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

SLIDE 1

Catalytic Conversion of Catalytic Conversion of Biomass to Biomass to Biofuels Biofuels

“ “Lignin Hydrogenation Lignin Hydrogenation” ”

Mate Nagy Mate Nagy

Georgia Institute of Technology Georgia Institute of Technology

SLIDE 2

Overview Overview

• Fossil fuels vs.

Fossil fuels vs. Biofuels Biofuels

• Available raw materials

Available raw materials

• Experimental setup

Experimental setup

– – Black liquor

Black liquor

– – Model compounds

Model compounds

SLIDE 3

The Carbon The Carbon-

• cycle

cycle

Broken cycle Closed cycle Fossils Biomass

SLIDE 4

Available raw materials Available raw materials

O O O OAc O O HO OAc O HO O O O AcO OH O-Xylan O O HO OAc O O AcO OAc O O HO HO O HO O HO HO OH HO O O HO OH O O O H3CO OH OH OH

Hemicelluloses Hemicelluloses

O O HO OH O O HO OH OH OH O HO OH O O HO OH O OH OH O

Cellulose Cellulose

Cellulose is the most abundant Cellulose is the most abundant renewable biomaterial on Earth, with renewable biomaterial on Earth, with a a 100 x 10 100 x 109

9 annual biosynthesis rate

annual biosynthesis rate Lignin is the second most abundant Lignin is the second most abundant biopolymer on Earth. Biosphere has an biopolymer on Earth. Biosphere has an estimated 300 x 10 estimated 300 x 109

9 metric tons of lignin

metric tons of lignin with a 20 x 10 with a 20 x 109

9 annual biosynthesis rate

annual biosynthesis rate

OH OH OCH3 HO OCH3 O HO HO H3CO O HO HO OCH3 O HO OCH3 O HO OH O O H3CO HO HO O OH OH OCH3 OCH3 OH OH O OCH3 O O OCH3 O OCH3 HO HO OCH3 O O OCH3 HO O HO HO OCH3

DP DP ≈ ≈ 90 90 -

• 110

110

• From total annual biomass produced

From total annual biomass produced biosynthetically on Earth: 170 x 10 biosynthetically on Earth: 170 x 109

9

tons: tons:

• Carbohydrates: ~ 70%

Carbohydrates: ~ 70%

• Lignin: ~ 20%

Lignin: ~ 20%

SLIDE 5

Differences between biomass based raw Differences between biomass based raw materials and gasoline or diesel materials and gasoline or diesel

Gasoline Gasoline Gas Gas

• il/diesel
• il/diesel

Carbohydrate Carbohydrate Lignin Lignin Carbon chain length Carbon chain length

5 5-

• 10

10 12 12-

• 20

20 [6 [6-

• 5]

5]

n n

[9 [9-

• 10]

10]n

n

O/C molar ratio O/C molar ratio

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 (ambient T) (ambient T)

liquid liquid liquid liquid solid solid liquid liquid-

• solid

solid

Polarity Polarity

a a-

• polar

polar a a-

• polar

polar polar polar a a-

• polar

polar

Preferred structure Preferred structure

branched/arom branched/arom atic atic /cyclic/unsatur /cyclic/unsatur ated ated linear/saturat linear/saturat ed ed linear/cyclic linear/cyclic branched branched (3D) (3D)

SLIDE 6

Pulp and Paper Industry Pulp and Paper Industry

• Most abundant biopolymers are available in

Most abundant biopolymers are available in the form of the form of lignocellulose lignocellulose matrix matrix “ “wood wood” ”. .

• 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 nation’ ’s current petroleum demand. s current petroleum demand.

• US timberland inventory is 21 10

US timberland inventory is 21 109

9 dry tons,

dry tons, with an annual production of 368 10 with an annual production of 368 106

6 tons

tons and consumption of 142 10 and consumption of 142 106

6 tons.

tons.

• US Pulp and Paper industry collects and

US Pulp and Paper industry collects and processes 108 10 processes 108 106

6 tons

tons anually anually. .

SLIDE 7

Chemical Pulping Chemical Pulping “ “Kraft Kraft” ”

Component Component Wood Components Wood Components Kraft Pulp 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 Glucomannan 15 15 -

• 20

20 2 2 -

• 5

5 5 5 1 1 Xylan Xylan 7 7 -

• 10

10 25 25 – – 30 30 5 5 16 16 Other carbohydrates Other carbohydrates 0 -

• 5

5 0 – – 4 4

• Lignin

Lignin 27 27 -

• 29

29 20 20 – – 22 22 2 2 – – 5 5 1.5 1.5 – – 3 3 Extraneous Extraneous compounds compounds 4 4 -

• 6

6 2 2 -

• 4

4 0.25 0.25 < 0.5 < 0.5

SLIDE 8

Catalytic conversion of biomass to Catalytic conversion of biomass to biofuels biofuels

Biofuel Biofuel precursor: precursor:

OH OH OCH3 HO OCH3 O HO HO H3CO O HO HO OCH3 O HO OCH3 O HO OH O O H3CO HO HO O OH OH OCH3 OCH3 OH OH O OCH3 O O OCH3 O OCH3 HO HO OCH3 O O OCH3 HO O HO HO OCH3

C C9

9

– – C C18

18

∼ ∼ C C800

800

– – C C900

900

Cracking Biopolymer Cracking Biopolymer Viable Viable Biodiesel Biodiesel

• r
• r Biogasoline

Biogasoline Component Component Current Research Activities: Current Research Activities:

• Utilization of conventional

Utilization of conventional heterogeneous hydrogenation heterogeneous hydrogenation catalysts catalysts

• Development of homogenous

Development of homogenous aqueous phase catalysis aqueous phase catalysis chemistry for hydrogenation chemistry for hydrogenation cleavage of: cleavage of: Aryl Aryl-

