IP Library Granted Patent US 12,215,292
Granted Patent B2
US 12,215,292 · App. 17/973,381 · Granted Feb 4, 2025

Catalytic upcycling of polyolefins into lubricants

Inventors: Gokhan Celik (Clarendon Hills, IL); Kimaya Prakash Vyavhare (Woodridge, IL); Robert M. Kennedy (Evanston, IL); Ryan Hackler (Chicago, IL); Ali Erdemir (Naperville, IL); Massimiliano Delferro (Chicago, IL)
Assignee: UCHICAGO ARGONNE, LLC
C10M111/04B01J21/04B01J23/002B01J23/02B01J23/42B01J23/755B01J35/23C10M105/04C10M107/02C10M177/00C10M2203/022C10M2205/0206
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,215,292
App. No.
17/973,381
Granted
Feb 4, 2025
Kind
B2
Abstract

A method of upcycling polymers to useful hydrocarbon materials. A catalyst with nanoparticles on a substrate selectively docks and cleaves longer hydrocarbon chains over shorter hydrocarbon chains. The nanoparticles exhibit an edge to facet ratio to provide for more interactions with the facets.

Claims (23)

1. A method of producing a lubricant comprising:

exposing, at a temperature of 150-350° C. and a pressure of 100-200 psi for 12-72 hours, a plurality of polymer molecules to a catalyst comprising a substrate having a plurality of catalytic nanoparticles deposited thereon;

cleaving at least one carbon-carbon bond of a first polymer molecule of the plurality of polymer molecules;

forming a plurality of hydrocarbon fragments from the cleaving;

cleaving at least one carbon-carbon bond of a second polymer molecule of the plurality of polymer molecules; and

forming a second plurality of hydrocarbon fragments.

2. The method of claim 1 , wherein exposing the plurality of polymer molecules is for at least 24 hours.

3. The method of claim 1 , wherein the plurality of catalytic nanoparticles comprise Pt or Ni.

4. The method of claim 1 , wherein the plurality of polymer molecules are solvent-free.

5. The method of claim 1 , wherein the plurality of polymer molecules have a number-average molecular weight ranging from 400-1000 Da.

6. The method of claim 1 , wherein the plurality of hydrocarbon fragments are C30 to C76 alkanes.

7. The method of claim 6 , wherein the plurality of hydrocarbon fragments have 10 branches per 1000 carbon to 400 branches per 1000 carbon.

8. A method of producing a lubricant comprising:

exposing, at a temperature of 150-350° C. and a pressure of 100-200 psi for 12-72 hours, a plurality of polymer molecules to a catalyst comprising a substrate having a plurality of catalytic nanoparticles deposited thereon; and

forming a plurality of hydrocarbon fragments from the plurality of polymer molecules by:

cleaving at least one carbon-carbon bond of a first polymer molecule;

cleaving at least one carbon-carbon bond of a second polymer molecule; and

mixing the plurality of hydrocarbon fragments with poly-α-olefin, wherein the mixture comprises 10-40 wt % of the plurality of hydrocarbon fragments and having a molar mass distribution of from 400 to 1000 Da and 90-60 wt % poly-α-olefin.

9. The method of claim 8 , wherein the plurality of hydrocarbon fragments are C30 to C76 alkanes.

10. The method of claim 9 , wherein the plurality of hydrocarbon fragments have 10 branches per 1000 carbon to 400 branches per 1000 carbon.

