Lignin Production and Conversion Technologies

Arvind Lali Aruna N, Prathamesh Wadekar, Mallikarjun Patil, Parmeshawar Patil, Nikhil Asodekar; Suveera Bellary

DBT-ICT Centre for Energy Biosciences Institute of Chemical Technology (formerly UDCT) Mumbai, INDIA 400019 [email protected]

Mumbai

INDIA

Institute of Chemical Technology (formerly UDCT) at Matunga (Central Suburb)

DBT-ICT Centre for Energy Biosciences Matunga, 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 Scientists in different disciplines of modern biological sciences and chemical engineering/technology

Centre’s Overall RDD&D Objectives Development, Demonstration and Transfer Cost effective and Sustainable Biomass to Biofuel technologies Building capacity in the field of Industrial Biotechnology

Capacity & Infra Building

HR Generation

Technology Development

Technology Deployment

Sustainable Platform Technologies

Waste Utilizable Carbon Smart Chemical/Biotech Conversion Technologies

Food/Feed/Energy/Materials & Chemicals

400

400

Biomass to Renewables: Technology Options Biomass Combustion

Digestion

Power

Biogas/BioCNG

Gasification Fast Pyrolysis/ SCWG

Syn-Gas Fermentation/ Chemical Catalysis

Catalysis FT Synthesis

Hydrocarbons

Platform Chemicals

Bio-Oil

Cracking

Gasoline, Diesel

Fermentable Sugars

Hydrocarbons & Chemicals Hydrocarbons

BioFuels Platform Chemicals

Biomass to Renewables: Technology Options Biomass Combustion

Digestion

Power

Biogas/BioCNG

Gasification Fast Pyrolysis/ SCWG

Syn-Gas Fermentation/ Chemical Catalysis

Preferred Technology Catalysis FT Synthesis Platform Hydrocarbons Hydrocarbons

Platform Chemicals

Bio-Oil

Cracking

Gasoline, Diesel

Fermentable Sugars

& Chemicals Hydrocarbons

BioFuels Platform Chemicals

TYPICAL PROCESS OUTLINE

Lignocellulosic Biomass STEP 1

Pre-Treatment Step

STEP 2

Saccharification

STEP 3

Fermentation

STEP 4

Separation/Purification

LIGNIN

Biofuel

Typical 2G-Bioethanol and Pulping Process

Biomass

Fractionation

Lignin to Boiler

Biomass

Kraft and Lignosulfonate Process

Enzyme hydrolysis of carbohydrates

Fermentation to ethanol

Does it deserve more than just burning

Paper and pulp

Routes to Lignin Utilization Lignin

Used in As-Derived form for integrating into More complex Polymeric structures e.g. formulating resins; as polymeric filler

Break-down partially or fully

Reconstruct Products through Biological or Chemical technologies

Routes to Lignin Utilization Lignin

Used in As-Derived form for integrating into More complex Polymeric structures e.g. formulating resins; as polymeric filler

Attempted with Limited successes

Way to go for Better value

Break-down partially or fully

Reconstruct Products through Biological or Chemical technologies

Next Generation Lignin Technologies Lignin Isolation & Deconstruction technologies Lignin  Depolymerization  Polishing

Conversion technologies Lignin monomers  Conversion  Products Biological Methods and Chemical Methods

Part 1 Lignin Isolation and Deconstruction Technologies Chemical and Biological

Lignin : A Polymeric structure closely linked with Itself, Cellulose and Hemicellulose

Lignin-Carbohydrate bonding

Lignin Intra-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-coumaryl alcohol

Softwood

75%

20%

5%

Hardwood

50%

40%

10%

20

2G Biofuels: Lignin Production Technologies Process

Typical Conditions

Lignin Recovery Method

Pulping based Lignin Production Technologies

Lignin

Properties

Dilute acid

MW 5000 10000 Da Sulphur content – 0 – 1.0 % (dilute Sulphuric acid process) Condensed structure

Alkali

MW 2700 -6000 Da Sulphur free process Accounts for nearly 5% of the total pulp production

Steam explosion (softwood)

MW 2500-11000 Da (lignin obtained from softwood) No Sulphur content Condensed structure, lower methoxy but higher hydroxyl group

AFEX

MW 5000Da No Sulphur content The method cannot be used for >25% lignin content biomass

Klason

MW 8000 – 9000 Da Sulphur content – 4-5% Condensed structure

Organosolve (Alcell process)

MW 3300 Da (Lignin obtained from hardwood) Sulphur free and less condensed structure

Kraft Process

MW 6000-10000Da 1.5–3 wt% Sulphur content Dominant pulping process in world

Lignosulfonate

MW 12000Da-65000 Da 4–8% Sulphur content (so higher mol wt) 10% of pulp is produced by this method

Comparison of different Isolated Polymeric Lignins

Isolated Lignin: Technologies for Deconstruction to its Monomeric Components Chemical Methods

Biological Methods

Chemical Depolymerization and Conversion of Lignin OH

HO

O

OH

O

Hydrothermal Liquefaction

Lignin Kraft Lignosulfonate Dilute acid Alkali Steam explosion AFEX Organosolve Klason Dil. Ammonia

