound CCOC(=O)CC(C)(OOC(C)(C)C)OOC(C)(C)C HARQWLDROVMFJE-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical class [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 description 1
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 description 1
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- VNJISVYSDHJQFR-UHFFFAOYSA-N tert-butyl 4,4-dimethylpentaneperoxoate Chemical compound CC(C)(C)CCC(=O)OOC(C)(C)C VNJISVYSDHJQFR-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- ZUSDEBDNDIJDMZ-UHFFFAOYSA-N tert-butyl 7-methyloctaneperoxoate Chemical compound CC(C)CCCCCC(=O)OOC(C)(C)C ZUSDEBDNDIJDMZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- YOEYNURYLFDCEV-UHFFFAOYSA-N tert-butyl hydroxy carbonate Chemical compound CC(C)(C)OC(=O)OO YOEYNURYLFDCEV-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/02—Multi-step carbonising or coking processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
- C10B7/10—Coke ovens with mechanical conveying means for the raw material inside the oven with conveyor-screws
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
Definitions
- Polyolefins such as polyethylene (PE) and polypropylene (PP) may be used to manufacture a varied range of articles, including films, molded products, foams, and the like. Polyolefins may have characteristics such as high processability, low production cost, flexibility, low density, and recyclability. While plastics such as polyethylene and polypropylene have many beneficial uses, there is a need for their correct disposal after use, or even their reuse or recycling so as to minimize the environmental impact of plastic wastes.
- PE polyethylene
- PP polypropylene
- Pyrolysis is a thermochemical treatment wherein a material (e.g., plastic) is exposed to high temperature in the absence of oxygen. This process results in thermal decomposition of the material which forms new molecules.
- US10131847B2 discloses a process to convert waste plastics material to fuel by using pyrolysis.
- Thermal cracking processes such as pyrolysis present several limitations regarding the heat distribution. To produce products with a consistent quality, it is important that the same heat is applied to the plastic. However, considering heating conductivity and low IR absorption of plastics, radiant heat and convection are not good ways to heat plastics in a pyrolysis reactor. The most efficient way of heating plastics is by contact heating, which means that the superficial area and the physical characteristics of the plastics (particle size, for example) and reactor design are very important to assure pyrolysis efficiency. While a lot of new technologies are being developed for chemical recycling of plastics, some reactors can be considered not efficient and obsolete, and it can be very slow and expensive to make changes to an operating reactor.
- embodiments disclosed herein are related to a method for producing an oil comprising:
- the olefin-based resin is a low molecular weight (LMW) olefin-based resin.
- LMW low molecular weight
- embodiments disclosed herein relate to an oil produced according to said method.
- FIG. 1 shows a schematic representation of a pyrolysis unit.
- FIG. 2 shows the molecular weight distribution of samples Wax C, Wax G, LLDPE 1, and LLDPE 2.
- FIG. 3 shows the viscosity profile at 140°C for samples Wax C, Wax G, LLDPE 1, and LLDPE 2.
- FIG. 4 shows TGA analysis (T onset) for samples Wax C, Wax G, LLDPE 1, and LLDPE 2.
- FIG. 5 shows condensable yields for samples Wax C, Wax G, LLDPE 1, and LLDPE 2 in a pyrolysis trial at 450°C, 30 minutes.
- FIG. 6 shows condensable yields for samples Wax C, Wax G, LLDPE 1, and LLDPE 2 in a pyrolysis trial at 450°C, 45 minutes.
- FIG. 7 shows the molecular weight distribution graph for samples PCR 1, Wax 2, Wax 3-2, and Wax 8.
- FIG. 8 shows viscosity profile at 140°C for samples PCR 1, Wax 2, Wax 3-2, and Wax 8.
- FIG. 9 shows TGA analysis (T onset) for samples PCR 1, Wax 2, Wax 3-2, and Wax 8.
- FIG. 10 shows condensable yields for samples PCR 1, Wax 2, Wax 3-2, and Wax 8 in a pyrolysis trial at 450°C, 30 minutes.
- FIG. 11 shows condensable yields for samples PCR 1, Wax 2, Wax 3-2, and Wax 8 in a pyrolysis trial at 450°C, 15 minutes.
- FIG. 12 shows condensable yields for samples PCR 1, Wax 2, and Wax 8 in a pyrolysis trial at 450°C, 45 minutes.
- FIG. 13 shows a schematic representation of the extruder working at 250 °C and feeding a chemical reactor.
- FIG. 14 shows a schematic representation of the extruder working at 450 °C and feeding a chemical reactor.
- FIG. 15 shows the energetic demand for samples of different molecular weight.
- Embodiments disclosed herein generally relate to a method of producing an oil by feeding a low molecular weight (LMW) olefin-based resin into a pyrolysis reactor, converting the LMW olefin-based resin into an oil, and recovering said oil.
- LMW low molecular weight
- embodiments of the present disclosure may improve heat transfer and increase the efficiency of advanced chemical recycling processes.
- the process of the present disclosure melts and cracks the polymer before it is introduced into the reactor.
- the polymer is introduced through an extruder, and thus the polymer enters into the thermal reactor already melted and with a very low viscosity, which significantly increases the heat transfer.
- the low viscosity also facilitates polymer transportation and homogeneity inside the reactor.
- the method for producing an oil in the present invention comprises the following steps:
- the olefin-based resin is a low molecular weight (LMW) olefin-based resin.
- LMW low molecular weight
- pyrolysis refers to a thermal degradation treatment wherein the polymeric chains of the resin are broken to form smaller molecules by heat and under an environment substantially free of oxygen.
- LMW olefin-based resin has a molecular weight of less than 50,000 g/mol, preferably less than 40,000 g/mol, measured by high temperature gel permeation chromatography (GPC) according to ISO 16014-4.
- the feeding step may occur by means of an extruder, preferably a twin-screw extruder.
