BioRefinery

서울대학교 화학생물공학부김병기

Petrochemicals and BioRenewables

Currently the non-availability of adequate processes limits the potential of biorenewables

Petrochemicals Production Price

Ethylene 110 M ton/yr 1147.7 $/ton Propylene 75 M ton/yr 1147.7$/ton Benzene 45 M ton/yr 891.8 $/tonGasoline 957.6 $/ton

BioRenewablesCellulose 320 M ton/yr 877.2 $/ton Sugar 143 M ton/yr 438.6 $/tonStarch 60 M ton/yr 409.4 $/tonBio-ethanol 36 M ton/yr 533.6 $/ton L-Glutamic acid 1.5 M ton/yr 1754.4 $/ton

BioEthanol : not for fuel, but for drinking.2nd generation from lignocellulose

Starch & Sugar & Glucose Lignocellulose

Definition of Biorefinery

Status Report Biorefinery 2007, by René van Ree & Bert

Annevelink

Schematic overview general biorefinery principle (Elbersen et al., 2003)

Biorefinery for Renewable Feedstocks to

Fuels,Chemicals, Power, Food, and Feed: after 1st

and 2nd oil shock

Hydrolysis

Lignocellulosics

Lignin

Sugars

Protein

Fuel

Chemical

conversionFermentation

Chemical

conversionProcessing

Electricity

Food

Feed

Furfural

Furans

Glycols

Methyl ethyl ketone

Adipic acid

Ethylene

Propylene

Ethanol Citric acid

Glycerol Fumaric acid

Lipids Lactic acid

Acetone Propionic acid

n-Butanol Succinic acid

Butanediol Itaconic acid

Isopropanol Acetic acid

Butyric acid Acetaldehyde

Phenols

Aromatics

Dibasic acids

Olefins

From C Wyman 1990

Biorefinery Classification System

• Conventional Biorefineries (CBR) • Green Biorefineries (GBR) • Whole Crop Biorefineries (WCBR) • Ligno Cellulosic Feedstock Biorefineries(LCFBR) • Two Platform Concept (TPCBR) Biorefineries• Thermo Chemical Biorefineries (TCBR) • Marine Biorefineries (MBR)

i) Raw material input (i.e. Green Biorefinery, Whole Crop Biorefinery, Ligno Cellulosic Feedstock Biorefinery, Marine Biorefinery)

ii) Type of technology (i.e. Two Platform Concept, Thermo Chemical Biorefinery) iii) Status-of-technology (Conventional and Advanced Biorefineries,

1st and 2nd Generation Biorefineries) iv) main (intermediate) product produced (Syngas Platform, Sugar Platform, Lignin Platform)

Biorefineries From Biomass

Sugars & Glucose

Enzymatic

hydrolysis

Microbial

fermentation

Chemical Feed

Stocks(Bio)Catalysis

Lignocellulose

Lignin

Byproduct

(extraction)

Polymers &

Fine Chemicals

Bio-based Product flow-chart for Biomass Feedstock

-Ethanol

- Glycerol and Other polyols

- Acetone / Isopropanol

- 2,3-butanediol

- Lactic acid

- Citric acid

- Gluconic acid

- Organic acid

- Acetic acid

- PHB and polyhydroxyalkanoic acid

- Amino acid

- Nucleotides

- Extracellular polysacchrarides

- Biosurfactant

Primary metabolism 의 종류

Biofuel의 정의

- 자연계에 있는 바이오매스(Biomass)로부터 만들어지는 지속가능한

너지원을 말한다.

Biofuel의 분류

- Bioethanol, Biobutanol

- Biodiesel

- Biohydrogen

Biofuel의 생산방법 및 산업현황

- Bioethanol

- Biodiesel

- Biohydrogen

12가지 유망 대체 화학물질 (DOE 선정)

3탄당

4탄당

5탄당

6탄당

5탄당HO OH

O

3-Hydroxypropionic

acid

OHOH

OH

Glycerol

OO

HO

3-Hydroxy

butyrolactone

OH

O

O

HO

NH2

Aspartic acid

OH

O

O

OH Succinic acid

OHHO

O

NH2

O

Glutamic acid

OHHO

O

CH2 O

Itaconic acid

CH3HO

O

O

Levulinic acid

HO OH

OH

OH

OH

Xylitol

O

OHHO

O O

2,5 Furandicar-

boxylic acid

HOOH

O

OH

OH

OH

OH

O

Glucaric

acid

HOOH

OH

OH

OH

OH

Sorbitol

구조식 명칭 구조식 명칭

Second-Tier Group 의 12 Chemicals

gluconic acid,

lactic acid,

malonic acid,

propionic acid,

the triacids (citric and aconitic)