Catalysis 1

O

Catalysis 2

Phenol, Phenolic derivatives and oligomeric aromatic phenols Char

+

Gases OH

Polymers C5-C9

Pyrolysis and Hydrocatapyrolysis Catalysis 1

Catalysis 2

Aromatic and aliphatic hydrocarbons, alkoxy phenol and darivative Char

Gasification

+

Bulk and Fine Chemical s

Gases

Char + Syngas CO,H2, CO2,CH4

Fuel

Catalysis/ Fermentation

Chemical Depolymerization and Conversion of Lignin OH

HO

O

OH

O

Hydrothermal Liquefaction

Lignin

Catalysis 1

O

Phenol, Phenolic derivatives and oligomeric aromatic phenols Char

+

Catalysis 2

Gases

Technology Bottlenecks OH Kraft Lignosulfonate Low conversions in Catalysis Step 1 C5-C9 Dilute acid Pyrolysis and ComplexHydrocatapyrolysis catalysis required in Step 2Catalysis 2 Alkali Aromatic and aliphatic hydrocarbons, Catalysis 1 Steam alkoxy phenol and darivative explosion + Char Gases AFEX Organosolve Catalysis/ Char Klason Fermentation + Gasification Dil. Ammonia Syngas CO,H2, CO2,CH4

Polymers Fuel Bulk and Fine Chemical s

Bioconversion of Lignin: Past, Present and Future 1990 – 2015 Bacterial lignin degradation studied in Nocardia, Pseudomonas and Actinomycetes 1950 –1999 Degradation studied in Trametes

1939 Lignin degradation studied in compost environment

Phanerochaete chrysosporium used as model organism

All peroxidases discovered Laccase mediator discovered, molecular biology of fungal enzymes studied.

Bacterial lignin degraders fall into three categories actinomycetes, αproteobacteria, γ-proteobacteria Sphingomonas paucimobilis SYK-6 extensively studied for catabolism of lignin compounds

Pseudomonas putida, Rhodococcus species, Bacillus species, Cupriviadus necator being 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

Microbial Depolymerization of lignin Microbial Lignin Depolymerization Enzyme Concoctions

Laccases

Peroxidases

Auxiliary Enzymes

Depolymerized Lignin components

Microbial Depolymerization of lignin Microbial Lignin Depolymerization Enzyme Concoctions

Technology Bottlenecks

 Re-polymerization of lignin a major issue Auxiliary Peroxidases Laccases pH and temperature critical factors Enzymes Slow processes Genetic manipulation of fungus tedious Isolated enzymes very expensive (if available)

Depolymerized Lignin components

Part 2 Lignin Conversion Technologies Chemical and Biological

Chemical Conversions of Lignin precursor chemicals obtained from thermo chemical treatment to lignin

Catalysis

PF Resins Polyester

Catalysis

BTX, Gasoline range hydrocarbon s

Syngas, Fermentation to Products

Biological Conversion of Lignin Designed microbial system to convert lignin derived aliphatic and aromatics into Value added products

Lignin

Lignin degrading microbes

Advantages Not energy intensive Eco-friendly Selectivity and specificity of end products

Value added chemicals

Future of Lignin Bioconversion Technologies

D Salavuchua et al. Green Chemistry, RSC Publishing, 2015

Development of Lignin Technologies at

DBT-ICT Centre for Energy Biosciences Mumbai, 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

-

ACID/HYDRO - Severe conditions - Ester & Ether Hydrolysis -- Considerable glycosidic Use of MF/UF/NF for hydrolysis - separation Simultaneous andsteps recovery Fractionation not performed of -base -- Distillation if Furanics formation used - aqueous Complex ammonia MOC

No furanic formation Simple stainless Steel OK Higher concentrations required - Low concentrations - Recovery not done Recovery essential

Technology components tested at A. Laboratory scale (ICT) B. Preparatory scale (ICT) C. Plant scale (IGL)

10 ton Biomass/day Pilot Plant at India Glycols Limited, Kashipur Phase 1: Functional from February 2012 Phase 2: To begin production in Oct 2014

Characterization of Lignin obtained from alkali and acid pretreated Rice Straw Lignin Types

NaOH Lignina

Compositional analysis

Elemental analysis, sugar and ash analysis

Functional group analysis

FT-IR

NH3 Ligninb

Molecular weight distribution

GPC

Acid Ligninc (Klason)

Thermal behavior

TGA

Structural studies

NMR

Pretreatment process a- 10% NaOH, 130°C, 30min b-12.5 to 25% NH3, 130°C to 150°C , 30min c- 72% H2SO4, 30 °C, 60min

Derived Lignin Analysis Elemental Analysis

Compositional Analysis Samples

Cellulose (%)

Hemicellulose as xylose (%)

Ash (%)

Purity (%)

Samples

C

H

O

N

S

NaOH lignin

6.08

26.14

2.18

65.60

NaOH lignin

52.88

6.18

39.08

0.59

0.07

NH3 lignin

2.88

2.53

7.74

86.85

NH3 lignin

56.51

5.18

27.02

4.71

0.71

Acid (Klason) lignin

13.50

1.21

4.30

80.99

Acid (Klason) lignin

49.50

4.53

32.69

0.56

4.51

Carbohydrate content was found to be higher in NaOH lignin as NaOH being stronger base, coextracts 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.

TGA analysis 0.9

0.8 0.7 Acid lignin

0.6

Decomposition temperature Ammonia lignin < NaOH lignin < Acid lignin

NaOH lignin 0.5

NH3 lignin

0.4

Condensation Ammonia lignin < NaOH lignin < Acid lignin

3520C

0.3

3410C

0.2

4100C

0.1 0 0

100

200

300

400

500

600

700

800

900

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 c Dilute ammonia Lignin

Catalytic Depolymerization c

Mining for Microbes with best c utilization and growth profiles

Metabolic Pathway Engineering and Fermentation c technology for Value Adds

DBT-ICT Centre for Energy Biosciences, India State-of-the-Art Facility with >100 scientists Collaborations with Australian, UK and German Groups Working with major companies in India and World Setting up 5 biorefinery demo-plants to go on-stream in 2016 Lignin specific collaborations most welcome

Thank you