TECHNOLOGY DEVELOPMENT ON BIOFUELS

Sustainable EnergyLecture Series

Jadavpur University Kolkata

DILIP KUMAR ADHIKARI PhD

Jadavpur University Kolkata

Chief Scientist & Head Biofuel DivisionCSIR-INDIAN INSTITUTE OF PETROLEUM

D h dDehradun18th July 2013

LCA & CFD

Challenges on Biofuel Technology Development

• Sustainable Biomass collection and supply• Energy efficient and Low cost conversion processgy p• Multidisciplinary activities under Biorefinery approach• Product recovery and distribution• Product recovery and distribution• Techno-economic sustainability• Carbon footprint from field to wheel

S i li i l d i• Socio-political drive

Physico‐chemical properties of fuels

B ili i t d b f t f l d bi f lBoiling point and carbon no of petro fuels and biofuels

Economic burden of oil importp

RATIONALE: RENEWABLE HYDROCARBONS

4

RATIONALE: RENEWABLE HYDROCARBONS

Fast pyrolysis oil

Vegetable oilsButanol

Ethanol

/C ra

tio

Mixed alcohols

Vegetable oils

Adjust H/C ratio/mol. Wt.

Lower oxygen

O/

Natural Gas GasolineIH2 product

Diesel

ratio/mol. Wt.

H/C  i

0

H/C ratio4 0

Petro‐refining and Bio‐refining to meet Gasoline composition

Petro‐refining and Bio‐refining to meet Diesel composition

Petro‐refining and bio‐refining to meet Jet fuel composition

BIOMASS IS COMPLEX

7

Composition of Lignocellulosic Biomass g

Glycerides/fatty acids/Lipidse g vegetable oils animal fats

Transesterification Fame BiodieselNegligible potential in India for 

ROAD MAP FOR BIOREFINERY

e.g. vegetable oils, animal fats

Sugar/starchl

Hydrodeoxygenations Green DieselIsomerisation

Ethanol fermentation Ethanol Scenario 1:5.4 mmt Scenario 2:7.5 mmt 

biodiesel or renewable diesel at present

e.g. sugarcane, molasses 

Biomass 

Butanol Iso‐butanol Scenario 1:1.4‐3.2 mmt BuOH; 1.4 mmt acetone Scenario 2:7.5 mmt  BuOH, 1.9 mmt acetone

Fischer Tropsch

Catalytic alcohol syn

Alkanes 

Al h l

Olefins

360 mmt

5.4 mmt diesel

feedstocks GasificationCatalytic alcohol syn.

Water  gas shift

Ethanol fermentation

Alcohols

Hydrogen

Ethanol Gasoline

16.1 mmt

12.3‐18.7 mmt

Lignocellulosic  biomasse.g. agro residue, energy crops, forestry waste

Pyrolysis liquifaction

Catalytic pyrolysis

Pyrolysis oils (Bio oils)(complex mixture of 

oxygenates)

Hydrodeoxygenations

Zeolite upgrading

Hydrocarbon liquids 

(Gasoline/diesel)

53 mmt

Pre treatment/acetic acid fermentation

Pre treatment/ethanol fermentation

Aqueous phase  reforming (Bio reforming)

Ethanol

Ethanol

Hydrocarbon liquids(Gasoline/diesel)(Direct catalytic processing of sugars)

10.8‐14.4 mmt

21.9 mmt

Catalytic process

Mineral acid fermentation (e.g. mix alc.)

Pre treatment/ butanol fermentation

Pre treatment/acetic acid fermentation

n‐butanol or iso‐butanol

Ethanol

Zeolite upgradingHydrocarbon liquids (gaoline/diesel)

Zeolite upgradingMixed alcohols Hydrocarbon liquids (gaoline/diesel)

21.9 mmt

22.3 mmt

Biochemical process

Thermochemical Process

Overview of Available Conversion Processes

C.A. Cardona et al (2010) Bioresource Technology 101:4754–4766 4

GASOLINE Vs. POTENTIAL BIOFUEL

FuelEnergy density

Air-fuel ratio

Specific energy

Heat of vaporization

RON MON

Unit MJ/l - MJ/kg air MJ/kg - -

Gasoline 32 14.6 2.9 0.36 91–99 81–89

Butanol 29.2 11.2 3.2 0.43 96 78

Ethanol 19.6 9.0 3.0 0.92 130 96

Methanol 16 6.5 3.1 1.2 136 104

14

T t l R id 155 MMTA

Biomass Atlas, India

Total Residue - 155 MMTAPower Generated - 14567 MWe

Total Agro Residue - 511 MMTATotal Agro Residue 511 MMTAPower Generated - 18729 MWe

Biomass Atlas, India

Biomass statisticsIndia Total Land A

non

India Total Land Area (sq. Km)

