Lignin Production and Conversion Technologies
Arvind LaliAruna N, Prathamesh Wadekar, Mallikarjun Patil,
Parmeshawar Patil, Nikhil Asodekar; Suveera Bellary
DBT-ICT Centre for Energy BiosciencesInstitute of Chemical Technology (formerly UDCT)
Mumbai, INDIA [email protected]
Mumbai
INDIA
Institute of Chemical Technology(formerly UDCT)
at Matunga (Central Suburb)
DBT-ICT Centre for Energy BiosciencesMatunga, Mumbai
DBT-ICT Centre of Energy Biosciences(Sanctioned Dec 2007; Functional May 2009)
- India’s first National Bioenergy Research Centre
- Set up at a cumulative cost of about 15 million USD
- Multidisciplinary State-of-the-Art facility with emphasis on developing cutting-edge science and translation to commercially viable technologies
- Networked with Institutions & Industry in India and abroad
>50 PhD scholars; >10 Senior Research Scientistsin different disciplines of modern biological sciences and chemicalengineering/technology
Centre’s Overall RDD&D Objectives
Development, Demonstration and TransferCost effective and Sustainable Biomass to Biofuel technologies
Building capacity in the field of Industrial Biotechnology
Capacity & Infra Building
HR GenerationTechnology
Development Technology
Deployment
Sustainable Platform Technologies
Waste
Utilizable Carbon
Smart Chemical/Biotech
Conversion Technologies
Food/Feed/Energy/Materials & Chemicals
400
400
Biomass
Syn-Gas
Platform Chemicals
Hydrocarbons
Gasoline, Diesel
Fermentation/Chemical Catalysis FT Synthesis
Cracking
Bio-Oil
Hydrocarbons &
Chemicals
Catalysis
Fast Pyrolysis/SCWG
Gasification
FermentableSugars
Platform Chemicals
Digestion
Biogas/BioCNG
BioFuels
Hydrocarbons
Combustion
Power
Biomass to Renewables: Technology Options
Biomass
Syn-Gas
Platform Chemicals
Hydrocarbons
Gasoline, Diesel
Fermentation/Chemical Catalysis FT Synthesis
Cracking
Bio-Oil
Hydrocarbons &
Chemicals
Catalysis
Fast Pyrolysis/SCWG
Gasification
FermentableSugars
Platform Chemicals
Digestion
Biogas/BioCNG
BioFuels
Hydrocarbons
Combustion
Power
Biomass to Renewables: Technology Options
Preferred TechnologyPlatform
Lignocellulosic Biomass
Pre-Treatment Step
Saccharification
Fermentation
Separation/PurificationBiofuel
TYP
ICA
L P
RO
CES
S O
UTL
INE
STEP 1
STEP 2
STEP 3
STEP 4
LIGNIN
Kraft and
Lignosulfonate
Process
Biomass Fractionation
Enzyme
hydrolysis of
carbohydrates
Fermentation
to ethanol
Lignin to
Boiler Does it deserve more than just burning
BiomassPaper and
pulp
Typical 2G-Bioethanol and Pulping Process
Routes to Lignin Utilization
Lignin
Used in As-Derived form for integrating into
More complex Polymeric structurese.g. formulating resins; as polymeric filler
Break-down partially or fully
Reconstruct Products through
Biological or Chemicaltechnologies
Routes to Lignin Utilization
Lignin
Used in As-Derived form for integrating into
More complex Polymeric structurese.g. formulating resins; as polymeric filler
Break-down partially or fully
Reconstruct Products through
Biological or Chemicaltechnologies
Attempted with Limited successes
Way to go for Better value
Next Generation Lignin Technologies
Lignin Isolation & Deconstruction technologiesLignin Depolymerization Polishing
Conversion technologiesLignin monomers Conversion Products
Biological Methods and Chemical Methods
Part 1Lignin Isolation and
Deconstruction TechnologiesChemical and Biological
Lignin : A Polymeric structure closely linked withItself, Cellulose and Hemicellulose
Lignin-Carbohydrate bonding
Linkage type % of total linkage
Softwood Hardwood
β-O-4 50 60
4-O-5 4 7
β-5 9-12 6
5-5 10-11 5
β-1 7 7
β-β 2 3
Wood type Coniferyl alcohol Sinapyl alcohol p-coumarylalcohol
Softwood 75% 20% 5%
Hardwood 50% 40% 10%
Lignin Intra-Bonding
20
2G Biofuels: Lignin Production Technologies
Process Lignin Recovery MethodTypical Conditions
Pulping based Lignin Production Technologies
Lignin Properties
Dilute acid MW 5000 10000 DaSulphur content – 0 – 1.0 % (dilute Sulphuric acid process)Condensed structure
Alkali MW 2700 -6000 DaSulphur free processAccounts for nearly 5% of the total pulp production
