Lignin valorization to chemicals - energy.gov · Lignin valorization to chemicals. 2 ... centric...
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National Renewable Energy Laboratory National Bioenergy Center Gregg T. Beckham Bioeconomy 2017 July 12, 2017 Lignin valorization to chemicals
Transcript of Lignin valorization to chemicals - energy.gov · Lignin valorization to chemicals. 2 ... centric...
National Renewable Energy LaboratoryNational Bioenergy Center
Gregg T. BeckhamBioeconomy 2017July 12, 2017
Lignin valorization to chemicals
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Lignin from 2G biorefineries will be quite abundant
At a high capacity factor, each plant could process up to 400 tons/day of lignin
Lignin can offer economic and sustainability value to biorefineries
3
-60!
-50!
-40!
-30!
-20!
-10!
0!
10!
0! 0.25! 0.5! 0.75! 1!
GHG
Em
issi
ons
(kg
CO2-
eq./G
GE)!
Lignin conversion to product!
$0.00 !
$1.00 !
$2.00 !
$3.00 !
$4.00 !
$5.00 !
$6.00 !
0%! 20%! 40%! 60%! 80%! 100%!Min
imum
Fue
l Sel
ling
Pric
e ($
/GG
E)!
Lignin conversion to product!
R. Davis, M.J. Biddy, et al., 2013
Lignocellulosic Biomass
O
O
HOOH
Adipic acid
Lignin-Platform Chemicals
Lignin Depoly-merization
Microbial Fermentation
Separations
Catalytic Hydrogenation
RENEWABLE MUCONIC & ADIPIC ACID
Saccharides
OHOHO
OHOH
OH
Glucose
OHOHO
OHOH
Xylose
Pretreatment- Fractionation
Muconic acid
O
OHO
HO
Vardon et al., EES 2015
Lignin valorization is essential for biochemical conversion
4
R. Davis, M.J. Biddy, et al., 2013
Native lignin structure (monocot)
5
Image from E.M. Anderson et al., ACS SusChemEng 2016
Lignin Hemicellulose
Multiple bond types, multiple monomer types- Common polysaccharide-centric treatments break labile C-O linkages and form more
recalcitrant C-C linked structures- More than a century of research in lignin depolymerization
Heterogeneity is the main barrier for lignin upgrading to chemicals
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?"HO
OO
OH
OHO
Oββ
γγ
αα OHO
55
44HO
HO
O
HO
OHO
O
O
O
αα
HOββ
γγHO
O 44
O
OHO Lignin
HO
OO
ββ γγ
OH
αα
OO
OH
HO
OOH
HOO
O
O
OH
O
OH
O OH
O
OHO
HO
OHO
OH OHO
O
OO
OH
OOHOH
OLignin
O
OHO
Deconstruction
OH
OH
OH
OHH3C
OH
OHH3C
OHOCH3
O CH3
H3CO
O
CH3
OCH3HO
OHOH
OHCH3
OH
OHOCH3
OHOCH3
CH3
O
OHOCH3 OH
OH
H3C
H3C
OHOCH3
O
O
HO
OHOCH3H3CO
HO
OH
CH3
CH3CH3
CH3
OH
CH3Deconstruction
Thermal, catalytic, enzymatic
HO
OO
OH
OHO
Oββ
γγ
αα OHO
55
44HO
HO
O
HO
OHO
O
O
O
αα
HOββ
γγHO
O 44
O
OHO Lignin
HO
OO
ββ γγ
OH
αα
OO
OH
HO
OOH
HOO
O
O
OH
O
OH
O OH
O
OHO
HO
OHO
OH OHO
O
OO
OH
OOHOH
OLignin
O
OHO
Deconstruction
OH
OH
OH
OHH3C
OH
OHH3C
OHOCH3
O CH3
H3CO
O
CH3
OCH3HO
OHOH
OHCH3
OH
OHOCH3
OHOCH3
CH3
O
OHOCH3 OH
OH
H3C
H3C
OHOCH3
O
O
HO
OHOCH3H3CO
HO
OH
CH3
CH3CH3
CH3
OH
CH3
Lignin’s Alkyl Aromatic Structure Depolymerization Product Slate
There is a world of difference between a valuable mixture of chemicals and a mixture of valuable chemicals (Art Power)- Overcoming lignin heterogeneity is the key problem in lignin valorization to chemicals
Emerging routes to overcome lignin heterogeneity: Engineering plants
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Lignin biosynthesis is plastic and can be successfully manipulated- The C-lignin discovery highlights that native lignin polymers remain to be discovered- Work in model systems can be transitioned to energy crops via emerging genome editing
Rick Dixon et al.
John Ralph et al.Clint Chapple et al.