India 3300000

arable land43%

non arable land 36%

Arable land 1410000

Non-arable land 1200000

Forest cover 690000forest cover21%

Forest cover 690000

Wasteland from Biomass Atlas 542527

Wasteland from Wasteland Atlas 472262

Total Agro Residue - 511 MMTAMMTA

Power Generated - 18729 MWe

Total F&W Residue - 155 MMTA

Power Generated - 14567 MWe Biomass Atlas, India

AN INTEGRATED APPROACH FOR UTILIZATION OF BAGASSE PITH FOR UTILIZATION OF BAGASSE PITH FOR

PRODUCTION OF BIOETHANOL & VALUE ADDED PRODUCTSADDED PRODUCTS

ORIGIN OF THE PROJECT

Paper industry uses bagasse after depithing (60‐70% depithingefficiency)y)

Presently paper mills use baggase pith as inefficient boiler feedand create environmental pollutionand create environmental pollution

In India an average 300 bagasse based paper mill consumes800 d SCB d h 160 d i h800 tpd SCB and thus generates 160 tpd pith

AIM OF THE PROJECT

We targeted to integrate a bagasse pith based biorefinery processwithin a paper / sugar mill premises where apart from paper or

f l dd d d d h / l i i ill bsugar, array of value added products and heat / electricity will begenerated

Which in turn

Will make lignocellulosic ethanol cost competitive due to arrayWill make lignocellulosic ethanol cost competitive due to arrayof value added productsProcess will reduce environmental issues

Pretreatment of bagasse biomass to extract pentose sugar stream

SSugarcane bagasse pith

steam and acid pretreatment at elevated temp & pressure with precise holding time

Pentose rich stream with ~ 90% C5 recovery

leftover biomass for 

tienzymatic saccharification

Saccharification of pretreated bagasse pith to extract hexose sugar stream

85% enzyme recovery and reuse

Pretreated bagasse pith

Enzymatic saccharification

Hexose rich stream with ~ 80% C6 recovery

l ft li i i hleftover lignin rich solid for 

gasification or lignin value gaddition

YEAST BIOMASS GENERATION

PROCESS NOVELTYA non Saccharomyces yeast

Thermophilic yeast grows and ferments at 50oC

It grows on pentose rich prehydrolysate

525

3

4

5

15

20

25

5); G

PL

mas; G

PL

0

1

2

0

5

10

Sugar (C5

Cell biom

000 5 10 15 20 25

hour

Kluyveromyces sp. IIPE453 (MTCC  5314)

High temperature Fermentation of hydrolysate to ethanol

High temperature (50oC) fermentation of hexose sugars to ethanol using

PROCESS NOVELTY

High temperature (50 C) fermentation of hexose sugars to ethanol usingKluyveromyces sp. IIPE453 grown on pentose sugars

Less chance of microbial contamination

Conversion factor is ~ 90% of the theoretical yield40% overall energy saving

Growth and fermentation on different carbon sources by Kluyveromyces sp. IIPE453

Substrate Dry cell  ( /l)

Biomass i ld (% Y )

Ethanol  (%)

Ethanol i ld (% Y )S mass (g/l) yield (% YX/S) conc. (%) yield (% YP/S)

Galactose 2 20 1.9 47

Mannose 1.2 12 0.7 33

Arabinose 0.1 6 0 0

Sucrose 1.3 13 8.68 50

Lactose 0 6 22 0 8 16 8Lactose 0.6 22 0.8 16.8

Cellobiose 0.7 35 0.16 4.3

R ffi 8Raffinose 1.1 34 0.8 11

Production of furfural from pentose rich prehydrolysate stream

CONVENTIONAL PROCESS FOR FURFURAL PRODUCTION BYHOMOGENEOUS ACID CATALYST

Quaker-Oats processQuaker Oats processPetrole-chimie ProcessRosenlew Process

CSIR IIP FURFURAL SYNTHESIS PROCESSCSIR-IIP FURFURAL SYNTHESIS PROCESS

Conversion of xylose rich prehydrolysate stream to furfuralusing heterogeneous catalyst in bi phasic systemusing heterogeneous catalyst in bi-phasic systemEasy product recovery

Initial ignin rich The residual char

Gasification of lignin rich leftover biomass after saccharification

Initial ignin rich biomass

The residual char obtained after gasification

gross calorific value (GCV) 4981 cal/g  5512 cal/gC 50.42 56.24H 4 56 1 69

Components of Fuel Concentration in (%)