xylonic acid,

levoglucosan,

lysine,

serine,

threonine

acetoin,

furfural,

OH

O

NH2

HO

HO

OH

OH

OH

HO

HO

O

HO

O

O

HO

OO

CH3

OH

HO

HO

H2NOH

O

NH2

HO

O

H2N

OH

HO

O

O

O

OH

OH

O

O

HO

HO

O

O

HO

O

OH

OH

O

OH

C1-C4 유기화학 제품 및 생산 공정

Mio = 106

Lactic acid derived C3 chemical monomers

and their reaction mechanisms

Ethyl Lactate: 500,000ton/yr 1.1 bil$,

alkylacrylate: 1800,000 ton/yr 4.0 bil $,

Propyleneglycol: 1500,000ton/yr , 3.3 bil $,

PLA: 160,000 ton/yr, 0.4 bil $

World production size

락틱산과 락틱산에서 유도된 C3 단량체의 종류와 활용분야

Glycerol-based chemicals

Levulinic acid as

platform chemical

Possible reactions with familiar

enzymes

OH

O

O

O

OH

NH2

O

OH

OH

O

OH

NH2

decarboxylase

aminotransferase

dehydrogenase hydrogenation

dehydrogenase

butane2-butanone 2-butanol

dehydration

omega-aminotransferase

sec-butylamine

Succinic acid derived C4 chemical monomers

and their reaction mechanisms

숙신산과 숙신산에서 유도된 C4 단량체의 종류와 활용분야

Expression of n-butanolpathway isozymes from a range of organisms in S. cerevisiae results in n-butanolproduction

Microb Cell Fact. 2008; 7: 36.

-The n-butanol biosynthetic pathway. The enzymes in green are from Clostridium beijerinckii.Enzymes in black are from other organisms: AtoB, Escherichia coli; Erg10, S. cerevisiae; -PhaA, Ralstonia eutropha; -PhaB, Ralstonia eutropha; - Ccr, Streptomyces

-Butanol toxicity to cell membrane

Shota Atsumi, Taizo Hanai & James C. Liao,Vol 451, 3 January 2008, pp. 86-90

HMF derivatized furan compounds and their

reaction mechanism

Paul M Dewick

Understanding of Cell Metabolism and Biosynthesis for Natural Products

1. Acetate Pathway: fatty acids and polyketides

2. Shikimic Pathway: aromatic amino acids and phenylpropanoids

3. Mevalonate and MEP Pathway: Terpenoidsand Steroids

Acetate Pathway: Polyketides

Acetate Pathway: Fatty Acids

Mevalonic aicdMethylerythritol

phosphate

C10

C10

C20

C25

C30

C40

Hemiterpenes(C5)

Monoterpenes (C10)

Sesquiterpenes (C15)

Diterpenes (C20)

Sesterterpenes (C25)

Triterpenoids (C30)

Tetraterpenes (C5)

Carotenoids

Dimethylallyl PP

(DMAPP) (C5)isopentenyl PP

(IPP) (C5)

Steroids (C18-C30)

There are two

pathways to IPP !!

or Methylerythritol

Phosphate(MEP)

pathway

Terpenoids/Carotenoids from

Mevalonate and Methyl erythritol

phosphate Pathways

IPP/DMAPP are formed from 3X Acetyl-CoA

L-Tyr

L-Phe

POLYMERS

LIGANANS LIGNIN

4-hydroxycinnanmyl alcohol

(p-coumaryl alcohol) coniferyl alcohol sinapyl alcohol

Sinapic acid 5-hydroxyferulic

acid

Ferulic acid caffeic acid 4-coumaric acid

(p-coumaric aicd)

