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Bob Allen, Greg Breyta, Jamie Garcia, Gavin Jones and Jim Hedrick IBM Almaden Research Center July 24, 2018
Polyester Digestion: VOLCAT
IBM Almaden; San Jose, CA
Summit on Realizing the Circular Carbon Economy
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IBM Materials Innovation: Polymer Materials
PET recycling Complex Separations
Materials Innovation AMD
Lithography/Albany COGNOZE
Purification Materials Cognitive Therapeutics
Energy Catalysis/Green
Experiment Computation/Machine Learning IBMTechnology
GrandChallenges
2 Next Gen Battery Antimicrobial Polymers
QBIT Fabrication
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Catalytic Polymer Recycling @ IBM
§ IBM invests in polymer science research to help enable next generation computing
§ Computational chemistry, materials simulation and accelerating materials discovery through AI/Machine Learning augment our experimental work
§ Catalysts have been developed for the creation and breakdown of polymers
§ We’ve developed a molecular sorter technology for r-PET (VOLCAT)
§ We are interested in demanding applications moving these technologies to the next level through partnership
Jim Hedrick
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Recycling of PET (r-PET): Challenges
Mechanical Recycling Chemical Recycling § Chemical Depolymerization
§ Reaction Product (Monomer) Requires Purification for Polymerization
§ Incorporated into Virgin PET Polymerization
§ Sorting, washing (zero contamination tolerance)
§ Only “non-colored” bottles
§ High Temp Processing (T > 250oC)
COST COLOR/Low Quality
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PET
EG
TBD
BHET
Yield~80%Purity:>99%
N N
N H H
O O
O
O O O
O H O
O H H
O O
O O
N H N
N
H O O H O
O
O
n
H O O H
O H O
O H
H
IBM’sOrganocatalyticdepolymerizationofPET
Fukushima, K; Coulembier, O.; Lecuyer, J. M.; Almegren, H. A.; Alabdulrahman, A. M.; Alsewailem, F. D.; McNeil, M. A.; Dubois, P.; Waymouth, R. M.; Horn, H. W.; Rice, J. E.; Hedrick, J.L. “Organocatalytic depolymerization of poly(ethylene terephthalate)” J. Polym. Sci. Part A: Polymer Chem. 2011, DOI: 10.1002/pola.24551.
Jim Hedrick
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PET
EG
TBD
BHET
Yield~80%Purity:>99%
N N
N H H
O O
O
O O O
O H O
O H H
O O
O O
N H N
N
H O O H O
O
O
n
H O O H
O H O
O H
H
IBM’sOrganocatalyticdepolymerizationofPET
Fukushima, K; Coulembier, O.; Lecuyer, J. M.; Almegren, H. A.; Alabdulrahman, A. M.; Alsewailem, F. D.; McNeil, M. A.; Dubois, P.; Waymouth, R. M.; Horn, H. W.; Rice, J. E.; Hedrick, J.L. “Organocatalytic depolymerization of poly(ethylene terephthalate)” J. Polym. Sci. Part A: Polymer Chem. 2011, DOI: 10.1002/pola.24551.
Jim Hedrick
Gen 1 Catalyst: High Activity, Difficult Recovery, $$
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IBM’sPETcatalyticdepolymerizationprocess(Gen2usingDBU)
Heatto190C,addcatalyst
CooltoBelow100CFilter
IsolateBHET(yieldapprox75%)
Solute,tobeRecycled.NegligibleWaste.
NewPETclean
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IBM’sPETcatalyticdepolymerizationprocess(Gen2usingDBU)
Heatto190C,addcatalyst
CooltoBelow100CFilter
IsolateBHET(yieldapprox75%)
Solute,tobeRecycled.NegligibleWaste.
NewPET
DBU Contamination/Loss!!
clean
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Catalyst Evolution
Computational prediction that the use of excess EG leads to a change in the mechanism allows for other types of amines to be used to catalyze PET depolymerization.
N
NH
OR2
R3
OR1
HHO
ONH
OR2
R3
OR1
HHO
O
Alk3Alk1Alk2
N
N
NH H
O
R2 R3
OR1
N
N
NH H
OR2
R3
OR1
HHO
O
Excess EG
DBU &
excess EG
Less activating amine bases
GavinJones
TBD &
excess EG TBD
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Catalyst Evolution
Computational prediction that the use of excess EG leads to a change in the mechanism allows for other types of amines to be used to catalyze PET depolymerization.
