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 400019am.lali@ictmumbai.edu.in

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