Fuel policy and Future fuels

Future fuels
Vehicular Emission Norms: - A road map for vehicular emission norms
for new vehicles would be as follows:
Coverage Passenger Cars, light commercial vehicles 2
/ 3 wheelers
& heavy duty diesel vehicles

Entire country Bharat Stage II - 1.4.2005 Bharat Stage II

1.4.2005
Euro III equivalent 1.4.2010 Bharat Stage III*
Preferably from 1.4.2008
but not later than
1.4.2010

11 major cities* Bharat Stage II - 1.4.2003

Euro III equivalent 1.4.2005
(*Delhi / NCR, Mumbai, Kolkata, Chennai, Bangalore, Hyderabad,
Euro IV equivalent* 1.4.2010
Ahmedabad, Pune, Surat, Kanpur & Agra)
- These schedules would be reviewed in the year 2006, when Euro-II
equivalent norms would be implemented in the entire country and
Euro-III equivalent norms would be implemented in 11 major cities.
Road map for emission of compliance of emission norms:

1.After 1.4.2007, inter-State buses/trucks would not be allowed to

originate/or terminate in Delhi unless they meet minimum of
India 2000 emission norms. The cut off point for meeting Bharat
Stage II norms will be 1.4.2011.

2. In respect of 10 other major cities, all inter-State buses will

have to meet w.e.f 1.4.2006 a minimum of 1996 emission norms
in case they were registered before 1.4.2000. They have to meet
w.e.f 1.4.2008, a minimum of India 2000 norms if they were
registered after 1.4.2000.

3. In respect of 10 other major cities, all inter-State buses would

need to meet a minimum of Bharat Stage-II emission norms w.e.f.
1.4.2011, if these vehicles are registered after 1.4.2005.
Energy Scenario in India
Renewable Energy
Sources
National Action Plan on Climate Change
(2010)
National Solar Mission,
National Mission on Enhanced Energy Efficiency,
National Mission on Sustainable Habitat,
National Water Mission,
National Mission for Sustaining the Himalayan Eco-
system,
National Mission for a Green India,
National Mission for Sustainable Agriculture and
National Mission on Strategic Knowledge for Climate
Change.
 Jawaharlal Nehru National Solar Miss
Objective of the National Solar Mission is to establish India as a global
leader in solar energy, by creating the policy conditions for its diffusion
across the country as quickly as possible.

The Mission will adopt a 3-phase approach, spanning

the remaining period of the 11th Plan and first year of the 12th Plan (up
to 2012-13) as Phase 1,
the remaining 4 years of the 12th Plan (2013-17) as Phase 2
and the 13th Plan (2017-22) as Phase 3.

At the end of each plan, and mid-term during the 12th and 13th Plans,
there will be an
evaluation of progress, review of capacity and targets for subsequent
phases, based
on emerging cost and technology trends, both domestic and global.

The aim would be to protect Government from subsidy exposure in case

expected cost reduction does not materialize or is more rapid than
expected.
The immediate aim of the Mission is to focus on setting up an enabling
environment for solar technology penetration in the country both at a
centralized and decentralized level.

The first phase (up to 2012- 2013) will focus on capturing of the low-
hanging options in solar thermal; on promoting off-grid systems to serve
populations without access to commercial energy and modest capacity
addition in gridbased systems.

In the second phase, after taking into account the experience of the initial
years, capacity will be aggressively ramped up to create conditions for up
Mission targets are:
scaled and competitive solar energy penetration in the country
To create an enabling policy framework for the deployment of 20,000 MW of s
power by 2022.

To ramp up capacity of grid-connected solar power generation to 1000 MW wi

three
years by 2013; an additional 3000 MW by 2017 through the mandatory use
the
renewable purchase obligation by utilities backed with a preferential tariff.

This capacity can be more than doubled reaching 10,000MW installed power
2017
 The ambitious target for 2022 of 20,000 MW or more, will be dependent
on the learning of the first two phases, which if successful, could lead to
conditions of grid-competitive solar power. The transition could be
appropriately up scaled, based on availability of international finance and
technology.
To create favourable conditions for solar manufacturing capability,
particularly solar thermal for indigenous production and market leadership.

To promote programmes for off grid applications, reaching 2000 MW by

2022 including 20 million solar lighting systems.