11. The method of claim 9 , wherein the mixture comprises 20-30 wt % of the plurality of hydrocarbon fragments.

12. The method of claim 8 , wherein mixing is at a temperature between 40° C. and 100° C.

13. The method of claim 8 , wherein the plurality of hydrocarbon fragments are saturated hydrocarbons.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 13, 2024
From: CELIK, GOKHAN; VYAVHARE, KIMAYA; KENNEDY, ROBERT M.; HACKLER, RYAN; ERDEMIR, ALI; DELFERRO, MASSIMILIANO
To: UCHICAGO ARGONNE, LLC
Reel/Frame 068586/0457 →
CONFIRMATORY LICENSE Recorded Aug 13, 2024
From: UCHICAGO ARGONNE LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 068590/0070 →
Continuity (2)
Division 17018702 · Sep 11, 2020
Related Publication 20230048467A1 · Feb 16, 2023
References Cited (82)
US 20050285421A1 · Novakovich et al. · 2005 [cited by applicant]
US 20070249497A1 · Tanaka et al. · 2007 [cited by applicant]
US 20100087349A1 · Lee · 2010 [cited by examiner]
US 20110172088A1 · Bedard et al. · 2011 [cited by applicant]
US 20120310023A1 · Huang et al. · 2012 [cited by applicant]
US 20140178262A1 · Tran et al. · 2014 [cited by applicant]
US 20150361374A1 · Kumar et al. · 2015 [cited by applicant]
US 20160369174A1 · Kool et al. · 2016 [cited by applicant]
US 20190169504A1 · Gu et al. · 2019 [cited by applicant]
US 20200238269A1 · Delferro et al. · 2020 [cited by applicant]
US 20210061971A1 · Delferro et al. · 2021 [cited by applicant]
JP 2003321682A · 2003 [cited by applicant]
JP 4154929B2 · 2008 [cited by applicant]
JP 5111246B2 · 2013 [cited by applicant]
WO WO2007126120A1 · 2007 [cited by applicant]
WO WO2007126123A1 · 2007 [cited by applicant]
WO WO2021041323A1 · 2021 [cited by applicant]
Celik, G, Kennedy, RM, Hackler, RA, Ferrandon, M, Tennakoon, A, Patnaik, S, LaPointe, AM, Ammal, SC, Heyden, A, Perras, FA., Pruski M, Scott, SL, Poeppelmeier KR, Sadow AD, Delferro M, “Upcycling Single-Use Polyethylene… [cited by examiner]
Quareshi, et al., “Catalytic consequences of ultrafine Pt clusters supported on SrTiO3 for photocatalytic overall water splitting,” Journal of Catalysis 376, pp. 180-190 (2019). [cited by applicant]
“Advancing Sustainable Materials Management: 2014 Fact Sheet,” United States Environmental Protection Agency, EPA530-R-17-01, 22 pages (2016). [cited by applicant]
Almithn & Hibbitts, “Comparing Rate and Mechanism of Ethane Hydrogenolysis on Transition-Metal Catalysts,” The Journal of Physical Chemistry C 123(9), pp. 5421-5432 (2019). [cited by applicant]
Almithn & Hibbitts, “Effects of Catalyst Model and High Adsorbate Coverages in ab Initio Studies of Alkane Hydrogenolysis,” ACS Catalysis 8(7), pp. 6375-6387 (2018). [cited by applicant]
Andersen, et al., “Pauling's rules for oxide surfaces,” Surface Science Reports 73(5), pp. 213-232 (2018). [cited by applicant]
Beyene, “Recycling of plastic waste into fuels, a review,” International Journal of Science, Technology and Society 2(6), pp. 190-195 (2014). [cited by applicant]
Burange, et al., “Heterogeneously catalyzed strategies for the deconstruction of high density polyethylene: plastic waste valorisation to fuels,” Green Chemistry 17(1), pp. 146-156 (2015). [cited by applicant]
Carr, et al., “Relationship between self-seeded and epitaxial crystallization from polymer solutions: A potentially new method for molecular weight separation and a new decoration method for alkali halides,” Journal of … [cited by applicant]
Celik, et al., “Upcycling Single-Use Polyethylene into High-Quality Liquid Products,” ACS Central Science 5(11), pp. 1795-1803 (2019). [cited by applicant]
Che & Bennett, “The Influence of Particle Size on the Catalytic Properties of Supported Metals,” Advances in Catalysis 36, pp. 55-172 (1989). [cited by applicant]
Chesters, et al., “The reflection-absorption infrared spectra of n-alkanes adsorbed on Pt(111),” Surface Science 209(1-2), pp. 89-99 (1989). [cited by applicant]
Christensen, et al., “Controlled Growth of Platinum Nanoparticles on Strontium Titanate Nanocubes by Atomic Layer Deposition,” Small 5(6), pp. 750-757 (2009). [cited by applicant]
Crosby, et al., “All Roads Lead to TiO2: TiO2-Rich Surfaces of Barium and Strontium Titanate Prepared by Hydrothermal Synthesis,” Chemistry of Materials 30(3), pp. 841-846 (2018). [cited by applicant]
Crosby, et al., “Wulff shape of strontium titanate nanocuboids,” Surface Science 632, pp. L22-L25 (2015). [cited by applicant]