- the LMW olefin-based resin is fed into the reactor in a molten state. Therefore, the LMW olefin-based resin may be fed above its melting temperature. In a preferred embodiment, the LMW olefin-based resin is maintained and fed in a temperature close to the reactor temperature, preferably equal to or greater than 300°C, preferably greater than 400 °C, more preferably greater than 450°C. In some embodiments, the LMW olefin-based resin is molten and fed (e.g. by using an extruder) in an environment substantially free of oxygen. [0031] In one or more embodiments, the conversion step occurs in a reactor selected from a batch reactor, semi-batch reactor, or a two-stage pyrolysis system.
- the conversion step occurs at a temperature ranging from 400 to 600°C, and a residence time from 15 min to 2 h, and in an environment substantially free of oxygen. In some embodiments, the converting step occurs in the presence of a catalyst.
- the method further comprises a cracking step (that may be also referred as pre-treatment or pre-cracking step) wherein a higher molecular (HMW) olefin-based resin is melted and cracked to produce the LMW olefin-based resin that is fed into the reactor.
- a cracking step may occur before or during the feeding step.
- the cracking step occurs by means of an extruder.
- the cracking step occurs in an extruder that is directly connected to the reactor. Therefore, the LMW olefin-based resin may be directly fed into the reactor.
- the extruder used in the cracking step is a twin- screw extruder.
- the molecular weight of the HMW olefin-based resin is reduced by at least 4 times (i.e. “4x”) in the cracking step.
- the cracking step may be performed above the onset degradation temperature, optionally in the presence of a visbreaking agent.
- the “onset degradation temperature” is the temperature wherein the polymer chains of the resin start to breakdown. This “onset degradation temperature” may be determined by thermogravimetric analysis (TGA), according to ASTM El 131 standard method.
- the cracking step is performed at a temperature above the melting temperature and below the onset degradation temperature of the HMW olefin-based resin and in the presence of a visbreaking agent.
- the visbreaking agents may be free radical generators selected from peroxides, nitroxides, and combinations thereof.
- the peroxides may be selected from 3 -hydroxy- 1,1 -dimethylbutyl peroxyneodecanoate, a-cumyl peroxyneodecanoate, 2-hydroxy- 1,1 -dimethylbutyl peroxyneoheptanoate a-cumyl peroxyneoheptanoate, t-amyl peroxyneodecanoate, t-butyl peroxyneodecanoate, di(2- ethylhexyl) peroxydicarbonate, di(n-propyl) peroxydicarbonate, di(sec -butyl) peroxydicarbonate, t-butyl peroxyneoheptanoate, t-amyl peroxypivalate, t-butyl peroxypivalate, diisononanoyl
- the nitroxides may be selected from nitroxide compound, such as 2,2,5,5-tetramethyl-l- pyrrolidinyloxy, 3-carboxy-2,2,5,5-tetramethyl-pyrrolidinyloxy, 2,2,6,6-tetramethyl- 1-piperidinyloxy, 4-hydroxy-2,2,6,6-tetramethyl-l-piperidinyloxy, 4-methoxy- 2,2,6,6-tetramethyl-l-piperidinyloxy, 4-oxo-2,2,6,6-tetramethyl-l-piperidinyloxy, bis-(l-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, 2,2,6,6-tetramethyl-4- hydroxypiperidine-l-oxyl)monophosphonate, N-tert-butyl-l-diethylphosphono-2,2- dimethyl propyl nitroxide, N-tert-butyl-l-dibenzyl
- a pro-degradant is further added in the cracking step.
- the pro-degradant may be selected from the group consisting of zinc stearate, tin stearate, iron (II) stearate, iron (III) stearate, cobalt stearate, manganese stearate, and any combinations thereof.
- the cracking step may be performed for a residence time of less than 2 min, preferably less than 90 s, most preferably less than 70 s.
- the cracking step may be performed as disclosed in patent applications US20220153976A1 and US20220153883A1, which are herein incorporated by reference in their entirety.
- the HMW olefin-based resin has an initial molecular weight Mw of 50,000 g/mol up to 1,000,000 g/mol, preferably 50,000 g/mol up to 500,000 g/mol measured according to ISO 16014-4.
- the olefin-based resins are selected from plastic waste (also known as recycled resins or plastics).
- the olefin-based resins are selected from post-consumer resins, postindustrial resins, resin scraps, and combinations thereof.
- the olefin-based resins may also be produced from petrochemical sources, biobased sources, or combinations thereof.
- olefin-based resins are selected from resins comprising more than 50% of olefin monomers, preferably selected from ethylene, olefins comprising from 3 to 10 carbon atoms, and combinations thereof.
- the method of the present disclosure comprises a further step of purifying the oil recovered from the reactor.
- the method of the present disclosure comprises the following steps:
- the HMW olefin-based resin is preferably a plastic waste.
- the condensables also referred as liquid or oil
- the condensables yield in the converting step is at least 10% higher in comparison to the condensables yield when feeding HMW into the pyrolysis reactor.
- the oil obtained according to the present disclosure may be further used in polymerization processes to produce new resins.
- the molecular weight of samples was measured according to ISO 16014-4 using high-temperature GPC experiments carried out in a gel permeation chromatograph coupled with an infrared detector IR6 from Polymer Char. A set of 4 columns (mixed bed, 13 pm, from Tosoh) at a temperature of 140°C is used. The conditions of the experiments are concentration of 1 mg/mL, flow rate of 1 mL/min, dissolution temperature and time of 160°C and 30 min, respectively, and an injection volume of 200 pL.
- the solvent used is ODCB (1,2-dichlorobenzene) stabilized with 100 ppm of BHT (butylated hidroxy toluene). Prior to the analyses, samples were dissolved for 60 min and filtered in an external filtration system (EFS, Polymer Char). TGA
- thermogravimetric analysis of samples was measured according to the ASTM El 131, Compositional Analysis by Thermogravimetry.
- the analysis was performed using a TA Instruments Model Q500 with a temperature ramp rate of 20 °C/min from room temperature to 800 °C in a nitrogen atmosphere. 10 mg of sample are used for each analysis.
- a fixed amount of 7 g of sample (polymer or wax) was degraded at a preselected temperature and time.