To achieve 20 million sq. solar thermal collector area by 2022.

 Biomass to fuel

Plant biomass, treated

industrial and municipal
wastes
Classification of biofuel
Technology Roadmap for 2nd
Generation Biofuels
National Policy on Biofuel
National Policy on Biofuel (2009)
Expected role of biofuel
First Generation (Conventional) Bi
Renewable Energy in India An
Overview
Ethanol utilization facts
Ethanol availability in India
 (Lignocellulosic Ethanol)
Lignocellulosic Biomass
Non starch based fibrous part of plant
material Lignin
Provides structure and rigidity to the plant Cellulose

Hemicelluloses

grass Corn Baggasse Wood chips

Stover
Lignin structure
Indias biomass production
Ethanol production routes
Approach

Creation Biofuels
(controlled supply of (by Green
energy, Process)
Water and Nutrients)

En Biomass
e CH1.4O0.7
rg Hydrotherma
y l Breakdown
(Excess supply of Bioethanol
Heat and Water

CO2

Water Biocrude

Nutrients (N, P,
K) Biochar
Water is a non-toxic, environmentally benign and
inexpensive
3
Ligno-cellulosic Pyrolysis Acids
Biomass Alcohols
Aldehydes
Bio-oil Ketones
Furan
Phenols
Sugars

Catalytic steam reforming of some oxygenated

molecules such as MeOH, Acetic acid, Ethanol,
Acetone, Phenol, Glycerol or Cresol, can be used as a
model compounds of Bio-Oils.
Steam reforming of such a mixture is very difficult
due to extensive coke formation and catalyst
deactivation.
 Pyrolysis followed by
reforming of
carbohydrate fraction of bio-
oil processes for the
Bio-oil is the basis of several
development of fuel chemicals and materials. (~172 g
H /kg bio-oil (11.2% based on wood)
2

Step : use of heat to dissociate complex molecules

into simple units.
Biomass + Energy Bio-oil +
Char + Gas
 Bio-oil + H2O CO + H2.

CO + H2O CO2 + H2.

The overall stoichiometry gives a maximum yield of

172 g H2/kg bio-oil (11.2% based on wood)

CH1.9O0.7 + 1.26 H2O CO2 + 2.21 H2.

Catalytic reactivation and high steam to biomass ratios

diminish the rate of deactivation
 For generic oxygenated molecule, the steam reforming
reaction proceeds according to the following equation:

CnHmOk + (n-k)H2O nCO + (n+(m/2)-k)H2 (SR)

nCO + nH2O nCO2 + nH2 (WGS)

Overall Process can be represented as follows:

CnHmOk + (2n-k)H2O nCO2 + (2n+(m/2)-k)H2

The thermal decomposition has also to be considered for most of the

oxygenated organic compounds.
CnHm Ok CxHyOz + Carbon + Gases (H2, CO,CO2, CH4, CxHx+2)

Development of catalyst for the conversion of these oxygenates will help in

the utilization of biomass as a sustainable source for hydrogen.
Hydrothermal Medium: Advantages and
Challenges
Hot compressed water either in liquid (subcritical) or
supercritical state is defined as hydrothermal medium

Advantages
No drying of biomas
Not dependent on the type of biomass
Reduced mass transfer resistance
Flexibility for the type of fuels (solid, liquid, and
gas)
Easier product separation
Challenges
Biomass feeding at high pressure specially for lab scale
studies
Salt precipitation and corrosion
Coking and deactivation of heterogeneous catalyst 38
Biocrude

Biocrude is defined as the solubilized fraction of

biomass after hydrothermal treatment
Hydrotherma
l Hydrogen
SCWR*
Lignocellulos Liquefaction Biocrud 141.9 MJ/kg

e e
17.5-18.1 MJ/kg APR** Liquid
Fuels/
Liquefaction proceeds Hydrogen
46.7 MJ/kg
through
Depolymerization of cellulose, hemicelluloses,
and lignin
Chemical and thermal decomposition
* SCWR: Supercritical water reforming
** APR: Aqueous phase reforming
39
 Biocrude Production from biomass using
Subcritical Water

Objectiv
e
Study the liquefaction of biomass in subcritical water
to produce biocrude
Effect of temperature and alkali (K2CO3) addition on
biomass liquefaction
Products characterization for understanding the
biomass decomposition process
40
 Reaction Pathway of Biomass
Cellulose