H 4.56 1.69N  1.22 0.91 S 0.47% 0.20%

Components of Fuel Gas

Concentration in (%) as analyzed by GC

Hydrogen 4.36Carbon Dioxide 58.49

Oxygen 0 34Oxygen 0.34Nitrogen 11.26

Carbon monoxide 8.26Methane 10.80Ethane 1.22

Ethylene 1.97Others 3.3Total 100

achievements in nutshellPROCESS TARGETED TARGET ACHIEVEDDepithing of bagasse > 70-80% removal of pith from sugarcane baggasePretreatment of bagasse pith > 90% extraction of C5 sugar by acid and steam treatmentEnzymatic saccharification of

t t d b ith> 80% extraction of C6 sugar by cellulase enzyme

pretreated bagasse pith 6 g y y

Recovery of enzyme for further reuse

> 85% recovery of cellulase from saccharified broth for further reuse in next cycle of saccharification

G ti f t biOptimum generation of yeast biomass from C5 sugar stream at

Generation of yeast biomassp g y 5 g

high temperature for ethanol fermentation

Pentose value additionCatalytic conversion of C5 stream into furfural (50% conversion)F t ti f th l t hi h t t (50OC) ith

Ethanol fermentationFermentation of ethanol at high temperature (50OC) with saccharified C6 broth with > 92% theoretical yield with 40% energy saving

E tiGeneration of producer gas from leftover lignin rich biomass

Energy generationp g g

after maximum extraction of C5 & C6 sugars

Lignin value additionIf not energy production then further lignin value addition like resins and lignosuphonates etc.

Ethanol Production Cost

122

92100

120

140

Cos

t, c/

l

9277

5460

80

100

oduc

tion

C

3925 22 20

20

40

than

ol P

ro

01979 1982 1985 1987 1999 2005 2010 2015

Year

Et

Year

Th t i t t h ll ?

It remains the same as ever getting to parity

The most important challenge? 

It remains the same as ever, getting to parity with fossil fuels. Here’s the cruel math, there. If gasoline trades at Rs 35/ L then on anIf gasoline trades at Rs.35/ L, then on an energy basis ethanol will need to trade at around Rs 28/Laround Rs.28/L. 

Enzyme Cost

Enzyme WarEnzyme War

• It is a battle over technology, feedstock t s a batt e o e tec o ogy, eedstoccosts, infrastructure investment, and to some extent biorefineries vs all‐in‐one refineries. 

• The makers of enzymes compete with each other, both to supply outside projects and their 

It i b ttl t h l b iown. It is a battle over technology, business model, investment and vision. 

• Should enzymes be produced by a vertically• Should enzymes be produced by a vertically integrated company, or by a specialized third parties? p

CSIR‐IIP Process on Fuels & chemicals in a Biorefinery

From 1 Tonne sugarcane bagasse pith…………….

1000 Kg sugarcane bagasse pith

95 Kg catalytic 

40 Kg acid & 8000 L steam

furfuralsteam and acid pretreatment

231 Kg pentose sugar

conversion

biomass

5 Kg enzyme

288 Kg hexose sugar

enzymatic saccharification with enzyme 

li

biomass growth

22.5 Kg yeast cell

Xylitol

enzyme hexose sugar210 L

ethanol

recycling

gasificationfermentation

producer gas 15-20 KWe

HYGROSCOPY : lower than ethanol

% iENERGY CONTENT : 16% higher

VAPOR PRESSURE : reid Value of 0.33 psi (11 times < ethanol)

CORROSIVENESS : less and it can be stored and transportedusing existing infrastructure

BLENDING PROPERTY bl di ith li d di lBLENDING PROPERTY : easy blending with gasoline and diesel

ANTI-KNOCKING PROPERTY : as oxygenates

36

Low butanol yield / conversion

BIOBUTANOL CHALLENGES

from sugar (0.25 g/g)Microorganism sensitive tobutanol toxicity ( > 3%)

slow growth

Anaerobic microorganismsgrow at slower rate anddifficult to handle in large scale

tiGAPS

rate

anaerobicsolvent operationRecovery of butanol fromdiluted broth by distillation is

tl

GAPS anaerobic in nature

solvent toxicity

costlyEmission profile and engineperformance on biobutanolblended with gasoline and

low solvent yield

blended with gasoline anddiesel needs to be established

7

METABOLIC ENGINEERING FOR BUTANOL

LCB h d l t

SYNTHESIS ON THERMOPHILIC YEAST

hydrolysate

Pyruvate THLPathway to be constructed

Pyruvate

Acetyl CoA

AcetoacetylCoA

AcetoacetylCoA

3 h d3 h d

CrotonylCoA

CrotonylCoA

ButyrylButyryl

CRT

y

Ethanol

3-hydroxy butyryl

CoA

3-hydroxy butyryl

CoA

ButyrylCoA

ButyrylCoAHBD BCD / ETFAB

ALDH

ButyraldehydeButyraldehyde

ALDH

ADHpathway exists in

THL : tholaseHBD :3-hydroxybutyryl CoA dehydrogenaseCRT : crotonase

ButanolButanol

ADHethanologens

10

BCD/ETFAB : butyryl CoA dehydrogenase complexALDH : aldehyde dehydrogenaseADH : alcohol dehydrogenase

Process development for biobutanol fermentation

hydrolysate

hydrolysate feed

hydrolysate feed

butanol recovery

A B C D

A: storage tank for feed; B: CSTR; C: PFR; D: cell settler

cell recycle

12

BIO‐JET FROM PLANT SEED OILBIO JET FROM PLANT SEED OIL DEVELOPED BY CSIR‐IIP

BIO-JET PRODUCTION IN PILOT-PLANT AT CSIR-IIP

Capacity: 100 kg feed/day.

