Mate Nagy Mate Nagy Georgia Institute of Technology Georgia - PowerPoint PPT Presentation

Catalytic Conversion of Catalytic Conversion of Biomass to Biofuels Biofuels Biomass to “Lignin Hydrogenation Lignin Hydrogenation” ” “ Mate Nagy Mate Nagy Georgia Institute of Technology Georgia Institute of Technology

Overview Overview Fossil fuels vs. Biofuels Biofuels Fossil fuels vs. � � Available raw materials Available raw materials � � Experimental setup Experimental setup � � Black liquor – Black liquor – Model compounds – Model compounds –

The Carbon- -cycle cycle The Carbon Biomass Fossils Closed cycle Broken cycle

Available raw materials Available raw materials • From total annual biomass produced • From total annual biomass produced 9 biosynthetically on Earth: 170 x 10 9 biosynthetically on Earth: 170 x 10 tons: tons: OCH 3 HO OH • Carbohydrates: ~ 70% • Carbohydrates: ~ 70% HO OH HO O • Lignin: ~ 20% • Lignin: ~ 20% OCH 3 H 3 CO HO O O OCH 3 Cellulose Hemicelluloses HO Cellulose Hemicelluloses HO OCH 3 HO OCH 3 HO O O HO OCH 3 Lignin is the second most abundant Lignin is the second most abundant O OCH 3 O OAc Cellulose is the most abundant Cellulose is the most abundant O OAc O O OH AcO HO O OH HO O O OH AcO O-Xylan O HO O OH HO O biopolymer on Earth. Biosphere has an biopolymer on Earth. Biosphere has an OAc O O OAc O OH O O O OH O OH O renewable biomaterial on Earth, with a renewable biomaterial on Earth, with HO a O OH O HO O O HO O H 3 CO O HO O 9 metric tons of lignin HO estimated 300 x 10 9 O estimated 300 x 10 metric tons of lignin O O OCH 3 O HO O OH OH OH O HO HO O OH OH O OCH 3 9 annual biosynthesis rate OH OH 100 x 10 9 100 x 10 annual biosynthesis rate OH HO 9 annual biosynthesis rate with a 20 x 10 9 with a 20 x 10 annual biosynthesis rate OH HO HO O HO O HO OCH 3 O H 3 CO OH HO OH HO O OCH 3 O ≈ DP ≈ DP 90 - 90 - 110 110 OCH 3 O

Differences between biomass based raw Differences between biomass based raw materials and gasoline or diesel materials and gasoline or diesel Gasoline Gas Carbohydrate Lignin Gasoline Gas Carbohydrate Lignin oil/diesel oil/diesel Carbon chain length Carbon chain length 5- 5 -10 10 12 12- -20 20 [6- [6 -5] 5] [9- [9 -10] 10] n n n n O/C molar ratio O/C molar ratio 0 0 0 0 1 1 0.3 0.3- -0.4 0.4 H/C molar ratio H/C molar ratio 1 1- -2 2 ~2 ~2 2 2 0.7- 0.7 -1.1 1.1 Phase behavior Phase behavior liquid liquid liquid liquid solid solid liquid- liquid -solid solid (ambient T) (ambient T) Polarity a- -polar polar a- -polar polar polar a- -polar polar Polarity a a polar a Preferred structure branched/arom linear/saturat linear/cyclic branched Preferred structure branched/arom linear/saturat linear/cyclic branched atic atic ed ed (3D) (3D) /cyclic/unsatur /cyclic/unsatur ated ated

Pulp and Paper Industry Pulp and Paper Industry � Most abundant biopolymers are available in Most abundant biopolymers are available in � the form of lignocellulose lignocellulose matrix matrix “ “wood wood” ”. . the form of � US agriculture and forestry reserves have US agriculture and forestry reserves have � the potential to address at least 30% of the the potential to address at least 30% of the nation’ ’s current petroleum demand. s current petroleum demand. nation US timberland inventory is 21 10 9 9 dry tons, • US timberland inventory is 21 10 dry tons, • 6 tons with an annual production of 368 10 6 tons with an annual production of 368 10 6 tons. and consumption of 142 10 6 tons. and consumption of 142 10 • US Pulp and Paper industry collects and US Pulp and Paper industry collects and • 6 tons processes 108 10 6 tons anually anually. . processes 108 10

Chemical Pulping “ “ Kraft Kraft” ” Chemical Pulping Component Wood Components Kraft Pulp Component Wood Components Kraft Pulp Components Components Pine Birch Pine Birch Pine Birch Pine Birch As a % of Original Wood As a % of Original Wood Cellulose Cellulose 38 38 – 40 40 40 40 – 41 41 35 35 34 34 – – Glucomannan 15 - - 20 2 - - 5 5 1 Glucomannan 15 20 2 5 5 1 Xylan 7 - - 10 25 25 – 30 30 5 16 Xylan 7 10 5 16 – Other carbohydrates 0 - - 5 0 – 4 - - Other carbohydrates 0 5 0 4 - - – Lignin 27 - - 29 20 – 22 2 – 5 1.5 – 3 Lignin 27 29 20 22 2 5 1.5 3 – – – Extraneous Extraneous 4 4 - - 6 6 2 - 2 - 4 4 0.25 0.25 < 0.5 < 0.5 compounds compounds