Cleavage of glycosidic linkages and endwise degradation

(peeling)

cellulose glucose decomposition products

Hemicellulose

Swelling, dissolution, peeling and glycosidic cleavage reactions

Lignin

Cleavage of aryl ether linkages, fragmentation, dissolution and

re-polymerization
Biomass components interact with each other,
and leads to a very complex chemistry

41
Product Separation and
Analysis
Biomass

Gas (Vent)
Liquid Solid

At Phase Separator In Reactor

Biocrude

Aqueous Solid Biochar

Phase Precipitate

TOC
HPLC
XRD XRD, FT-IR, SEM
GC-MS
Heating value Composition
42
Composition
 Hydrothermal Carbonization of biomass for
Biochar Production
Biochar: Solid carbonaceous product having high energy density resulting
from the thermal degradation of biomass

Hydrothermal

Lignocellulose Biochar
Carbonization
17.5-18.1 MJ/kg 27.0-28.0 MJ/kg

Challenges
Low energy density of lignocellulosic biomass
High moisture content
Fibrous structure of biomass brings engineering challenges in
43
material handling
Overall biorefinery concept
- a new chemical industry sector
Challenges in Production of H/C oil from Pyro oil
 Major research thrust is removal of oxygen from
biomass derived pyro oil with minimum H2
consumption. HDO must be carried out without
saturation of Aromatics.
Bio oil contains high MW substances but do not have
long hydrocarbon chain as in petroleum feed. Hydro
cracking catalyst will have to be adapted to
accommodate the differences.
Key technical problem is the answer to how to open
up the inaccessible solid fibrous woody material
( Cellulose ) so that it can be effectively transformed
 Biofuel value chain

Biomass resources Supply systems Conversion End products

Chemical Transportation fuels

Oil bearing plants (transesterification) (biodiesel, bioethanol)
Harvesting,
Agricultural crops Physical chemical Solid fuels
and residues collection, (extraction) (wood pellets, charcoal)

Woody biomass handling, Biochemical Heat

(fermentation) Electricity
Industrial and and storage
municipal waste Thermochemical High added-value
(gasification) chemicals
(pharmaceuticals,
polymers)
 Biomass to high added value chemicals,
an emerging chemistry

Biomass

Extraction Biodiesel Sugar Thermochemical

of chemicals production fermentation conversion

Proteins Ethanol
Glycerol Lactic acid Bio-SNG
Vitamins
Fragrances
Pharmaceuticals Chemicals Chemicals Chemicals
 Fischer-Tropsch
Technology
Steam
Gas-to-Liquids (GTL) Power
Synthesis Fischer

Gas Clean-up
Natural gas
Gas
Generation
CO + H2 Tropsch Tail gas
Synthesis
Biomass/Coal-to-Liquids
(BTL/CTL) CO2 Sequestration
Oil Recovery
Coal/Biomass Enhancement
Petroleum coke
Production
Separation
& Upgrading

Diesel Naphtha
DIAGRAM OF APPROXIMATE REACTION CONDITIONS FOR THE CATALYTIC PROCESSING OF

PETROLEUM VERSUS BIOMASS-DERIVED CARBOHYDRATES

 Algae are photosynthetic efficient organisms with rapid
growth and can double biomass in a day
Algae can be grown on non-arable land in saline water.
The estimated yield for biodiesel production from algae is
very high as compared
to other sources and require less land.
Some Funding agencies for Biofuel
research
Biomass as a Source of Hydrogen
 Water
Tc= 374 oC
Pc= 221 bar
Supercritical
c= 0.375 g cm-3 Region

Path from liquid to vapor without
encountering a phase transition
Pressure

Critical Point
Liquid

Solid Gas

Triple Point

Temperature
Tuning Water Properties for Biofuels
Application

60
Is Supercritical water different
than ambient water?

Water is environmentally benign and inexpensive

Supercritical water is like an organic
solvent!

