jj leahy expo

2nd Generation biomass conversion - biorefining

J J Leahy –University of Limerick

2nd Generation biomass conversion

• 2nd Generation; new sustainable indigenous industry based on carbohydrate biomass of which a major component is lignocellulosic biomass

• Nonfood biomass transport fuel, fuel additives, chemicals (plastics, food ingredients, medical products)

1st Generation biomass conversion

• Vegetable oils biodiesel

• Biomass starch ethanol

Biomass

Sugar/starchcrops

LignocellulosicBiomass

Oil plants

extraction

Vegetable oil

hydrolysis

sugar

fermentation

Bio-ethanol

pyrolysis gasification Anaerobicdigestion

hydrolysis

refining

Catalyticupgrading

syngas

Catalytic reforming

Bio-oil

Motor fuels & Chemicals

biogas

methane

sugar

fermentation

esterify

biodiesel

Bioalcohol

Biofuels: a significant opportunity for Ireland

• Resources: grass, biomass, agricultural residues

• Global Biofuels Market: $160b in 2012 - growth of 13.0% p/a to 2017

• Global Biorefining Market: multi-sectorial, e.g. 20% of sales in global chemical industry = $250b, c. 400,000 jobs.

• Need to integrate Ireland into EU strategy and maximize business opportunities

Technologies, feedstock prices and policy framework

Ireland’s response• Policy: Cleantech focus by Agencies

• IDA/EI: Competence Centre for Biorefining and Bioenergy

– Grass and algae (desk studies) as feedstock, ethanol as primary fuel target. Near to market or technology importation to establish Irish-based activity

• need to develop strategic research base focused on

next generation technologies, to attract key industrial players and to position Ireland for success

1

Gasification Pyrolysis

Feedstock selection

Biosyn gas Char Bio oil

Biochar Activated carbon

Catalytic Upgrading

Diesel Miscible Biofuels

Gas cleaning & conditioning

Residue

Potential of microalgae (desktop)

Feedstocks 1. Grass (conserved & fresh) 2. Miscanthus

Primary Conversion Enzymatic Hydrolysis Pyrolysis & Gasification

An

alysis of Feedstocks &

products

Secondary Conversion Chemical (catalytic) Enzymatic Microbial

Biopolymers e.g PHA

Platform Chemicals Oils, Sugars.

Proteins, Phenols, Lignins,

Bioactives

Liquid Transport Fuels

Fermentation Optimisation

Catalysis (incl. enzymatic)

Enzymatic Hydrolysis

Fine chemicals Pharma

compounds

Competence Centre for Biorefinery and Bioenergy (CCBB) Initial Research Phase Overview

Next Steps• Address strategic gaps: field to wheel• Engage key industrial players through cutting edge

research• Exploit competitive advantages:

– Future feedstock development

– Future transport usage

– Novel, high-value co-products

– Sustainable procesess

• Education sector - Graduates, IP, leveraged funding,

Significant economic and commercial impacts

Need to select “good” varieties of plants?Novel varieties of Ryegrass, Miscanthus and

Sweet Sorghum easier to bioprocess

Smarter biofuels - Butanol: major advantages– production?Biogas methane: flexible fuel but production efficiency low?

Processes based on novel enzyme technologies or chemical routes (catalysis)

Demonstration-scale production

New Irish businesses: 2nd and 3rd G biogas and butanol technologies

Co-products and residues

Bioenergy alone not sustainable – dependent on nature &value of co-products

Residues minimized, converted to added value products

D-xylose (C5) conversion to bioplasticBiochar production process from residues

Novel non-GM protein supplement for animal

nutrition

University of Limerick Biorefining research

• Thermochemical processing of biomass through pyrolysis and thermal gasification to 2nd generation biofuels and biochar

• Chemical hydrolysis of lignocellulosic biomass to levulinic acid

University of Limerick

Catalytic Conversion

• Nonfood biomass levulinic acid fuel additives, chemicals

• Biomass derived bio-oil fuels, chemicals, hydrogen

• Biomass derived chemicals (by-products) fuels, hydrogen

• Vegetable oils biodiesel

• Biomass ethanol

Carbolea• Research group comprised mainly of chemists, chemical

engineers;• Group consist of 2 professors 2 Senior faculty, 2 CPI

research fellows; 5 post-docs & 10 PhD students• Research goes from field to engine & back to field• Extensive involvement in 1st generation biofuels

– 3 EU; several national programs; currently involved with ESB on fleet trials

– Waste cooking oil & tallow feedstocks– Modifying the low temperature behaviour of Biodiesel– Effect of biofuel deployment on fleet management.

• 2nd Generation; new sustainable indigenous industry based on carbohydrate biomass of which a major component is lignocellulosic biomass

Thermochemical-pyrolysis

NONFOOD BIOMASS (grasses or residue from fermentation, etc)

lignin (15-30%), cellulose (35-50%), hemicellulose (15-25%)

Pyrolysis

Gases,Char,Bio-oil

T=450-550oC,Residence time <2s,

Heating rates 103-104 K/s

70-80% yield

Bio-oil Properties

Mixture >300 compounds acetic acid 1-32%, formic acid 1-20%, phenols,

aromatics, water, etc.