- the reaction system comprised a quartz reactor 101 (internal diameter of 3 cm and height of 60 cm) and a fixed bed 102, which was aligned in series with the exhaust line 103 of the pyrolysis reactor.
- the reactors were located inside two independent cylindrical electrical furnaces (furnace A 104 and furnace B 105), used to control the reaction temperature, and were isolated with glass wool.
- Two thermocouples (“A" 106 and “B” 107) were attached to the furnaces and used to provide temperature readings to the controller 108.
- thermocouple (“C” 109) was connected to a datalogger (USB-501-TC-ECD Series) and placed inside the melting pot 110 to record the heating profile with sampling interval of 10 seconds.
- a heating coil 111 surrounded the quartz reactor and was used to preheat the nitrogen stream 112, used to maintain the reaction environment free of oxygen and to drag the generated gases. The nitrogen gas flow was kept constant in all trials (80 mL/min).
- a cylindrical quartz melting pot (internal diameter of 2 cm and height of 12 cm) was used to place the polymer material inside the pyrolytic reactor. Before the start of the reaction, the melting pot was suspended by a wire 113 above the furnace; after reaching the desired temperature, the melting pot was placed into the reactor to initiate the pyrolysis reaction. The generated products were condensed with help of an electrostatic precipitator condenser 114 after flowing through the catalyst bed and the liquid fraction was stored in a glass flask 115. A tedlar bag 116 for collecting gas may be fluidly connected to the flask.
- the main objective is to evaluate the influence of different feedstock sources and how they can affect pyrolysis conditions and products.
- LLDPE 1 is a commercial resin from Braskem produced using metallocene catalyst, MFI 190°C/2.16kg is 25g/10 min (ASTM D1238), density 0.910g/cm 3 (ASTM D792).
- LLDPE 2 is a commercial resin from Braskem, produced using metallocene catalyst, MFI 190°C/2.16kg is lg/10 min (ASTM D1238), density 0.917g/cm 3 (ASTM D792).
- WAX C is a commercial linear polyethylene wax with very low molecular weight.
- Wax G is a commercial resin Braskem polyethylene-based wax produced with green ethylene.
- Table 1 lists Mw values for samples of HMW (LLDPE 1 1 and LLDPE2) and LMW (Wax C and Wax G).
- Figure 2 shows the molecular weight distribution, where it is observed that the samples presented in this example have a significant difference in the Mw that reflects in the difference in viscosity of more than 5 orders of magnitude, measured at 140°C ( Figure 3).
- TGA analysis is usually used to correlate pyrolysis results because it can simulate, on a small scale, a proof of concept for the thermal behavior of polymers.
- TGA analysis comparing the samples of this example indicates the influence of molar mass on thermal behavior, as is shown in Figure 4. It is shown that the T onset (temperature of the beginning of degradation) is lower for samples with LMW and higher for samples of HMW.
- Sample PCR1 is a Braskem PCR sample, with MFI ranging from 0.10 up to 0.90 g/lOmin and density ranging from 0.910 up to 0.915g/cm 3 , its main component being LLDPE.
- Sample PCR 1 (HMW) was pre-cracked in an extruder at temperature around 450°C for 60 s and fed to a pyrolysis reactor in the following different ways:
- PP PCR is a post-consumer PP composed of a mixture of PP heterophasic copolymer and LLDPE, with MFI of 14g/ 10 min;
- TGA analysis comparing the samples of this example indicates the influence of molar mass on thermal behavior, as is shown in Figure 9. It is shown that the T onset (temperature of the beginning of degradation) is lower for samples with LMW and higher for samples of HMW and it is even possible to see differences among the LMW samples.
- Waxes 2, 3-2 and 8 have a better liquid yield than PCR1 ( Figure 11 and Figure 12).
- the chemical recycling reactor is fed with the polymer at room temperature (around 25°C).
- the starting polymer has a molecular weight of around 200,000 g/mol.
- the polymer is heated from 25°C up to 500°C.
- the polymer is cracked until C25 - C35.
- the chemical recycling reactor is fed by an extruder operating at 250°C.
- the polymer is heated from room temperature (around 25°C) up to 250°C.
- the starting polymer has a molecular weight of around 200,000 g/mol. The molecular weight does not change in the extruder.
- the polymer is heated from 250°C up to 500°C.
- the polymer is cracked until C25 - C35, or less.
- the chemical recycling reactor is fed by an extruder operating at 450°C.
- the polymer is heated from room temperature (around 25°C) up to 450°C, in less than 2 minutes ( Figure 14).
- the starting polymer has a molecular weight of around 200,000 g/mol and breaks down during the extrusion, in a cracking reaction, ending the extrusion process and entering the chemical recycling reactor with a molecular weight of around 10,000 g/mol.
- the polymer is cracked until C25 - C35, or less.
- the chemical recycling reactor can operate at 450°C, consuming even less energy.
- a potentiometer was used to measure the energy needed to heat samples of different molecular weight from 200°C up to 450°C. The results are listed in Figure 15 and it is possible to see that the energy required to heat samples of LMW is at least 40% lower than the HMW.
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Abstract
Provided is a method for producing an oil comprising feeding an olefin-based resin in a pyrolysis reactor, converting the olefin-based resin into oil, and recovering the produced oil wherein the olefin-based resin is a low molecular weight (LMW) olefin-based resin. The LMW olefin-based resin comprises a molecular weight of less than 50,000 g/mol, preferably less than 40,000 g/mol measured according to ISO 16014-4. In certain embodiments, the method further comprises the steps of feeding a higher molecular weight (HMW) olefin-based resin into an extruder, cracking the HMW olefin-based resin to produce a LMW olefin-based resin. Also provided are an oil produced according to the method and a use of the oil for as a feedstock for production of olefin-based resins.
Description
METHOD TO PRODUCE AN OIL FROM OLEFIN-BASED RESINS BY PYROLYSIS
BACKGROUND
[0001] Polyolefins such as polyethylene (PE) and polypropylene (PP) may be used to manufacture a varied range of articles, including films, molded products, foams, and the like. Polyolefins may have characteristics such as high processability, low production cost, flexibility, low density, and recyclability. While plastics such as polyethylene and polypropylene have many beneficial uses, there is a need for their correct disposal after use, or even their reuse or recycling so as to minimize the environmental impact of plastic wastes.