N
NH
OR2
R3
OR1
HHO
ONH
OR2
R3
OR1
HHO
O
Alk3Alk1Alk2
N
N
NH H
O
R2 R3
OR1
N
N
NH H
OR2
R3
OR1
HHO
O
Excess EG
DBU &
excess EG
Less activating amine bases
GavinJones
TBD &
excess EG TBD
Volatile Amines? Greg Breyta
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Volcat Technology
• Fast/SelectiveCatalyticProcess,lowtemperature,easycatalystremoval/recovery• KeyAttribute–VOLCATisa“MolecularSorter”
• Minimizesorting,washingandrinsingofflakes• Reduce/eliminatecolorsorting
• Outstandingresultswithdirtyclearandmixed/coloredflakeinputs
PET Waste
BHET Monomer
PET
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§ Distinguishing Features: – Volatile Catalyst is active and easily recovered; – Low Grade Mixed PCR PET input can produce high grade r-PET – Sorted Colored Flake can produce high grade r-PET
§ Economic Outlook: – Lowest Cost Feedstocks and inexpensive catalyst – All chemicals used/recovered (no waste); – Low temperature/fast process
§ Other Advantages: – Potential to reduce / eliminate sorting – Potential to reduce / eliminate washing and rinsing
VOLCAT approach to recycled PET
12
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VOLCAT Process Flow Today – a closed loop (as batch) process
• Complete recovery of catalyst • Complete reuse of EG • Only waste is that which arrived with PCR • Adaptable to Flow Process • Modular input to existing PET polymerization
DECOLOR
FILTER
DISTILLATION COLUMN
CATALYST RECYCLE
DEPOLYMERIZATION REACTOR
METALS REMOVAL
Catalyst recovery
CRYSTAL
FILTER DRY
EG RECYCLE
PET
PET + EG
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Robustprocesstolerantofhighdegreesofcontamination
Unsorted,uncleanedflake;cheapinput-Aconsiderableamountofdirtispresent(~4%)
CleanMixedFlake
AllcoloredFlakefrompost-sorting/cleaningCheapestinput–littlecommercialuse
DirtyMixedFlake
Worstoftheworst.“Curbsidepickup”-Largeamount(~8%)of“dirt”ispresent;cheapestinput
PET/Nylon&PET/PVCflakesample
- PETflakewith3wt%Nylon- PETflakewith3&0.1wt%PVC(NURRC+Aldrich)
DirtyMixedFlake
14
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VolCatProcesswithCleanColorFlake
TheVOLCATproductfilteredtoremovethissmallamountof“bluestuff”(&someflake)
TogivethisturbidsolutionTOWHICHcarbonwasadded
Filtrationofcarbon(left)toIXTreatmentflask
Solutionafterpost-IXfiltration.Faintlyblue,lefttocrystallize
Toproducethis!!–Filtrationnext.
Fromreactor
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VolCatProcessedColoredFlake(5kg)
All inputs provide similar results
BHET Product (polymerization grade)
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FiltrationStepComparison
DirtyMixed2.1g(4.2%)
CleanColored0.05g(0.5%)
CurbsideDirtyMixed3.6g(7.2%)
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BHET polymerization to PET*: Polymer Characterization
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BHET Monomer Source Transparency (L*) Color (b*)
Virgin PET (from TPA/EG) 93 2.3 Virgin PET; Glycolysis (re-polymerized) 87 8.0
VOLCAT BHET (clean, clear flake) 93 2.1 VOLCAT BHET (dirty clear) 92 5.9 VOLCAT BHET (colored flake) 92 5.6 VOLCAT BHET (curbside, dirty) 92 4.5
* Performed by DAK Americas, an Alpek Polyester Business
- EG
Any/all feeds can be “VOLCAT-ed” to produce bottle grade BHET (50%)
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PET Waste
BHET Monomer
PET
PET Chemical Recycling via VOLCAT Feedstock Insensitivity
Process Scalability? Process Economics? New Materials?
High Monomer Purity
High Polymer Purity
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PET Waste
BHET Monomer
PET
PET Chemical Upcycling via VOLCAT
Feedstock Insensitivity
Process Scalability? Process Economics? New Materials?
High Monomer Purity
High Polymer Purity PET-derived AMIDE Monomers
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Catalytic Polymer Recycling @ IBM: Other Processes
§ PHT Thermosets: Depolymerization at low pH
§ Conversion of Poly(carbonate) to Poly(ether sulfone)
Jeannette Garcia
O O O
O
Me Me
H
n
SO O
F F
CHP, K2CO3, 190 °C, 18 hone-pot O O
Me Me
H
-CO2
S
OHn
O O
poly(BPA carbonate)Mn ~12,000 Da
poly(aryl ether sulfone)Mn ~11,000 Da
OH
Me Me