Image from Ragauskus et al. Science 2014
Emerging routes to overcome lignin heterogeneity: Plant diversity
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Lignin in many species can be quite diverse
Image from Studer et al. PNAS 2011
Emerging routes to overcome lignin heterogeneity: Biological funneling
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Biological funneling enables metabolism of heterogeneous aromatics
Microorganisms have evolved aromatic-catabolizing pathways Diverse battery of native enzymes to “funnel” lignin aromatics to central metabolism
OH
OH
OH
OH
O
O
OH
COO-
O
-OOC
O COO-COO-
OH
COO-
O
?"HO
OO
OH
OHO
Oββ
γγ
αα OHO
55
44HO
HO
O
HO
OHO
O
O
O
αα
HOββ
γγHO
O 44
O
OHO Lignin
HO
OO
ββ γγ
OH
αα
OO
OH
HO
OOH
HOO
O
O
OH
O
OH
O OH
O
OHO
HO
OHO
OH OHO
O
OO
OH
OOHOH
OLignin
O
OHO
Deconstruction
OH
OH
OH
OHH3C
OH
OHH3C
OHOCH3
O CH3
H3CO
O
CH3
OCH3HO
OHOH
OHCH3
OH
OHOCH3
OHOCH3
CH3
O
OHOCH3 OH
OH
H3C
H3C
OHOCH3
O
O
HO
OHOCH3H3CO
HO
OH
CH3
CH3CH3
CH3
OH
CH3
Lignin Depolymerization Product Slate
COO-
COO-COO-
COO-
-OOC
to TCA-cycle…
Catechol Protocatechuate
intra-diol extra-diol intra-diol extra-diol
β-KETOADIPATE PATHWAY
O
OMe
O
O
Me
HCOO-!
2H2O!
+!
cis,cis-muconate
β-ketoadipate O
OMe
O
O
Me
HCOO-!
2H2O!
+!
“Upper Pathways”
“Upper Pathways”
Microbes can funnel lignin-derived aromatics to central metabolismSignificant body of work going into process development around this concept to optimize biocatalysts, biological cultivation processes, separations, and chemical catalysis
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Biopolymer production from lignin
11Linger, Vardon, Guarnieri, Karp, et al. Proc. Natl. Acad. Sci., 2014
0
20
40
60
80
100
Hydroxy acids
Com
posi
tion
(wt.%
)
HA6 HA14
HA-12
HA-10
HA-8
MWw 124 kDa PDI 1.93 Tg Tm Td 259°C
50°C -47°C
Lignin Liquor Stream Poly-saccharide
Stream Biological Funneling
Ferulic acid
Upper Pathways
p-Coumaric acid
Protocatechuic acid
β-ketoadipic acid
β-KA Pathway
Vanillic acid
Acetyl-CoA
Lignocellulosic Biomass
Alkaline Pretreatment
Biological/Catalytic
Upgrading
Polyhydroxyacid (PHA)
Depolymerization Depoly-Deoxy
Hydroxyacid monomers Hydrocarbons
Direct Use
Renewable Chemicals, Materials, & Fuels
PHA Valorization
Alkaline Pretreatment Black Liquor
Enzymatic/ Catalytic Depolym.
Hydroxy-methylfurfural
Recovered Solids
HO
O
OHHO
O
OHMeO
O COOHCOOH
OH
OHCOOH
O
SCoA
O
O
R
O
OH
R
HO
OHOHO
OHOH
OH
Glucose OHO
HOOHOH
Xylose
OOHO
OHOHO OH
OH
Arabinose
HO
O
OHMeO
Atom-efficient intermediates from lignin
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OH
OH
COO-
HO OH
COO-
COO--OOC
COO--OOC
O
O
-OOCCOO-
OH
COO-
OH
COO-
COO-
OH
COO-
COO-
O
COO-
OH
COO-
OHO
COO-
-OOC OH
O
-OOC COO-
OH
O
-OOC COO-
O
COO-OH
-OOC COO-
COO-O
-OOC COO-
COO-O
-OOC COO-
OH
Pyruvate +Oxaloacetate
2 Pyruvate
COO-
COO-
COO-
O
O
COO-
O
O
COO-
COO-O
COO-
COSCoAO
Succinate +Acetyl-CoA
O
O
Pyruvate +Acetaldehyde
Pyruvate + Acetyl-CoA
LigAB
LigC
LigI
LigU
LigJ
LigK
LigK
PcaHG
PcaB
PcaC
PcaD
PcaIJ
PcaF
PraA
PraH
XylG
XylH
XylI
XylJ
XylK
XylQ
spont.
CatA
CatB
CatC
XylEProtocatechuate Catechol
AroY
COO-
O
CHOOH
XylF
O
OH
O
-O
OH
O
-O
Ferulate p-Coumarate
Vanillate
O
-O
4-Hydroxybenzoate
OH
O
-O
Benzoate
OH
O
-OO
O
OH
GuaiacolPhenolOH
O
COO-
OHHO
OH
GallateDesB / LigAB
COO-
OHO
OH
LigM
COO-
OO
OH
DesA
COO-
O HO COO-O
LigAB / DesZ
DesZ
spont.