Cinnamic acid

NADPH

E2

E3

E1

E4 E5 E6 E5

Phenylpropanoids are formed from

Shikimate Pathway

PAL: Phenylalanine ammonia lyases

TAL: Tyrosine ammonia lyases

C4H: Cinnamate 4-hydrolylase

C3H: p-Coumarate 3-hydrolylase

4CL: 4-Coumarate:CoA ligase

COMT: Caffeate O-methyltransferase

CCOMT: Caffeoyl CoA

O-methyltransferase

CCR: Cinnamoyl Co A reductase

CAD: Cinanmyl alcohol

dehydrogenase

LIGNINSand

LIGNANS

OH

OHO

HO O

OHOMe

OMeOH

OHO

MeO

O

OH

CoAS

MeO

O

OHOMe

OMeOH

OCoAS

CoAS

O

OHOMe

OMeOH

O

MeO

OH

O

H

H

H

CCR

OH

OMeOH

OH

OH

CAD

C3H

COMT

4CL

HO O

C4HPAL

OHOH

OHO CoAS O

OHOH

OMe

OHO

HOOH OH

HO

O

OMe

CoAS

COMT

COMT CCOMT

4CL

4CL

4CL

4CL

CCR

CCR

CAD

CAD

TAL p-Coumaryl

Coniferyl

Sinapyl

NH2

CO2H

CO2H

NH2

OH

MeOOH

OMe

OH

PAL: Phenylalanine ammonia lyases

TAL: Tyrosine ammonia lyases

C4H: Cinnamate 4-hydrolylase

C3H: p-Coumarate 3-hydrolylase

4CL: 4-Coumarate:CoA ligase

COMT: Caffeate O-methyltransferase

CCOMT: Caffeoyl CoA

O-methyltransferase

CCR: Cinnamoyl Co A reductase

CAD: Cinanmyl alcohol

dehydrogenase

LIGNINSand

LIGNANS

OH

OHO

HO O

OHOMe

OMeOH

OHO

MeO

O

OH

CoAS

MeO

O

OHOMe

OMeOH

OCoAS

CoAS

O

OHOMe

OMeOH

O

MeO

OH

O

H

H

H

CCR

OH

OMeOH

OH

OH

CAD

C3H

COMT

4CL

HO O

C4HPAL

OHOH

OHO CoAS O

OHOH

OMe

OHO

HOOH OH

HO

O

OMe

CoAS

COMT

COMT CCOMT

4CL

4CL

4CL

4CL

CCR

CCR

CAD

CAD

TAL p-Coumaryl

Coniferyl

Sinapyl

NH2

CO2H

CO2H

NH2

OH

MeOOH

OMe

OH

LIGNINSand

LIGNANS

OH

OHO

HO O

OHOMe

OMeOH

OHO

MeO

O

OH

CoAS

MeO

O

OHOMe

OMeOH

OCoAS

CoAS

O

OHOMe

OMeOH

O

MeO

OH

O

H

OH

OHO

HO O

OHOMe

OMeOH

OHO

MeO

O

OH

CoAS

MeO

O

OHOMe

OMeOH

OCoAS

CoAS

O

OHOMe

OMeOH

O

MeO

OH

O

H

H

H

CCR

OH

OMeOH

OH

OH

CAD

C3H

COMT

4CL

HO O

C4HPAL

OHOH

OHO CoAS O

OHOH

OMe

OHO

HOOH OH

HO

O

OMe

CoAS

COMT

COMT CCOMT

4CL

4CL

4CL

4CL

CCR

CCR

CAD

CAD

TAL p-Coumaryl

Coniferyl

Sinapyl

NH2

CO2H

NH2

CO2H

CO2H

NH2

OH

CO2H

NH2

OH

MeOOH

OMe

OH

MonolignolMonolignolPathwayPathway

LignificationLignificationPhenylpropanoidPhenylpropanoidPathwayPathway

Phenylpropanoid(PPP) pathway

Application of Phenylpropanoid Pathway

Lignin Degradation and its

monomer modification

Next Generation Projects !!