Kritzer and Dinjus, Chemical Engineering Journal (2001), 83(3), 207-214

Expected Advantage of Gasification in
supercritical water

Homogeneous reaction mixture allows lowering

the impact of resistance caused by transport
phenomena in a heterogeneous reaction

High solid conversion resulting in a low level of

solid residue

Hydrogen yield approaches stoichiometric limit

due to the operating conditions

Hydrogen is produced at high pressure directly,

which means smaller reactor volume and lower
operating costs due to reduced compression costs
Hydrogen Production in Supercritical
Water

Direct high-pressure H2 is obtained

Compact reactors: reactions time in seconds
In-situ separation
Energy integration
Possible use of sulfur containing fuels
Carbon dioxide can be easily sequestered
Avoids char formation
 SCW H2 Production Apparatus
T
T

Rupture
Feed disc Tubular reactor Water cooled
tank P Back
heat exchanger pressure
regulator

HPLC pump Tube furnace with

temperature
controller

GC with
TCD

Gas flow
6-port injection meter
valve for online Glass
sampling phase
Peak analysis on Data acquisition separator
PC system

Liquid phase
TOC analysis
Mass flow rate
Thoughts:Why a short reaction
time should be better?

CH3OH -2
3H
2

+ ol 92 H2
O
J/m kJ/
-H 1k
2
m
ol
-5
- H2O + H2
- 41 kJ/mol
CO2 CO
H2
-3 l
l
/mo

131 2 - H2
O

ol
H 2 J /m o

kJ/m
-

+
4H 2

6k

l
J

kJ/mo
k
H 2O

O
20
165

2
+H

+ CO
2

173
+

- 2H2
75 kJ/mol
CH4 C
Glucose Reforming (Thermal)
Desired reaction: C6H12O6 + 6H2O 6CO2 +
12H2

Typical Composition (mol%)

Conditions H2 CO CH4 CO2

T=700C, P=3600
psi, 1.0 wt%
glucose 54.0% 1.7% 10.2% 34.1%
Methane Suppression is Needed

Methane has much lower value than H2

Each mole of methane takes away

Two moles of H2

One mole of carbon (equivalent to 2 moles of H2)

 Glucose Reforming (Catalytic)

Typical Composition (mol%)

Conditions H2 CO CH4 CO2 H2 Yield
T=700C, P=3600
psi, 1.0 wt%
glucose 68.9% 0.1% 1.3% 29.8% ~12
Glucose Reforming (Catalytic)

Typical Composition (mol%)

Conditions H2 CO CH4 CO2 H2 Yield

T=700C, P=3600 psi,

5.0 wt% glucose 64.7% 1.3% 5.1% 28.9% ~10
 Observations

Supercritical water gasification is a suitable

technique for hydrogen production from
Oxygenates since H2 is produced directly at high
pressure.

Hydrogen yield from biomass materials can be

maximized by reducing methane formation by
lowering the residence time so that equilibrium
is not allowed to be reached

The energy recovery is the key point in the

supercritical water reforming of biomass material
as the endothermic chemical reaction needs
high temperature
 On Board Hydrogen Storage : Challenges
Fuel Total Fuel wt Tank wt(lb) Total fuel Volume(g
energy (lb) system al)
(Btu) wt(lb)

5 gallon 629,500 30.8 14 45 5

gasoline

Liquid 629500 10.3 41 51 47

Hydrogen(
20K)

Metal hydride 629500 10.3 1210 1220 50

FeTi(1.2%)

Compressed 629500 10.3 140-190 150-200 108-60

Hydrogen(
207-690
bar)
Typical cost of Hydrogen production

Feed stocks Process Tech Approximate cost(in

dollars per gallons of
gas
equivalent(GGE))

Natural gas Steam reforming $ 3/GGE

Nuclear Electrolysis of water $2.5/GGE

Solar Electrolysis of water $9.5/GGE

Wind Electrolysis of coal $3.0/GGE

Biomass Steam reforming $1.9/GGE

Coal gasification $1.0/GGE

 Towards Sustainable Mobility
Government Auto Manufacturers
Energy-Mix Strategy FC Technology
Codes and Standards Cost
Vehicle Attractiveness

Fuel Industry Universities

Technical Schools
bio oil/ H2 Production,
Distribution and
Biofuel/ Human Resource
Hydrogen- Development
Storage Technology
H2 Storage Technology
Hydrogen Based
Infrastructures Basic Research (XTL)
Society

R&D Organizations
General Public
R&D on FC
Understanding of a
XTLH2 Production,
Biofuel/ Hydrogen
Society Distribution and
Awareness Storage Technology
(Incl. CO2 Sequestration)