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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