[0002] Mechanical recycling techniques are being widely used due to their simplicity and relative low cost. Those techniques preserve the molecular structure of polymers. They usually comprise process steps such as sorting, shredding, washing, melting, etc. Although simple, mechanical recycling techniques present some limitations. The separation of different types of polymers and contaminants is a great challenge, especially when dealing with poor quality waste sources.
[0003] On the other hand, advanced recycling techniques are being considered as a promising alternative. The goal of those techniques is converting plastic waste into oil and building blocks (e.g., monomers) that would be ultimately feed back into the plastic production.
[0004] An example of advanced recycling is pyrolysis. Pyrolysis is a thermochemical treatment wherein a material (e.g., plastic) is exposed to high temperature in the absence of oxygen. This process results in thermal decomposition of the material which forms new molecules. As an example, US10131847B2 discloses a process to convert waste plastics material to fuel by using pyrolysis.
[0005] Thermal cracking processes such as pyrolysis present several limitations regarding the heat distribution. To produce products with a consistent quality, it is important that the same heat is applied to the plastic. However, considering heating conductivity and low IR absorption of plastics, radiant heat and convection are not good ways to heat plastics in a pyrolysis reactor. The most efficient way of heating
plastics is by contact heating, which means that the superficial area and the physical characteristics of the plastics (particle size, for example) and reactor design are very important to assure pyrolysis efficiency. While a lot of new technologies are being developed for chemical recycling of plastics, some reactors can be considered not efficient and obsolete, and it can be very slow and expensive to make changes to an operating reactor.
SUMMARY
[0006] This summary is provided to introduce a selection of concepts that are further described below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.
[0007] In one aspect, embodiments disclosed herein are related to a method for producing an oil comprising:
- feeding an olefin-based resin into a pyrolysis reactor,
- converting the olefin-based resin into oil, and
- recovering the produced oil, wherein the olefin-based resin is a low molecular weight (LMW) olefin-based resin.
[0008] In another aspect, embodiments disclosed herein relate to an oil produced according to said method.
BRIEF DESCRIPTION OF DRAWINGS
[0009] FIG. 1 shows a schematic representation of a pyrolysis unit.
[0010] FIG. 2 shows the molecular weight distribution of samples Wax C, Wax G, LLDPE 1, and LLDPE 2.
[0011] FIG. 3 shows the viscosity profile at 140°C for samples Wax C, Wax G, LLDPE 1, and LLDPE 2.
[0012] FIG. 4 shows TGA analysis (T onset) for samples Wax C, Wax G, LLDPE 1, and LLDPE 2.
[0013] FIG. 5 shows condensable yields for samples Wax C, Wax G, LLDPE 1, and LLDPE 2 in a pyrolysis trial at 450°C, 30 minutes.
[0014] FIG. 6 shows condensable yields for samples Wax C, Wax G, LLDPE 1, and LLDPE 2 in a pyrolysis trial at 450°C, 45 minutes.
[0015] FIG. 7 shows the molecular weight distribution graph for samples PCR 1, Wax 2, Wax 3-2, and Wax 8.
[0016] FIG. 8 shows viscosity profile at 140°C for samples PCR 1, Wax 2, Wax 3-2, and Wax 8.
[0017] FIG. 9 shows TGA analysis (T onset) for samples PCR 1, Wax 2, Wax 3-2, and Wax 8.
[0018] FIG. 10 shows condensable yields for samples PCR 1, Wax 2, Wax 3-2, and Wax 8 in a pyrolysis trial at 450°C, 30 minutes.
[0019] FIG. 11 shows condensable yields for samples PCR 1, Wax 2, Wax 3-2, and Wax 8 in a pyrolysis trial at 450°C, 15 minutes.
[0020] FIG. 12 shows condensable yields for samples PCR 1, Wax 2, and Wax 8 in a pyrolysis trial at 450°C, 45 minutes.
[0021] FIG. 13 shows a schematic representation of the extruder working at 250 °C and feeding a chemical reactor.
[0022] FIG. 14 shows a schematic representation of the extruder working at 450 °C and feeding a chemical reactor.
[0023] FIG. 15 shows the energetic demand for samples of different molecular weight.
DETAILED DESCRIPTION
[0024] Embodiments disclosed herein generally relate to a method of producing an oil by feeding a low molecular weight (LMW) olefin-based resin into a pyrolysis reactor, converting the LMW olefin-based resin into an oil, and recovering said oil. According to the present disclosure, it was surprisingly found that feeding a pyrolysis reactor
with low molecular weight olefin-based resins increases the process efficiency and reduces energy consumption.
[0025] Specifically, embodiments of the present disclosure may improve heat transfer and increase the efficiency of advanced chemical recycling processes. As described herein, the process of the present disclosure melts and cracks the polymer before it is introduced into the reactor. The polymer is introduced through an extruder, and thus the polymer enters into the thermal reactor already melted and with a very low viscosity, which significantly increases the heat transfer. Besides increasing the heat transfer efficiency, the low viscosity also facilitates polymer transportation and homogeneity inside the reactor.
[0026] In some embodiments, the method for producing an oil in the present invention comprises the following steps:
- feeding an olefin-based resin into a pyrolysis reactor,
- converting the olefin-based resin into an oil, and
- recovering the produced oil, wherein the olefin-based resin is a low molecular weight (LMW) olefin-based resin.
[0027] In the present invention, the term “pyrolysis” refers to a thermal degradation treatment wherein the polymeric chains of the resin are broken to form smaller molecules by heat and under an environment substantially free of oxygen.
[0028] In some embodiments, LMW olefin-based resin has a molecular weight of less than 50,000 g/mol, preferably less than 40,000 g/mol, measured by high temperature gel permeation chromatography (GPC) according to ISO 16014-4.
[0029] In accordance with one or more embodiments, the feeding step may occur by means of an extruder, preferably a twin-screw extruder.