?
PobAVanAB ?Dmp
O
-O
O
O-
TPA
BsdBCD
Fcs
Ech
Vdh
Fcs
Ech
Vdh
PHA2
BenABCBenD
GuaiacylLignin
SyringylLignin
TCAcycle
O
HO
O
OOH
HO
O
O
O
HO
HO
O
O
O
O
O
OH
OH
HO
OH
OH
HO
O
OH
O
OH
O
OH
O
O
HO O
O
HO
OH
O
HO
O
HO
O
O
HO
O OH
OHO
O
OHO
OH
OH
HO
OO
O
O
OH
OH
OH
O
O
O
O
O
O
O
OH
OH
OHOH
HO
OH
O
O
OH
HO
OHOH
OHOH
OH
O
O
OH
HO
OH
O
O
OH
OH
COO-
HO OH
COO-
COO--OOC
COO--OOC
O
O
-OOCCOO-
OH
COO-
OH
COO-
COO-
OH
COO-
COO-
O
COO-
OH
COO-
OHO
COO-
-OOC OH
O
-OOC COO-
OH
O
-OOC COO-
O
COO-OH
-OOC COO-
COO-O
-OOC COO-
COO-O
-OOC COO-
OH
Pyruvate +Oxaloacetate
2 Pyruvate
COO-
COO-
COO-
O
O
COO-
O
O
COO-
COO-O
COO-
COSCoAO
Succinate +Acetyl-CoA
O
O
Pyruvate +Acetaldehyde
Pyruvate + Acetyl-CoA
LigAB
LigC
LigI
LigU
LigJ
LigK
LigK
PcaHG
PcaB
PcaC
PcaD
PcaIJ
PcaF
PraA
PraH
XylG
XylH
XylI
XylJ
XylK
XylQ
spont.
CatA
CatB
CatC
XylEProtocatechuate Catechol
AroY
COO-
O
CHOOH
XylF
O
OH
O
-O
OH
O
-O
Ferulate p-Coumarate
Vanillate
O
-O
4-Hydroxybenzoate
OH
O
-O
Benzoate
OH
O
-OO
O
OH
GuaiacolPhenolOH
O
COO-
OHHO
OH
GallateDesB / LigAB
COO-
OHO
OH
LigM
COO-
OO
OH
DesA
COO-
O HO COO-O
LigAB / DesZ
DesZ
spont.
?
PobAVanAB ?Dmp
O
-O
O
O-
TPA
BsdBCD
Fcs
Ech
Vdh
Fcs
Ech
Vdh
PHA2
BenABCBenD
GuaiacylLignin
SyringylLignin
TCAcycle
O
HO
O
OOH
HO
O
O
O
HO
HO
O
O
O
O
O
OH
OH
HO
OH
OH
HO
O
OH
O
OH
O
OH
O
O
HO O
O
HO
OH
O
HO
O
HO
O
O
HO
O OH
OHO
O
OHO
OH
OH
HO
OO
O
O
OH
OH
OH
O
O
O
O
O
O
O
OH
OH
OHOH
HO
OH
O
O
OH
HO
OHOH
OHOH
OH
O
O
OH
HO
OH
O
O
Muconic Acid
Titer ~ 30-48 g/LRate ~ 0.4-0.6 g/L/hrYield ~ 100%
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Towards selective lignin valorization
Biological funneling (along with other emerging techniques) may enable a solution to overcome lignin heterogeneity- Significant opportunity in co-designing in planta lignin with biological and catalytic conversion- Emerging 2G biorefineries offer space for new lignin valorization processes
Biological Valorization of Lignin to Chemicals
Biomass
Lignin Deconstruction
Microbial Conversion
Separations Catalysis & Polymerization
Beckham, Johnson, Karp, Salvachua, Vardon, Current Opinion in Biotechnology, 2016
Conference announcement!
For your calendars!
The inaugural Lignin Gordon Research Conference will be held in the August 5-10, 2018
The goal of this proposed GRC on lignin is to bring together leading researchers, postdocs, and students involved in multiple aspects of lignin including its characterization, in planta engineering, depolymerization and upgrading, and material science.
Interaction and discussion between plant researchers, chemists, engineers, and material scientists working on this recalcitrant polymer is critical to move the field forward.
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Collaborators:• John McGeehan, Portsmouth • Linda Broadbelt, Keith Tyo, Northwestern • Ellen Neidle, UGA • Adam Guss, ORNL• Yuriy Román-Leshkov, MIT • Lindsay Eltis, Bill Mohn, UBC• John Dorgan, MSU • Rick Dixon, Fang Chen, UNT• Sam Purvine, Erika Zink, EMSL • M. Sandgren, Jerry Ståhlberg, SLU’• Jen DuBois, Montana State
Acknowledgements
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Thank you for your attention!