Advantages: transportable, storable, much higher energy density than biomass and cleaner

Disadvantages: corrosive (pH=2.5), unstable, immiscible with petrofuels, low heating values

Bio-oil vs Transport Fuels

Bio-oil Gasoline DieselCarbon chainlength up to 100 5-10 12-

20 branched alkanes, linear

alkanes aromaticsH/C ratio ~1.3 1-2

~2

O/C ratio 0.5 0 0

Upgrading of bio-oil is necessary

Hydrodeoxygenation of Bio-oil

Bio-oil

Hydrocarbons(naphtha equivalent)

Diesel

Refining,catalysts

Hydrodeoxygenation,Mesoporous silica supported catalysts

Bio-oil + H2 Hydrocarbons + H2O

350-400oC

Bio-oil + R-OH Upgraded Bio-oil + H2O

Esterification

R1COOH + R-OH <-> R1COOR + H2O

AcetalizationAcid catalysts

Acid catalysts, 50-80oC

Acid catalysts

Esterification

R1CHO + 2 R-OH <-> R1CH(OR)2 + H2O

Gasification pyrolysis

Feedstock analysis

Feedstock selection& optimisation

Biosyn gas

Alcoholsynthesis

Bioethanol higher alcohols

Catalytic upgrading

Liquid hydrocarbon fuels

Char Bio oil

Biochar Activatedcarbon

CatalyticUpgrading

Diesel MiscibleBiofuels

Platform Chemicals

Gas cleaning & conditioning

ChemicalHydrolysis (Solid Acid Catalysts)

Pretreatment(Ionic Liquids)

Platform Chemicals

& optimisati

on

Lignin Residue

Sugars

Liquid Transport Fuels

Alternatives to Petrol-Derived Products

Fermentation

Catalysis

Gasification

TemperatureFluidising velocity

Inert material CharacteristicsResidence time

Particle sizeMoisture

Mineral contentFixed carbon

volatiles

Feedstock parameters Process variables

Gas quality

Gasification of Bio-oil

Bio-oil

Steam and autothermal reforming, >700oCSupported metals

Fischer-TropschProcess (FT), supported Co or Fe catalysts

MethanolMethanol to gaso-line process (MTG)

Diesel

CO + H2

Gasoline

Cu/Zn/Al2O3 catalysts,

high pressure

Bio-oil + H2O (+ O2) CO + H2 Hydrocarbons + H2O

Dimethyl ether(diesel substitute)

zeolites

synthesis gas

HydrogenClean fuel

Present industrial production:

coal natural gas (CH4, C2H6, etc) + H2O H2 + CO, steam-reforming

naphtha

CO + H2O CO2 + H2, water-gas shift reaction

50 million tons per year

Hydrogen from Bio-oil

Water soluble Bio-oil

Steam and autothermal reforming, supported metals,

>600oC

H2 + CO2 + some COPreferential oxidation

process (PROX),supported metals

H2 + CO2

Energy

Low temperaturefuel cell

Bio-oil + H2O (+ O2) CO2 + H2

YIELDS – up to 90%

Bio-oilH2O

extraction

Hydrogen production from bio-oil looks attractive

Hydrogen from Chemicals Derived from Biomass

Steam reforming over supported metals and oxides as catalysts

H2 + CO2

Formic acid, HCOOH

Ethanol, C2H5OH

Glycerol

Levulinic acid –platform chemical & primary goal of DIBANET (UL led FP7)

CROPS

ARGICULTURAL

RESIDUES

CELLULOSIC

SLUDGES

WOOD

STARCH

WASTE

PAPER

MOLASSES

THE

BIOFINE

PROCESS

LEVULINIC

ACID

FORMIC

ACID

FURFURAL

LIGNEOUS

CHAR

DOWNSTREAM

CONVERSION

SPECIALTY

CHEMICALS

COMMODITY

CHEMICALS

HERBICIDES

PESTICIDES

ENERGY

FUELS

AUTOMOTIVE

FUELS

FEEDSTOCKS

“BIOMASS”

PRODUCTS

Cellulose

Sugars

Intermediates I

HMF

Intermediates II

Levulinic Acid (50wt %)

First Stage

Plug Flow

Reactor

Second Stage

Back Mixed

Reactor

Chemical hydrolysis of cellulose to LA

Fast Reaction

(Seconds)

Slow Reaction

(Minutes)

Tars (30 wt%)

Formic Acid (20 wt %)

OCH2OHOHC

BIOREFINERY YIELDS

TYPICAL MOLAR YIELDS

(OF THEORETICAL)

TYPICAL MASS YIELDS

(PER TONNE OF FEED)

LEVULINIC ACID

FORMIC ACID

FURFURAL

LIGNEOUS CHAR

70%

70%

70%

100% (MASS)

0.25

0.10

0.15 (VARIES)

0.45

50% Cellulose

30% Hemicellulose

20% Lignin

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