Steam explosion(softwood)
MW 2500-11000 Da (lignin obtained from softwood)No Sulphur contentCondensed structure, lower methoxy but higher hydroxyl group
AFEX MW 5000DaNo Sulphur contentThe method cannot be used for >25% lignin content biomass
Klason MW 8000 – 9000 DaSulphur content – 4-5%Condensed structure
Organosolve (Alcell process)
MW 3300 Da (Lignin obtained from hardwood)Sulphur free and less condensed structure
Kraft Process MW 6000-10000Da1.5–3 wt% Sulphur contentDominant pulping process in world
Lignosulfonate MW 12000Da-65000 Da4–8% Sulphur content (so higher mol wt) 10% of pulp is produced by this method
Comparison of different Isolated Polymeric Lignins
Isolated Lignin: Technologies for Deconstructionto its Monomeric Components
Chemical Methods
Biological Methods
Lignin
KraftLignosulfonateDilute acidAlkaliSteam explosionAFEXOrganosolveKlasonDil. Ammonia
HydrothermalLiquefaction
Pyrolysis andHydrocatapyrolysis
Gasification
Phenol, Phenolic derivatives and oligomeric aromatic phenols
OH
O
HO OH
O
O
Aromatic and aliphatic hydrocarbons,alkoxy phenol and darivative
OH
C5-C9
SyngasCO,H2, CO2,CH4
Catalysis 1
Catalysis 1
Catalysis 2
Catalysis 2
Catalysis/ Fermentation
GasesChar
GasesChar
Char
+
+
+
Polymers
Fuel
Bulk and FineChemical s
Chemical Depolymerization and Conversion of Lignin
Lignin
KraftLignosulfonateDilute acidAlkaliSteam explosionAFEXOrganosolveKlasonDil. Ammonia
HydrothermalLiquefaction
Pyrolysis andHydrocatapyrolysis
Gasification
Phenol, Phenolic derivatives and oligomeric aromatic phenols
OH
O
HO OH
O
O
Aromatic and aliphatic hydrocarbons,alkoxy phenol and darivative
OH
C5-C9
SyngasCO,H2, CO2,CH4
Catalysis 1
Catalysis 1
Catalysis 2
Catalysis 2
Catalysis/ Fermentation
GasesChar
GasesChar
Char
+
+
+
Polymers
Fuel
Bulk and FineChemical s
Chemical Depolymerization and Conversion of Lignin
Technology BottlenecksLow conversions in Catalysis Step 1Complex catalysis required in Step 2
1939
Lignin degradation studied in compost environment
1950 –1999
Degradation studied in Trametes
Phanerochaetechrysosporium used as model organism
All peroxidases discovered
Laccase mediator discovered, molecular biology of fungal enzymes studied.
1990 – 2015
Bacterial lignin degradation studied in Nocardia, Pseudomonas and Actinomycetes
Bacterial lignin degraders fall into three categories actinomycetes, α-proteobacteria, γ-proteobacteria
Sphingomonas paucimobilis SYK-6 extensively studied for catabolism of lignin compounds
Pseudomonas putida, Rhodococcus species, Bacillus species, Cupriviadus necatorbeing targeted for genetic manipulation for biotransformation of lignin to chemicals and fuels
Annele Hatakka in Bugg et al. Natural Products Reports, RSC Publishing, 2011, 1871-1960
Bioconversion of Lignin: Past, Present and Future
Microbial Depolymerization of lignin
Microbial Lignin Depolymerization
Enzyme Concoctions
Laccases Peroxidases
Depolymerized Lignin components
Auxiliary Enzymes
Microbial Depolymerization of lignin
Microbial Lignin Depolymerization
Enzyme Concoctions
Laccases Peroxidases
Depolymerized Lignin components
Auxiliary Enzymes
Technology Bottlenecks Re-polymerization of lignin a major issuepH and temperature critical factorsSlow processesGenetic manipulation of fungus tediousIsolated enzymes very expensive (if available)
Part 2Lignin Conversion Technologies
Chemical and Biological
Chemical Conversions of Lignin precursor chemicals obtained from
thermo chemical treatment to lignin
PF ResinsPolyester
BTX,Gasoline range hydrocarbon s
Syngas,Fermentation to Products
CatalysisCatalysis
Designed microbial system to convert lignin derived aliphatic and aromatics into Value added products
Lignin Lignin degrading microbes
AdvantagesNot energy intensiveEco-friendlySelectivity and specificity of end products
Value added chemicals
Biological Conversion of Lignin
D Salavuchua et al. Green Chemistry, RSC Publishing, 2015
Future of Lignin Bioconversion Technologies
Development of Lignin Technologies at
DBT-ICT Centre for Energy BiosciencesMumbai, India
Base Catalyzed Biomass Pretreatment .vs.
