BioRefinery - KOCWelearning.kocw.net/contents4/document/wcu/2013/Seoul/...Biorefinery for Renewable...
Transcript of BioRefinery - KOCWelearning.kocw.net/contents4/document/wcu/2013/Seoul/...Biorefinery for Renewable...
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
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
-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
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
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
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
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
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
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
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
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
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
Recent pulping process
• Organosolv process
– Alcell process (Canada)
• Autohydrolysis of wood components in an ethanol and water solution
– Organocell process (Germany)
• Methanol-AQ process
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