• O

O-

• Aryl

Aryl Aryl Aryl-

• O

O-

• Aliphatic Ethers

Aliphatic Ethers

SLIDE 9

Selected hydrogenation catalysts Selected hydrogenation catalysts

Complexes Complexes Non Non-

• water

water-

• soluble

soluble hydrogenation complexes hydrogenation complexes Water Water-

• soluble

soluble hydrogenation complexes hydrogenation complexes

Ruthenium Ruthenium Ru(Cl) Ru(Cl)

2 2 ( PPh

( PPh

3 3 )

)

3 3

[Ru(Cl) [Ru(Cl)

2 2 ( TPPMS)

( TPPMS)

2 2 ]

]

2 2

Ru(H)(Cl)( PPh Ru(H)(Cl)( PPh

3 3 )

)

3 3

Ru(H)(Cl)(TPPMS) Ru(H)(Cl)(TPPMS)

3 3

Ru(H) Ru(H)

2 2 (PPh

(PPh

3 3 )

)

3 3

Ru(H) Ru(H)

2 2 (TPPMS)

(TPPMS)

3 3

Ru(Cl)(H)(CO)(PPh Ru(Cl)(H)(CO)(PPh

3 3 )

)

3 3

Rhodium Rhodium RhCl(PPh RhCl(PPh

3 3 )

)

3 3

RhCl(TPPMS) RhCl(TPPMS)

3 3

Other hydrogenation Other hydrogenation catalysts catalysts Non Non-

• water

water-

• soluble

soluble Water Water-

• soluble

soluble

Nickel Nickel Raney Raney-

• nickel (hetero)

nickel (hetero) 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

SLIDE 10

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

Under on-

• line controlled

line controlled time and pressure. time and pressure.

SLIDE 11

Black Liquor Lignin Hydrogenation Black Liquor Lignin Hydrogenation

Extraction Extraction

SLIDE 12

Black Liquor Lignin Hydrogenation Black Liquor Lignin Hydrogenation

180 160 140 120 100 80 60 40 ppm DMSO

12 10 8 6 4 2 0 ppm TSP

OH OH OCH3 HO OCH3 O HO HO H3CO O HO HO OCH3 O HO OCH3 O HO OH O O H3CO HO HO O OH OH OCH3 OCH3 OH OH O OCH3 O O OCH3 O OCH3 HO HO OCH3 O O OCH3 HO O HO HO OCH3

1 1H

H-

• NMR:

NMR:

13 13C

C-

• NMR:

NMR:

SLIDE 13

Modelling the lignin Modelling the lignin polymer polymer

H3CO O O OCH3 HO O OH O OCH3 OCH3

β β-

• O

O-

• 4

4

HO OH O O OCH3 H3CO

α α-

• O

O-

• 4

4

O H3CO O OCH3

5 5-

• 5

5 4 4-

• O

O-

• 5

5 β β-

• 5

5

O OCH3 H3CO O OH

β β-

• 1

1

O OCH3 HO HO H3CO O OH OH OH OH O O OCH3 H3CO

β β-

• β

β Dibenzodioxocin Dibenzodioxocin

O H3CO O HO OCH3 O OCH3

OH OH OCH3 HO OCH3 O HO HO H3CO O HO HO OCH3 O HO OCH3 O HO OH O O H3CO HO HO O OH OH OCH3 OCH3 OH OH O OCH3 O O OCH3 O OCH3 HO HO OCH3 O O OCH3 HO O HO HO OCH3

SLIDE 14

Modelling the lignin Modelling the lignin polymer polymer

Linkage type Linkage type Dimer Dimer structure structure Approximate Approximate percentage percentage

β β-

• O

O-

• 4

4 Phenylpropane Phenylpropane β β-

• aryl ether

aryl ether 45 45-

• 50

50 α α-

• O

O-

• 4

4 Phenylpropane Phenylpropane α α-

• aryl ether

aryl ether 6 6-

• 8

8 β β-

• 5

5 Phenylcoumaran Phenylcoumaran 9 9-

• 12

12 5 5-

• 5

5 Biphenyl and Biphenyl and dibenzodioxocin dibenzodioxocin 18 18-

• 25

25 4 4-

• O

O-

• 5

5 Diaryl Diaryl ether ether 4 4-

• 8

8 β β-

• 1

1 1,2 1,2-

• Diaryl propane

Diaryl propane 7 7-

• 10

10 β β-

• β

β β β-

• β

β-

• Linked structures

Linked structures 3 3

SLIDE 15

Modelling the lignin Modelling the lignin polymer polymer

O OCH3 O OCH3 HO OH

Phenol, 4 Phenol, 4-

• [2

[2-

• (2

(2-

• methoxyphenoxy)ethyl])

methoxyphenoxy)ethyl])

O OCH3 OH

β β-

• O

O-

• 4

4

SLIDE 16

( (β β-

• O

O-

• 4)

4)-

• model compound

model compound hydrogenation hydrogenation

ppm (t1) 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 10000 20000 30000 40000 ppm (t1) 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 50000 10000 15000 20000 25000

1 1H

H-

• NMR:

NMR:

Blank Blank-

• run

run RaneNi RaneNi

SLIDE 17

( (β β-

• O

O-

• 4)

4)-

• model compound

model compound hydrogenation hydrogenation

O HO OMe O HO OMe O HO OMe HO HO

MeO HO

SLIDE 18

Acknowledgments Acknowledgments

Art Art Ragauskas Ragauskas

Georgia Institute of Technology Georgia Institute of Technology

George George Britovsek Britovsek

Imperial College of London Imperial College of London

SLIDE 19

Questions: Questions Questions: :