[0030] In one or more embodiments, the LMW olefin-based resin is fed into the reactor in a molten state. Therefore, the LMW olefin-based resin may be fed above its melting temperature. In a preferred embodiment, the LMW olefin-based resin is maintained and fed in a temperature close to the reactor temperature, preferably equal to or greater than 300°C, preferably greater than 400 °C, more preferably greater than 450°C. In some embodiments, the LMW olefin-based resin is molten and fed (e.g. by using an extruder) in an environment substantially free of oxygen.
[0031] In one or more embodiments, the conversion step occurs in a reactor selected from a batch reactor, semi-batch reactor, or a two-stage pyrolysis system.
[0032] In one or more embodiments, the conversion step occurs at a temperature ranging from 400 to 600°C, and a residence time from 15 min to 2 h, and in an environment substantially free of oxygen. In some embodiments, the converting step occurs in the presence of a catalyst.
[0033] In some preferred embodiments, the method further comprises a cracking step (that may be also referred as pre-treatment or pre-cracking step) wherein a higher molecular (HMW) olefin-based resin is melted and cracked to produce the LMW olefin-based resin that is fed into the reactor. Thus, in one or more embodiments, the cracking step may occur before or during the feeding step.
[0034] In one or more embodiments, the cracking step occurs by means of an extruder.
[0035] In one or more embodiments, the cracking step occurs in an extruder that is directly connected to the reactor. Therefore, the LMW olefin-based resin may be directly fed into the reactor.
[0036] In some preferred embodiments, the extruder used in the cracking step is a twin- screw extruder.
[0037] In one or more embodiments, the molecular weight of the HMW olefin-based resin is reduced by at least 4 times (i.e. “4x”) in the cracking step.
[0038] In one or more embodiments, the cracking step may be performed above the onset degradation temperature, optionally in the presence of a visbreaking agent. The “onset degradation temperature” is the temperature wherein the polymer chains of the resin start to breakdown. This “onset degradation temperature” may be determined by thermogravimetric analysis (TGA), according to ASTM El 131 standard method.
[0039] In some alternative embodiments, the cracking step is performed at a temperature above the melting temperature and below the onset degradation temperature of the HMW olefin-based resin and in the presence of a visbreaking agent.
[0040] When present, the visbreaking agents may be free radical generators selected from peroxides, nitroxides, and combinations thereof. The peroxides may be selected from 3 -hydroxy- 1,1 -dimethylbutyl peroxyneodecanoate, a-cumyl
peroxyneodecanoate, 2-hydroxy- 1,1 -dimethylbutyl peroxyneoheptanoate a-cumyl peroxyneoheptanoate, t-amyl peroxyneodecanoate, t-butyl peroxyneodecanoate, di(2- ethylhexyl) peroxydicarbonate, di(n-propyl) peroxydicarbonate, di(sec -butyl) peroxydicarbonate, t-butyl peroxyneoheptanoate, t-amyl peroxypivalate, t-butyl peroxypivalate, diisononanoyl peroxide, didodecanoyl peroxide, 3 -hydroxy- 1,1- dimethylbutylperoxy-2-ethylhexanoate, didecanoyl peroxide, 2,2'- azobis(isobutyronitrile), di(3 -carboxypropionyl) peroxide, 2,5-dimethyl-2,5-di(2- ethylhexanoylperoxy)hexane, dibenzoyl peroxide, t-amylperoxy 2-ethylhexanoate, t- butylperoxy 2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxy-(cis-3- carboxy)propenoate, 1 , 1 -di(t-amylperoxy)cyclohexane, 1 , 1 -di(t-butylperoxy)-3 ,3 ,5- trimethylcyclohexane, l,l-di(t-butylperoxy) cyclohexane, OO-t-amyl O-(2- ethylhexyl) monoperoxycarbonate, OO-t-butyl O-isopropyl monoperoxycarbonate, OO-t-butyl O-(2-ethylhexyl) monoperoxycarbonate, polyether tetrakis(t- butylperoxycarbonate), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-amyl peroxyacetate, t-amyl peroxybenzoate, t-butyl peroxyisononanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, di-t-butyl diperoxyphthalate, 2.2-di(t- butylperoxy )butane, 2,2-di(t-amylperoxy)propane, n-butyl 4,4-di(t- butylperoxy)valerate, ethyl 3,3-di(t-amylperoxy)butyrate, ethyl 3.3-di(t- butylperoxy)butyrate, dicumyl peroxide, a,a'-bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, di(t-amyl) peroxide, t-butyl a-cumyl peroxide, di(t-butyl) peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, dicetil peroxi-dicarbonato, 3,6,9-triethyl-3,6,9-trimethyl-l,4,7-triperoxonane, tertbutylperoxy 2-ethylhexyl carbonate, tert-butyl-peroxide n-butyl fumarate(benzoate), dimyristoyl peroxydiicarbonate, 3,3,5,7,7-pentamethyl-l,2,4-trioxepane, tert-butyl hydroperoxide, bis(4-t-butylcyclohexyl) peroxydicarbonate, and 1, 2, 4, 5,7,8- hexoxonane, 3,6,9-trimethyl-3,6,9-tris(ethyl and propyl derivatives). The nitroxides may be selected from nitroxide compound, such as 2,2,5,5-tetramethyl-l- pyrrolidinyloxy, 3-carboxy-2,2,5,5-tetramethyl-pyrrolidinyloxy, 2,2,6,6-tetramethyl- 1-piperidinyloxy, 4-hydroxy-2,2,6,6-tetramethyl-l-piperidinyloxy, 4-methoxy- 2,2,6,6-tetramethyl-l-piperidinyloxy, 4-oxo-2,2,6,6-tetramethyl-l-piperidinyloxy, bis-(l-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, 2,2,6,6-tetramethyl-4- hydroxypiperidine-l-oxyl)monophosphonate, N-tert-butyl-l-diethylphosphono-2,2- dimethyl propyl nitroxide, N-tert-butyl-l-dibenzylphosphono-2,2-dimethylpropyl
nitroxide, N-tert-butyl-l-di(2,2,2-trifluoroethyl)phosphono-2,2dimethylpropyl nitroxide, N-tert-butyl-(l-diethylphosphono)-2-methyl-propyl nitroxide, N-(l- methylethyl)- 1 -cyclohexyl- 1 -(diethylphosphono) nitroxide, N-( 1 -phenylbenzyl)-( 1 - diethylphosphono)-l -methyl ethylnitroxide, N-phenyl-l-diethylphosphono-2,2- dimethyl propyl nitroxide, N-phenyl-l-diethylphosphono-l-methyl ethyl nitroxide, N-(l-phenyl 2-methyl propyl)- 1 -diethylphosphono- 1 -methyl ethyl nitroxide, N-tert- butyl-l-phenyl-2-methyl propyl nitroxide, and N-tert-butyl-l-(2-naphthyl)-2-methyl propyl nitroxide, or a mixture thereof.