Deak, “Strontium titanate surfaces,” Materials Science and Technology 23(2), pp. 127-136 (2007). [cited by applicant]
Defaud & Basset, “Catalytic Hydrogenolysis at Low Temperature and Pressure of Polyethylene and Polypropylene to Diesels or Lower Alkanes by a Zirconium Hydride Supported on Silica-Alumina: A Step Toward Polyolefin Degra… [cited by applicant]
Dendooven, et al., “Independent tuning of size and coverage of supported Pt nanoparticles using atomic layer deposition,” Nature Communications 8, 1074, 12 pages (2017). [cited by applicant]
Engelhardt, et al., “Structure Sensitivity of Acrolein Hydrogenation by Platinum Nanoparticles on BaxSr1-xTiO3 Nanocuboids,” ChemCatChem 10(3), pp. 632-641 (2018). [cited by applicant]
Enterkin, et al., “Epitaxial Stabilization of Face Selective Catalysts,” Topics in Catalysis 56(18-20), pp. 1829-1834 (2013). [cited by applicant]
Enterkin, et al., “Oriented Catalytic Platinum Nanoparticles on High Surface Area Strontium Titanate Nanocuboids,” Nano Letters 11(3), pp. 993-997 (2011). [cited by applicant]
Enterkin, et al., “Propane Oxidation over Pt/SrTiO3 Nanocuboids,” ACS Catalysis 1(6), pp. 629-635 (2011). [cited by applicant]
Erdemir, et al., “Carbon-based tribofilms from lubricating oils,” Nature 536, pp. 67-71 (2016). [cited by applicant]
Erdman, et al., “Surface Structures of SrTiO3 (001): A TiO2-rich Reconstruction with a c(4×2) Unit Cell,” Journal of the American Chemical Society 125(22), pp. 10050-10056 (2003). [cited by applicant]
Flaherty & Iglesia, “Transition-State Enthalpy and Entropy Effects on Reactivity and Selectivity in Hydrogenolysis of n-Alkanes,” Journal of the American Chemical Society 135(49), pp. 18586-18599 (2013). [cited by applicant]
Flaherty, et al., “Catalytic Ring Opening of Cycloalkanes on Ir Clusters: Alkyl Substitution Effects on the Structure and Stability of C—C Bond Cleavage Transition States,” The Journal of Physical Chemistry C 119(5), pp… [cited by applicant]
Flaherty, et al., “Metal-Catalyzed C—C Bond Cleavage in Alkanes: Effects of Methyl Substitution on Transition-State Structures and Stability,” Journal of the American Chemical Society 136(27), pp. 9664-9676 (2014). [cited by applicant]
Flaherty, et al., “Theoretical and kinetic assessment of the mechanism of ethane hydrogenolysis on metal surfaces saturated with chemisorbed hydrogen,” Journal of Catalysis 311, pp. 350-356 (2014). [cited by applicant]
Goodenough, “Electronic and ionic transport properties and other physical aspects of perovskites,” Reports on Progress in Physics 67(11), pp. 1915-1993 (2004). [cited by applicant]
Grillo, et al., “From Single Atoms to Nanoparticles: Autocatalysis and Metal Aggregation in Atomic Layer Deposition of Pt on TiO2 Nanopowder,” Small 14(23), 1800765, 11 pages (2018). [cited by applicant]
Hahladakis, et al., “An overview of chemical additives present in plastics: Migration, release, fate and environmental impact during their use, disposal and recycling,” Journal of Hazardous Materials 344, pp. 179-199 (2… [cited by applicant]
Hazrat, et al., “Utilization of Polymer Wastes as Transport Fuel Resources—a Recent Development,” Energy Procedia 61, pp. 1681-1685 (2014). [cited by applicant]
Hibbitts, et al., “Effects of Chain Length on the Mechanism and Rates of Metal-Catalyzed Hydrogenolysis of n-Alkanes,” The Journal of Physical Chemistry C 120(15), pp. 8125-8138 (2016). [cited by applicant]
Hopewell, et al., “Plastics recycling: challenges and opportunities,” Philosophical Transactions of the Royal Society B: Biological Sciences 364(1526), pp. 2115-2126 (2009). [cited by applicant]
Hsieh, et al., “Shape-Tunable SrTiO3 Crystals Revealing Facet-Dependent Optical and Photocatalytic Properties,” The Journal of Physical Chemistry C 123(22), pp. 13664-13671 (2019). [cited by applicant]
Inoue, et al., “Structural and dynamical studies of 13C-labeled polyethylene adsorbed on the surface of silica gel by high-resolution solid-state 13C NMR spectroscopy,” Acta Polymerica 46, pp. 420-423 (1995). [cited by applicant]
International Search Report & Written Opinion for PCT/US2020/047654 dated Nov. 20, 2020, 9 pages. [cited by applicant]
Jena, et al., “Studies on the ionic transport and structural investigations of La0.5Li0.5TiO3 perovskite synthesized by wet chemical methods and the effect of Ce, Zr substitution at Ti site,” Journal of Materials Scienc… [cited by applicant]
Jia, et al., “Efficient and selective degradation of polyethylenes into liquid fuels and waxes under mild conditions,” Science Advances 2(6), e1501591, 7 pages (2016). [cited by applicant]