Acid/Hydrothermal Pretreatment
BASE - Milder- Ester hydrolysis- Limited glycosidic hydrolysis- Progressive steps
- delignification- hemicellulose leaching
- No furanic formation- Simple stainless Steel OK- Higher concentrations required- Recovery essential
ACID/HYDRO - Severe conditions- Ester & Ether Hydrolysis- Considerable glycosidic hydrolysis- Simultaneous steps
- Fractionation not performed
- Furanics formation- Complex MOC- Low concentrations- Recovery not done
Base Catalyzed Biomass Pretreatment.vs.
Acid/Hydrothermal Pretreatment
BASE - Milder- Ester hydrolysis- Limited glycosidic hydrolysis- Progressive steps
- delignification- hemicellulose leaching
- No furanic formation- Simple stainless Steel OK- Higher concentrations required- Recovery essential
ACID/HYDRO - Severe conditions- Ester & Ether Hydrolysis- Considerable glycosidic hydrolysis- Simultaneous steps
- Fractionation not performed
- Furanics formation- Complex MOC- Low concentrations- Recovery not done
- Use of MF/UF/NF for separation and recovery of base
- Distillation if aqueous ammonia used
10 ton Biomass/day Pilot Plant at
India Glycols Limited, KashipurPhase 1: Functional from February 2012Phase 2: To begin production in Oct 2014
Technology components tested at
A. Laboratory scale (ICT)B. Preparatory scale (ICT)
C. Plant scale (IGL)
Pretreatment process a- 10% NaOH, 130°C, 30minb-12.5 to 25% NH3, 130°C to 150°C , 30minc- 72% H2SO4, 30 °C, 60min
Characterization of Lignin obtained from alkali and acid pretreated Rice Straw
Lignin Types
Acid Ligninc (Klason)
Elemental analysis, sugar and ash analysis
NaOH Lignina NH3 Ligninb
FT-IR TGA NMR
Compositional analysis
Functional group analysis
Thermalbehavior
GPC
Molecular weight distribution
Structural studies
Samples Cellulose (%)
Hemicellulose as xylose (%)
Ash (%)
Purity (%)
NaOHlignin
6.08 26.14 2.18 65.60
NH3
lignin2.88 2.53 7.74 86.85
Acid(Klason)
lignin
13.50 1.21 4.30 80.99
Samples C H O N S
NaOHlignin
52.88 6.18 39.08 0.59 0.07
NH3 lignin 56.51 5.18 27.02 4.71 0.71
Acid(Klason)
lignin
49.50 4.53 32.69 0.56 4.51
Compositional Analysis Elemental Analysis
Carbohydrate content was found to be higher in NaOH lignin as NaOH being stronger base, co-extracts hemicellulose with lignin.
Higher ash content in NH3 lignin was mainly due to the insolubility of ammonium silicate in water
Reactivity of ammonia and sulphuric acid was confirmed from higher nitrogen and sulphur content in NH3 and acid lignin.
Derived Lignin Analysis
TGA analysis
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0 100 200 300 400 500 600 700 800 900
Acid lignin
NaOH lignin
NH3 lignin
Decomposition temperatureAmmonia lignin < NaOH lignin < Acid lignin
CondensationAmmonia lignin < NaOH lignin < Acid lignin
3410C
3520C
4100C
Temperature (deg C)
Decomposition temperature of acid lignin was found to be higher than alkali lignins, confirming undesirable condensation in acid pretreatment
DBT-ICT Lignin Technologies
cDilute ammonia Lignin
cMining for Microbes with best utilization and growth profiles
cMetabolic Pathway Engineering and Fermentation technology for Value Adds
cCatalytic Depolymerization
Thank you
DBT-ICT Centre for Energy Biosciences, IndiaState-of-the-Art Facility with >100 scientistsCollaborations with Australian, UK and German GroupsWorking with major companies in India and WorldSetting up 5 biorefinery demo-plants to go on-stream in 2016Lignin specific collaborations most welcome