[0041] In one or more embodiments, a pro-degradant is further added in the cracking step. The pro-degradant may be selected from the group consisting of zinc stearate, tin stearate, iron (II) stearate, iron (III) stearate, cobalt stearate, manganese stearate, and any combinations thereof.
[0042] The cracking step may be performed for a residence time of less than 2 min, preferably less than 90 s, most preferably less than 70 s.
[0043] In one or more embodiments, the cracking step may be performed as disclosed in patent applications US20220153976A1 and US20220153883A1, which are herein incorporated by reference in their entirety.
[0044] In some embodiments, the HMW olefin-based resin has an initial molecular weight Mw of 50,000 g/mol up to 1,000,000 g/mol, preferably 50,000 g/mol up to 500,000 g/mol measured according to ISO 16014-4.
[0045] The methods of the present disclosure are particularly useful in the recycling field. Therefore, in a preferred embodiment the olefin-based resins (LMW and/or HMW) are selected from plastic waste (also known as recycled resins or plastics). Preferably, the olefin-based resins are selected from post-consumer resins, postindustrial resins, resin scraps, and combinations thereof. The olefin-based resins may also be produced from petrochemical sources, biobased sources, or combinations thereof.
[0046] In one or more embodiments, olefin-based resins are selected from resins comprising more than 50% of olefin monomers, preferably selected from ethylene, olefins comprising from 3 to 10 carbon atoms, and combinations thereof.
[0047] In one or more embodiments, the method of the present disclosure comprises a further step of purifying the oil recovered from the reactor.
[0048] In one or more embodiments, the method of the present disclosure comprises the following steps:
- feeding an HMW olefin-based resin into an extruder,
- cracking the HMW olefin-based resin to produce a LMW olefin-based resin,
- feeding the LMW olefin-based resin into a pyrolysis reactor,
- converting the LMW olefin-based resin into an oil, and
- recovering the produced oil, wherein the HMW olefin-based resin is preferably a plastic waste.
[0049] It has been found that by performing pyrolysis using a LMW olefin-based resin as feedstock, the condensables (also referred as liquid or oil) yield of the pyrolysis reaction is increased. It was observed that in the presently disclosed method, the condensables yield in the converting step is at least 10% higher in comparison to the condensables yield when feeding HMW into the pyrolysis reactor.
[0050] The oil obtained according to the present disclosure may be further used in polymerization processes to produce new resins.
Examples
Measurement methods description
GPC
[0051] The molecular weight of samples was measured according to ISO 16014-4 using high-temperature GPC experiments carried out in a gel permeation chromatograph coupled with an infrared detector IR6 from Polymer Char. A set of 4 columns (mixed bed, 13 pm, from Tosoh) at a temperature of 140°C is used. The conditions of the experiments are concentration of 1 mg/mL, flow rate of 1 mL/min, dissolution temperature and time of 160°C and 30 min, respectively, and an injection volume of 200 pL. The solvent used is ODCB (1,2-dichlorobenzene) stabilized with 100 ppm of BHT (butylated hidroxy toluene). Prior to the analyses, samples were dissolved for 60 min and filtered in an external filtration system (EFS, Polymer Char).
TGA
[0052] The thermogravimetric analysis of samples was measured according to the ASTM El 131, Compositional Analysis by Thermogravimetry.
[0053] The analysis was performed using a TA Instruments Model Q500 with a temperature ramp rate of 20 °C/min from room temperature to 800 °C in a nitrogen atmosphere. 10 mg of sample are used for each analysis.
Rheometry
[0054] Rheological measurements were performed in flow regime at 140°C, using 25 mm cone and plate geometry, with a shear rate varying from 0.1 up to 1000 s’1. A soaking time of 60s was used.
Density
[0055] All density data was obtained following ASTM D792.
Melt flow index (MFI)
[0056] All MFI data was obtained according to ASTM D1238. For PE samples, the conditions used were 190°C and 2.16kg.
Description of the pyrolysis methodology
[0057] The experiments were conducted in a pyrolysis unit, as shown in Figure 1.
[0058] A fixed amount of 7 g of sample (polymer or wax) was degraded at a preselected temperature and time. The reaction system comprised a quartz reactor 101 (internal diameter of 3 cm and height of 60 cm) and a fixed bed 102, which was aligned in series with the exhaust line 103 of the pyrolysis reactor. The reactors were located inside two independent cylindrical electrical furnaces (furnace A 104 and furnace B 105), used to control the reaction temperature, and were isolated with glass wool. Two thermocouples (“A" 106 and “B" 107) were attached to the furnaces and used to provide temperature readings to the controller 108. A third thermocouple (“C" 109) was connected to a datalogger (USB-501-TC-ECD Series) and placed inside the melting pot 110 to record the heating profile with sampling interval of 10 seconds. A heating coil 111 surrounded the quartz reactor and was used to preheat the nitrogen
stream 112, used to maintain the reaction environment free of oxygen and to drag the generated gases. The nitrogen gas flow was kept constant in all trials (80 mL/min).