Kanbur, et al., “Catalytic carbon-carbon bond cleavage and carbon-element bond formation give new life for polyolefins as biodegradable surfactants,” Chem 7(5), pp. 1347-1362 (2021). [cited by applicant]
Kennedy, et al., “Replication of SMSI via ALD: TiO2 Overcoats Increase Pt-Catalyzed Acrolein Hydrogenation Selectivity,” Catalysis Letters 148(8), pp. 2223-2232 (2018). [cited by applicant]
Kienzle & Marks, “Surface transmission electron diffraction for SrTiO3 surfaces,” CrystEngComm 14(23), pp. 7833-7839 (2012). [cited by applicant]
Kienzle, et al., “Vacant-site octahedral tilings on SrTiO3 (001), the ([sqrt]13 x [sqrt]13)R33.7 surface, and related structures,” Physical Review Letters 106(17), 176102, 4 pages (2011). [cited by applicant]
Kresse & Furthmuller, “Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set,” Computational Materials Science 6(1), pp. 15-50 (1996). [cited by applicant]
Kresse & Furthmuller, “Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set,” Physical Review B 54(16), pp. 11169-11186 (1996). [cited by applicant]
Kresse & Hafner, “Ab initio molecular dynamics for liquid metals,” Physical Review B 47(1), pp. 558-561 (1993). [cited by applicant]
Kresse & Hafner, “Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium,” Physical Review B 49(20), pp. 14251-14269 (1994). [cited by applicant]
Kurosu, et al., “Structural characterization of 13C-labeled n-tetracosane adsorbed on the surface of silica gel by high-resolution solid-state 13C NMR spectroscopy,” Journal of Molecular Structure 516(2-3), pp. 177-184 … [cited by applicant]
Lin, et al., “Synthesis-Dependent Atomic Surface Structures of Oxide Nanoparticles,” Physical Review Letters 111(15), 156101, 5 pages (2013). [cited by applicant]
Manner, et al., “Melting of Rodlike Molecules on Pt(111). Infrared Spectroscopic Studies of Isotopically Labeled n-Alkanes,” The Journal of Physical Chemistry B 102(44), pp. 8816-8824 (1998). [cited by applicant]
Marks & Peng, “Nanoparticle shape, thermodynamics and kinetics,” Journal of Physics: Condensed Matter 28(5), 053001, 48 pages (2016). [cited by applicant]
Mastral, et al., “Catalytic degradation of high density polyethylene over nanocrystalline HZSM-5 zeolite,” Polymer Degradation and Stability 91(12), pp. 3330-3338 (2006). [cited by applicant]
Nakaji, et al., “Regioselective hydrogenolysis of alga-derived squalane over silica-supported ruthenium-vanadium catalyst,” Fuel Processing Technology 176, pp. 249-257 (2018). [cited by applicant]
Non-Final Office Action on U.S. Appl. No. 17/018,702 dtd Apr. 7, 2022. [cited by applicant]
Notice of Allowance on U.S. Appl. No. 17/018,702 dtd Jul. 21, 2022. [cited by applicant]
Oya, et al., “Catalytic Production of Branched Small Alkanes from Biohydrocarbons,” ChemSusChem 8(15), pp. 2472-2475 (2015). [cited by applicant]
Rabuffetti, et al., “Synthesis-Dependent First-Order Raman Scattering in SrTiO3 Nanocubes at Room Temperature,” Chemistry of Materials 20(17), pp. 5628-5635 (2008). [cited by applicant]
Rahimi & Garcia, “Chemical recycling of waste plastics for new materials production,” Nature Reviews Chemistry 1, 0046, 11 pages (2017). [cited by applicant]
Tennakoon, et al., “Catalytic upcycling of high-density polyethylene via a processive mechanism,” Nature Catalysis 3, pp. 893-901 (2020). [cited by applicant]
Wong, et al., “Catalytic Cracking of LDPE Dissolved in Benzene Using Nickel-Impregnated Zeolites,” Industrial & Engineering Chemistry Research 55(9), pp. 2543-2555 (2016). [cited by applicant]
Wu, et al., “Formation and Nature of Carbon-Containing Tribofilms,” ACS Applied Materials & Interfaces 11(17), pp. 16139-16146 (2019). [cited by applicant]
Yang & Somorjai, “Adsorption and Reactions of C6 Hydrocarbons at High Pressures on Pt(111) Single-Crystal Surfaces Studied by Sum Frequency Generation Vibrational Spectroscopy: Mechanisms of Isomerization and Dehydrocyc… [cited by applicant]
Zhang, et al., “Adhesion of Pt Nanoparticles Supported on y-Al2O3 Single Crystal,” The Journal of Physical Chemistry C 117(41), pp. 21407-21412 (2013). [cited by applicant]
Zhang, et al., “Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization,” Science 370(6515), pp. 437-441 (2020). [cited by applicant]
Zhuo & Levendis, “Upcycling waste plastics into carbon nanomaterials: A review,” Journal of Applied Polymer Science 131(4), 39931, 14 pages (2014). [cited by applicant]