Catalytic conversion of biomass to Catalytic conversion of biomass to biofuels biofuels Biofuel precursor: Biofuel precursor: ∼ OCH 3 ∼ C 800 – C 900 C – C HO 800 900 OH HO C 9 – C 18 C – C OH HO O 9 18 OCH 3 Cracking Biopolymer Cracking Biopolymer H 3 CO HO Viable Biodiesel Viable Biodiesel O O OCH 3 HO HO OCH 3 or Biogasoline or Biogasoline HO OCH 3 Current Research Activities: Current Research Activities: HO O Component Component O HO - Utilization of conventional - Utilization of conventional OCH 3 O OCH 3 heterogeneous hydrogenation heterogeneous hydrogenation HO OH O OH catalysts catalysts OH H 3 CO O O - Development of homogenous - Development of homogenous O OCH 3 HO OCH 3 OH HO aqueous phase catalysis aqueous phase catalysis OH O HO OCH 3 chemistry for hydrogenation chemistry for hydrogenation HO cleavage of: cleavage of: O OCH 3 O Aryl- Aryl -O O- -Aryl Aryl OCH 3 Aryl- Aryl -O O- -Aliphatic Ethers Aliphatic Ethers O

Selected hydrogenation catalysts Selected hydrogenation catalysts Complexes Non- -water water- -soluble soluble Water- -soluble soluble Complexes Non Water hydrogenation complexes hydrogenation complexes hydrogenation complexes hydrogenation complexes Ruthenium Ruthenium Ru(Cl) Ru(Cl) 2 ( PPh ( PPh 3 ) ) [Ru(Cl) [Ru(Cl) 2 ( TPPMS) ( TPPMS) 2 ] ] 3 2 2 3 3 2 2 2 Ru(H)(Cl)( PPh Ru(H)(Cl)( PPh 3 ) ) Ru(H)(Cl)(TPPMS) Ru(H)(Cl)(TPPMS) 3 3 3 3 3 Ru(H) (PPh ) Ru(H) (TPPMS) Ru(H) 2 (PPh 3 ) Ru(H) 2 (TPPMS) 2 3 3 3 2 3 3 Ru(Cl)(H)(CO)(PPh ) Ru(Cl)(H)(CO)(PPh 3 ) 3 3 3 Rhodium Rhodium RhCl(PPh ) RhCl(TPPMS) RhCl(PPh 3 ) RhCl(TPPMS) 3 3 3 3 3 Other hydrogenation Other hydrogenation Non- Non -water water- -soluble soluble Water Water- -soluble soluble catalysts catalysts Nickel Nickel Raney- -nickel (hetero) nickel (hetero) Raney Platinum Platinum Pt/C (Carbon supp./hetero) Pt/C (Carbon supp./hetero) Palladium Palladium Pd/C(Carbon supp./hetero) Pd/C(Carbon supp./hetero) Ruthenium Ruthenium Ru Ru- -(PVP) (PVP) nanoparticle nanoparticle

Experimental setup Experimental setup 4560 Mini Parr reactor 4560 Mini Parr reactor � � equipped with a 4842 equipped with a 4842 temperature controller. temperature controller. Pressurized with UHP Pressurized with UHP � � Hydrogen gas. Hydrogen gas. Under on- -line controlled line controlled Under on � � time and pressure. time and pressure.

Black Liquor Lignin Hydrogenation Black Liquor Lignin Hydrogenation Extraction Extraction

Black Liquor Lignin Hydrogenation Black Liquor Lignin Hydrogenation OCH 3 TSP HO 1 H H- -NMR: NMR: 1 OH HO OH HO O OCH 3 H 3 CO HO O O OCH 3 HO HO OCH 3 HO OCH 3 HO O O HO OCH 3 12 10 8 6 4 2 0 ppm O OCH 3 DMSO HO OH O OH 13 C C- -NMR: NMR: 13 OH H 3 CO O O O OCH 3 HO OCH 3 OH HO OH O HO OCH 3 HO O O OCH 3 OCH 3 O 180 160 140 120 100 80 60 40 ppm

Modelling the lignin Modelling the lignin polymer polymer OCH 3 H 3 CO HO OH O HO H 3 CO OCH 3 OCH 3 HO OH HO O O O OH OCH 3 O 5- 5 -5 5 α - -O O- -4 4 α H 3 CO HO O O OCH 3 HO H 3 CO OCH 3 HO OCH 3 OCH 3 HO O O O OCH 3 OCH 3 HO HO O O H 3 CO O O O OCH 3 HO HO OCH 3 OCH 3 O O OCH 3 OH HO OH O OH β - β -O O- -4 4 Dibenzodioxocin Dibenzodioxocin 4- -O O- -5 5 4 OH H 3 CO O O O OCH 3 OH HO HO OH OCH 3 OH HO O H 3 CO OH HO OH O HO O OH OH OCH 3 OCH 3 HO O O OCH 3 H 3 CO H 3 CO OCH 3 OCH 3 O O O O OCH 3 β - β -1 1 β - - β β β β - -5 5 O β

Modelling the lignin Modelling the lignin polymer polymer Linkage type Dimer structure Approximate Linkage type Dimer structure Approximate percentage percentage -O O- -4 4 Phenylpropane -aryl ether aryl ether 45- -50 50 β - Phenylpropane β - 45 β β -O O- -4 4 Phenylpropane -aryl ether aryl ether 6- -8 8 α - Phenylpropane α - 6 α α β - -5 5 Phenylcoumaran 9- -12 12 Phenylcoumaran 9 β 5- 5 -5 5 Biphenyl and dibenzodioxocin Biphenyl and dibenzodioxocin 18 18- -25 25 4- 4 -O O- -5 5 Diaryl Diaryl ether ether 4- 4 -8 8 -1 1 β - 1,2- 1,2 -Diaryl propane Diaryl propane 7- 7 -10 10 β - β - β -Linked structures Linked structures 3 β - β - β - 3 β β β

Modelling the lignin Modelling the lignin polymer polymer OCH 3 OCH 3 O O OH HO OCH 3 O OH β - β -O O- -4 4 Phenol, 4 Phenol, 4- -[2 [2- -(2 (2- -methoxyphenoxy)ethyl]) methoxyphenoxy)ethyl])