[0059] A cylindrical quartz melting pot (internal diameter of 2 cm and height of 12 cm) was used to place the polymer material inside the pyrolytic reactor. Before the start of the reaction, the melting pot was suspended by a wire 113 above the furnace; after reaching the desired temperature, the melting pot was placed into the reactor to initiate the pyrolysis reaction. The generated products were condensed with help of an electrostatic precipitator condenser 114 after flowing through the catalyst bed and the liquid fraction was stored in a glass flask 115. A tedlar bag 116 for collecting gas may be fluidly connected to the flask.
[0060] The final gas, liquid, and solid mass fractions were quantified through mass balance. Also, note that, experimentally, the gas fraction is obtained by mass difference.
Pyrolysis Example
[0061] The main objective is to evaluate the influence of different feedstock sources and how they can affect pyrolysis conditions and products.
[0062] The following samples were evaluated:
[0063] LLDPE 1 is a commercial resin from Braskem produced using metallocene catalyst, MFI 190°C/2.16kg is 25g/10 min (ASTM D1238), density 0.910g/cm3 (ASTM D792).
[0064] LLDPE 2 is a commercial resin from Braskem, produced using metallocene catalyst, MFI 190°C/2.16kg is lg/10 min (ASTM D1238), density 0.917g/cm3 (ASTM D792).
[0065] WAX C is a commercial linear polyethylene wax with very low molecular weight.
[0066] Wax G is a commercial resin Braskem polyethylene-based wax produced with green ethylene.
[0067] Table 1 lists Mw values for samples of HMW (LLDPE 1 1 and LLDPE2) and LMW (Wax C and Wax G). Figure 2 shows the molecular weight distribution, where
it is observed that the samples presented in this example have a significant difference in the Mw that reflects in the difference in viscosity of more than 5 orders of magnitude, measured at 140°C (Figure 3).
Table 1. Molecular weight (Mw) information for samples of HMW (LLDPE 1 and LLDPE2) and LMW (Wax C and Wax G)
[0068] Comparing low and high molecular weight samples, different energy gains in the pyrolysis process are observed, such as a reduction of temperature or time in the reactor.
[0069] TGA analysis is usually used to correlate pyrolysis results because it can simulate, on a small scale, a proof of concept for the thermal behavior of polymers.
[0070] TGA analysis comparing the samples of this example indicates the influence of molar mass on thermal behavior, as is shown in Figure 4. It is shown that the T onset (temperature of the beginning of degradation) is lower for samples with LMW and higher for samples of HMW.
[0071] The different pyrolysis products are described as liquid (or condensable or oil), gas (or volatile), and solid residue. The best result is to obtain a higher concentration of liquid, and consequently, less solid residue in the reactor.
[0072] Four samples of different molar masses were tested at three different temperatures and at three residence times. The yields obtained were compared:
At 450° C, 30 min, it was possible to identify significant differences between the samples as shown in Figure 5; thus, proving the direct influence of the molar mass on the liquid yields (approximately 50%);
At all temperatures and residence times tested is possible to see the effect of molecular weight (Figure 6).
PCR Example
[0073] In this example the same thermal treatment procedure described for the former example was done for 4 samples. In this case the samples are PCR (post-consumer resin). Sample PCR1 is a Braskem PCR sample, with MFI ranging from 0.10 up to 0.90 g/lOmin and density ranging from 0.910 up to 0.915g/cm3, its main component being LLDPE. Sample PCR 1 (HMW) was pre-cracked in an extruder at temperature around 450°C for 60 s and fed to a pyrolysis reactor in the following different ways:
1) in the presence of a peroxide. The resulting LMW product is Wax 3-2.
2) Mixed with 10% wt. of polypropylene (PP) PCR and the resulted LMW sample is Wax 8. PP PCR is a post-consumer PP composed of a mixture of PP heterophasic copolymer and LLDPE, with MFI of 14g/ 10 min;
3) Only PCR 1 was added to the extruder and the resulting LMW is Wax 2.
[0074] The molecular weight distribution graph of the referenced samples is shown in Figure 7, where it is possible to observe that, besides the Mw difference (shown in Table 2) between PCR1 and Waxes, it is also possible to observe a narrowing of the MWD.
Table 2. Molecular weight (Mw) information for samples of HMW (PCR 1) and LMW (Wax 2, Wax 3-2 and Wax 8)
[0075] The Mw of cracked samples is around 10 times lower than the original sample. The influence of this difference in the viscosity can be seen in Figure 8, where it is shown that PCR 1 has a viscosity of more than 2 orders of magnitude higher than the generated waxes.
[0076] TGA analysis comparing the samples of this example indicates the influence of molar mass on thermal behavior, as is shown in Figure 9. It is shown that the T onset (temperature of the beginning of degradation) is lower for samples with LMW and
higher for samples of HMW and it is even possible to see differences among the LMW samples.
[0077] From low and high molecular weight samples, different energy gains in the pyrolysis process are observed, such as a reduction of temperature or time in the reactor.
[0078] Four samples of different molar masses were tested at three different temperatures and at three residence times. The yields obtained were compared:
At 450° C, 30 min of residence time, it was possible to identify significant differences between the samples as shown in Figure 10; thus, proving the direct influence of the molar mass on the liquid yields (approximately 40%);
At all temperatures and times tested it is possible to see the effect of molecular weight: Waxes 2, 3-2 and 8 have a better liquid yield than PCR1 (Figure 11 and Figure 12).
Energetic Benefit Example
Extruder Energy
[0079] In order to quantify the energy spent to melt and crack the polymer in the extruder, the equations used are described in Table 3 and Equation 1. This calculation method is according to literature references: 2010 - Rauwendaal, C. - How to Get Peak Performance & Efficiency Out of Your Extrusion Line, Part I; 2014 - Abeykoon et al - Process efficiency in polymer extrusion: Correlation between the energy demand and melt thermal stability; 2014 - Abeykoon et al - Investigation of the process energy demand in polymer extrusion: A brief review and an experimental study; 2021 - Abeykoon et al - Energy efficiency in extrusion-related polymer processing: A review of state of the art and potential efficiency improvements.