125 Liters of Bio‐Jet Fuel preparedp p

The Bio‐Jet Fuel Meets all the MajorSpecifications for Aviation‐Fuel.

300 Liters of Bio‐Jet Fuel to beprepared for OEM Engine‐Test

Algal Biofuel Technologyg gy

BIOCHEMICAL CONVERSION TO RENEWABLE HYDROCARBONSHYDROCARBONS

Lactic Acid from Biomass by Consolidated Bio‐Processing

Pretreated Biomass L‐lactic acidBiomass

Biofuel activities at CSIR‐IIP

PATENT GRANTED

Strain and a Novel Process for ethanol production from lignocellulic Biomass at HighTemperature; Adhikari Dilip Kumar, Sachin Kumar, Sharma Chandra Dutt, Deep

PATENT GRANTED

p ; p , , , pChand; US Patent: US 8,268,600 B2 Sep. 18, 2012.

PATENT FILEDPATENT FILED

D K Adhikari, Savita Kaul, Debashish Ghosh, Deepti Agarwal, Rashmi, DiptarkaDasgupta, Sunil K Suman, Dinesh Bangwal, M S Negi, U K Jaiswal, Pankaj K Arya, RK J i V h V Th k R M M h Di k P d Dh d K (2012)K Jain, Vasantha V Thakur, R M Mathur, Diwaker Pandey, Dhermendra Kumar (2012)Process for production of renewable fuel and chemicals in a biorefinery from bagassepith; Patent Application No 3444Del 2012 filed on 7-11-2012

Catalytic Fast Pyrolysis of LignocellulosicBiomass into Automotive FuelsBiomass into Automotive Fuels

Status of major fast pyrolysis technologies

Reactor Technology Owned by Capacity,TPD

ConstructionYear

Location Biomass Application Status

INTERNATIONAL STATUS:CFB Ensyn Ensyn 100 2007 Renfrew,

OntarioCHP In 

operation pAblative Pytec Pytec 6 2005 Hamberg,

GermanyCHP In 

operationBFB Dynamotiv Dynamotiv 20 2007 Guleph,

O t iHydrocarbo

e e Ontario,Canada

ns

RCR BTG GentingBio‐Oil Sdn

50 2005 Malaysia Empty fruit 

Energy  In operation

Bhd bunch p

INDIA STATUS:India does not have any single commercial fast pyrolysis technology as of now.y g py y gy

ObjectiveCatalytic fast pyrolysis of lignocellulosic biomass into hydrocarbons

Feedstock planned

Catalytic

p

Hydrocarbons Rice Straw

Catalyticfast  

pyrolyzerHydrotreater

Poplar woodPoplar wood

Pine wood Metal oxide catalyst Zeolite catalyst

Proposed process

Automotive Fuel

H dHydrotreaterGases

Catalytic reactor

Stable bio‐oil

Gases recycle

Catalytic reactor

Soot separatorSoot

Aqueous fraction

Catalyst /char separator

Catalyst regeneartorBiomass 

Pretreatment

Novel 

Catalytic 

fluidized bed

Drying & Grinding

Off gasesBiomass

fluidized bed

pyrolyzer

Features of fluidized bed reactor 

Uniform temperature across the riser 

i h h & f

Dynamotive BFB Reactor

Higher heat & mass transfer

Easy scale up

Suitable for large throughputs

ENSYN‐RTP CFB ReactorCSIR‐IIP BFB Reactor

Scheme on Advanced Fuel Technology

algal strain selection 

oil  rich algal cell

growth / harvesting

biomassLCB

hydrolysis / saccharification

fermentable sugars

yeast bioconversion

lipid rich yeast  cell

oil extraction from wet algae / yeast cell

hydrocarbons(fuels)

gasoline / Jet fuel / diesel / aromatics /

algal / yeast  oil

de‐oiled algal / yeast cake

lignin rich leftover biomass

N I N G

testing and 

aromatics / petrochemicalscatalytic 

conversionpyrolysis / catalytic conversion

R E F I N evaluation in 

enginesVGO

Bi CBMBio‐CBM

FACILITIES

Biomass Fast PyrolysisBiodiesel Pilot Plant

BFDBioreactors