stem structurestem structure

ligninligninligninligninligninligninextractivesextractives

HO

OH

O

O

OH

OH

OH

HO O

OH

OH

HO

OH

O

OH

OH

OH

OH

O

OH

HO

HO

OH

extractivesextractives

HO

OH

O

O

OH

OH

OH

HO

OH

O

O

OH

OH

OH

HO O

OH

OH

HO

OH

O

OH

OH

OH

OH

O

OH

HO

HO

OH

HO O

OH

OH

HO

OH

O

OH

OH

OH

OH

O

OH

HO

HO

OH

CelluloseCellulose

OH

O

O

O

O

HO

O

OH

O

OH

HO

O

O

OH O

O

O

O

O

O

O

CelluloseCellulose

OH

O

O

O

O

HO

O

OH

O

OH

HO

O

O

OH O

O

O

O

O

O

O

wood fibre

cellwall structure

wood fibre

cellwall structure

fibrilsfibrils

HO

O

oO

HO

O O

OHHO

MeO

COOH

O

O

o

O

O

OH

OH

HOOH

OO

O

HO O C

O o

hemicelluloseshemicelluloses

HO

O

oO

HO

O O

OHHO

MeO

COOH

O

O

o

O

O

OH

OH

HOOH

OO

O

HO O C

O o

HO

O

oO

HO

O O

OHHO

MeO

COOH

O

O

o

O

O

OH

OH

HOOH

OO

O

HO O C

O o

HO

O

oO

HO

O O

OHHO

MeO

COOH

O

O

o

O

O

OH

OH

HOOH

OO

O

HO O C

O o

hemicelluloseshemicelluloses

Annual production of lignocellulosic biomass : approx. 4 x 1010 tons

Structure of wood Biomass

Lignin

Syngas

Methanol/DME

Green biodiesel

H2+CO2

AnaerobicFermentationto liquid fuels

As fuelsWGS

OlefineGreen gasoline

Ethanol, Fuel alcoholHigher value alcohol

chemicals

FT

Pyrolysis Gasification

As biofuels Raw materialsfor

green chemicals

Lignin utilization

FT: Fischer-Tropsch synthesisWGS: water gas shift

An example of a possible lignin structure

Main bonding pattern of lignin:

ether linkage (50 - 60%)

Inter-unit linkages in native lignin

Lignin Degradation Products

Biological Lignin

degradation

Catalytic lignin degradation and transformation

A. Peroxidase – Lignin peroxidase (LiP, glycoprotein, high structural

similarity to Cytochrome C peroxidase), Manganese peroxidase (MnP,

structural similarity with LiP), various LiP or MnP mutants

B. Laccase (oxidizes the phenolic units in lignin to phenoxy radicals

leading to aryl-C cleavage)

C. Glyoxal Oxidase (copper radical oxidase, uses the substrates of

glycoaldehyde produced by the oxidation of β-O-4 model substructure

using lignin peroxidase, structural correlation with galactose oxidase)

D. FAD(Flavin Adenine Dinucleotide) Enzymes - Pyranose 2-oxidase, Aryl

alcohol oxidase, Cellobiose dehydrogenase

E. Auxiliary enzymes – methanol oxidase, 1,4-benzoquinone reductase,

methyltransferase, P450, L-phenylalanine ammonia lyase, 1,2,4-

trihydroxybenzene 1,2-dioxygenase, glutathione transferase,

superoxide dismutase, catalase

Lignin degrading enzymes

Lignin Distribution & Basic Units

Synringyl (=S)Guaiacyl (=G)

OH

OCH

3

OCH

3OHH3C

OOHHydroxyphenyl (=H)

H-CHCHCH2OH

p-coumaryl alcohol

C-H

OH

H2C-OH

C-H

C-H

OH

H2C-OH

C-H

OCH3 OCH3

C-H

OH

H2C-OH

C-H

H3C

O

G-CHCHCH2OH

coniferyl alcohol

S-CHCHCH2OH

sinapyl alcohol

Species Lignin contents

Softwood 25-30 (G)

Hardwood 18-25 ( G, S)

Annual plant 17-24(H, G, S)

Wood pulp production (2007)

Wood pulp type Quantity

Mil. tons %

Chemical pulp

Kraft Unbleached 33.380 18.2

Bleached 96.904 52.7

Sulfite Unbleached 0.958 0.5

Bleached 3.965 2.2

Semi-chemical pulp 9.765 5.3

Mechanical pulp 35.418 19.3

Dissolving pulp 3.345 1.8

Total 183.735 100

FAO Stat

Chemical and semi-chemical pulping

Basic principles

• Principles of chemical pulping processes

– To achieve fiber separation by lignin removal

– To make lignin to become soluble in the cooking liquor

• Two basic principles

– Formation of hydrophilic groups in lignin • Sulfite process : HSO3

-

– Degradation of lignin to low molecular weight fragments• Soda and kraft processes

Kraft vs. Sulfite process

Recent pulping process

• Organosolv process

– Alcell process (Canada)

• Autohydrolysis of wood components in an ethanol and water solution

– Organocell process (Germany)

• Methanol-AQ process

Example of Organosolv process

<표 1. 세가지 다른 리그닌 전처리 분해 공정에 의한 리그닌의 종류

Fig. 1: current lignin treatment process in paper industry

Fig. 2: Future lignin treatment process in biorefinery industry

Carbon black Insectcides Herbicides Pigment

분산제

유화제접착제

첨가제

고분자복합제

페놀모노머

DMSO, 바닐린 페놀 유도체C6C3, C6C2, C6C1

BTX (C6)

Urea-formaldehyde Urethanes Epoxides Isocyanates

Animal feed pellets Laminates Foundry cores

Drill muds Concrete grinding Tanning agent Rubber/vinyl plastic

Soils Road surfaces Asphalts Oil in water

Application of Lignin

Modification

of Lignin

Monomers