Equation 1
Chemical Recycling Reactor Energy
[0080] In order to quantify the energy spent to melt and crack the polymer in the thermal degradation reactor, the equations used are described in Table 4 and Equation 2. This calculation method is according to the following literature reference: Szostak, Elzbieta, et al. "Characteristics of plastic waste processing in the modern recycling plant operating in Poland." Energies 14.1 (2021): 35.
Table 4. Equations for calculation of different kinds of heat during thermal degradation in the chemical recycling reactor
Chemical Recycling Reactor
[0081] The chemical recycling reactor is fed with the polymer at room temperature (around 25°C). The starting polymer has a molecular weight of around 200,000 g/mol.
In the chemical recycling reactor, the polymer is heated from 25°C up to 500°C. In the reactor the polymer is cracked until C25 - C35.
Extruder operating at 250°C + Chemical Recycling Reactor
[0082] As represented in Figure 13, the chemical recycling reactor is fed by an extruder operating at 250°C. The polymer is heated from room temperature (around 25°C) up to 250°C. The starting polymer has a molecular weight of around 200,000 g/mol. The molecular weight does not change in the extruder. In the chemical recycling reactor, the polymer is heated from 250°C up to 500°C. In the reactor the polymer is cracked until C25 - C35, or less.
Extruder operating at 450°C + Chemical Recycling Reactor
[0083] According to the present disclosure, the chemical recycling reactor is fed by an extruder operating at 450°C. The polymer is heated from room temperature (around 25°C) up to 450°C, in less than 2 minutes (Figure 14). The starting polymer has a molecular weight of around 200,000 g/mol and breaks down during the extrusion, in a cracking reaction, ending the extrusion process and entering the chemical recycling reactor with a molecular weight of around 10,000 g/mol. In the reactor, the polymer is cracked until C25 - C35, or less.
Table 6. Energy spent to heat and crack samples in the extruder and reactor, considering two different MW.
[0084] Considering the performance of the high amount of condensables as demonstrated in the previous example, the chemical recycling reactor can operate at 450°C, consuming even less energy.
Table 7. Energy spent to heat and crack samples in the extruder and reactor, considering two different MW
[0085] Considering the calculations discussed above, it is possible to save around 30% of energy when an extruder operating at 450°C is feeding inline the thermal degradation reactor and the entering material (LMW) is cracked during the extrusion, reaching a low viscosity characteristic that improves the heating transfer.
Energetic benefit Example 2
[0086] A potentiometer was used to measure the energy needed to heat samples of different molecular weight from 200°C up to 450°C. The results are listed in Figure 15 and it is possible to see that the energy required to heat samples of LMW is at least 40% lower than the HMW.
Claims
1. A method for producing an oil comprising:
- feeding an olefin-based resin into a pyrolysis reactor,
- converting the olefin-based resin into oil, and
- recovering the produced oil, wherein the olefin-based resin is a low molecular weight (LMW) olefin-based resin.
2. The method according to claim 1 wherein the feeding step occurs by means of an extruder, preferably a twin-screw extruder.
3. The method according to claims 1 or 2 wherein the LMW olefin-based is fed in a molten state.
4. The method according to any of claims 1 to 3 wherein the LMW olefin-based is fed at a temperature of equal to or above 300°C, preferably above 400 °C, more preferably above 450°C.
5. The method according to any of claims 1 to 4 wherein the pyrolysis reactor is selected from a batch reactor, semi-batch reactor, or two-stage pyrolysis system.
6. The method according to any of claims 1 to 5 wherein the converting step occurs at a temperature ranging from 400 to 600°C, a residence time from 15 min to 2 h, and in an environment substantially free of oxygen.
7. The method according to any of claims 1 to 6 wherein the converting step occurs in the presence of a catalyst.
8. The method according to any of claims 1 to 7 comprising a further step of cracking a higher molecular (HMW) olefin-based resin to produce the LMW olefin-based resin wherein the cracking may occur before or during the feeding step.
9. The method according to claim 8 wherein in the cracking step the molecular weight of the HMW olefin-based resin is reduced by at least 4 times.
10. The method according to claims 8 or 9 wherein the cracking step occurs in an extruder.
11. The method according to and of claims 8 to 10 wherein the LMW olefin-based resin is directly fed into the reactor.
12. The method according to any of claims 8 to 11 wherein the cracking step is performed above the onset degradation temperature, optionally in the presence of a visbreaking agent.
13. The method according to any of claims 8 to 11, wherein the cracking step is performed in a temperature above the melting temperature and below the onset degradation temperature of the HMW olefin-based resin and in the presence of a visbreaking agent.
14. The method according to any of claims 8 to 13 wherein the cracking step is performed at a residence time of less than 2 min, preferably less than 90 s, most preferably less than 70 s.
15. The method according to any of claims 8 to 14 wherein the condensables yield in the converting step is at least 10% higher in comparison to the condensables yield when feeding HMW into the pyrolysis reactor.
16. The method according to any of claims 8 to 15 wherein the HMW olefin-based resin has an initial molecular weight Mw of 50,000 g/mol to 1,000,000 g/mol, preferably 50,000 g/mol to 500,000 g/mol measured according to ISO 16014-4.
17. The method according to any of claims 1 to 16 wherein the LMW olefin-based resin is a plastic waste, preferably a post-consumed resin, post-industrial resin, or scrap source.
18. The method according to any of claims 1 to 16 wherein the LMW olefin-based resin is from petrochemical or biobased source.
19. The method according to any of claims 1 to 18 wherein the LMW olefin-based resin comprises olefin monomers selected from ethylene, olefins comprising 3 to 10 carbon atoms, and combinations thereof.
20. The method according to any of claims 1 to 19 wherein the LMW olefin-based resin comprises a molecular weight of less than 50,000 g/mol, preferably less than 40,000 g/mol measured according to ISO 16014-4.
21. The method according to any of claims 1 to 20 comprising a further step of purifying the oil recovered from the reactor.
22. An oil obtained according to the process of any of claims 1 to 21.
23. Use of the oil according to claim 22 as a feedstock for production of olefin- based resins.
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US20220153883A1 (en) | 2020-11-13 | 2022-05-19 | Braskem S.A. | Processing of polyethylene-based compositions and products therefrom |
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