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HYDROGEN
Water + energy hydrogen + oxygen


Hydrogen + oxygen water + energy
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 Hydrogen is ~75% of the known universe

 On earth, it’s not an energy source like oil or coal
Only an energy carrier like electricity or gasoline —
a form of energy, derived from a source, that can be
moved around

 The most versatile energy carrier
- Can be made from any source and used for any
service
- Readily stored in large amounts

 Almost never found by itself; must be liberated
- “Reform” HCs or CHs with heat and catalysts
- “Electrolyze” water (split H
2
O with electricity)
- Experimental methods: photolysis, plasma,
microorganisms,…

 1 kg of H
2
contains same energy as 1 gallon
of gasoline, which weighs 6.2 pounds

Why is hydrogen so important?
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 All fuels produce hazardous gases, but…

 Hydrogen is comparably or less so, but
different:

 Clear flame, not visible from a distance and no
smoke

 Hard to make explode; can’t explode in free
air; burns first

 22× less explosive power


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Where Does Hydrogen Come From?

95% of hydrogen is currently produced by steam reforming
Partial Oxidation
Steam Reforming
Electrolysis
Thermochemical
Fossil Fuels
Water
Biomass
currently most energy
efficient
requires improvements
not cost effective
requires high
temperatures
Gasification
Microbial
requires
improvements
slow
kinetics
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Sources of hydrogen
• Hydrogen is one of the most abundant
element in the universe.

• It can be produced from various sources as
75% of the materials contains hydrogen
atoms.

• Water is an important source for hydrogen
production using electrolysis.
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Biological/fermentation

Acetate formation
C6H12O6 + 2H2O ------- 2CH3COOH + 2CO2 +4H2
Butyrate formation
C6H12O6 -----CH3CH2CH2COOH + 2CO2 +2H2
Propionate formation
C6H12O6 +2H2O --- 2CH3CH2COOH + 2H2
Acetate + Ethanol production
C6H12O6 + 2H2O → CH3CH2OH + CH3COOH + 2H2
+ 2CO2
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Why Biomass to hydrogen?

• Biomass has the potential to produce hydrogen
as a major fuel of the future.

• Biomass is renewable, consumes atmospheric
CO
2
during growth and is able to recycle CO
2.


• Biomass is abundantly available in the form of
residual crops and wastes
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H
2
From Biomass
Biomass conversion technologies are

1. Fischer Troph Reaction
The Fischer–Tropsch process is a collection of chemical reactions that
converts a mixture of carbon monoxide and hydrogen into liquid
hydrocarbons
1. Pyrolytic gasification
2. Biological treatment of biomass
3. Thermochemical H2 production

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Pathways From Biomass to H
2
Biomass
Thermochemical
Gasification
High Pressure
Aqueous
Pyrolysis
H
2
/CO CH
4
/CO
2
CH
3
OH/CO
2
H
2
/CO
2
CH
4
/CO
2
CH
4
/CO
2
H
2
/CO
2
H
2
/C

H
2
/CO
2
Bio-shift
Shift
Synthesis
Reforming
shift

H
2
/CO
2
Reforming
shift

H
2
/CO
2
Reforming
shift

Severe
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Pathways from Biomass to H
2
Biomass
Biological
H
2
/CO
2
Anaerobic
Digestion
Metabolic
Processing
Fermentation
CH
4
/CO
2
CH
3
CH
2
OH/CO
2
H
2
/CO
2
H
2
/C
H
2
/CO
2
Bio-shift
Reforming
shift
Pyrolysis

Reforming
shift

Photo-
biology

H
2
/O
2
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Metabolic Processing of Biomass
H
2
from biomass can also be produced by metabolic
processing to split water via photosynthesis or to
perform the shift reaction by photo biological
organisms.

An artificial leaf is developed by Harvard Professor
?
http://nocera.harvard.edu/DanielGNocera
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Direct Production of H
2
From
Biomass
• Gasification coupled with water-gas shift is the
most widely practiced process route for biomass to
H
2
.

• Thermal, steam and partial oxidation gasification
technologies are under development around the
world.

• Feedstocks include both residual crops and
agricultural and forest residues.
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Oxidative Pyrolysis

By including O
2
in the reaction separate supply of
energy is not required

Biomass + O
2
CO + H
2
+ CO
2
+ Energy


If air is used to supply O
2
then N
2
is also present.


Examples : GTI high pressure O
2
blown gasifier,
CFBD (TPS Termiska), High pressure slurry bed
entrained flow gasifier (Texaco)
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Direct Solar Gasification
• Several investigators have examined the use of
solar process heat for gasification or organic
solid wastes to produce H
2
.

• Studies have shown favourable economic
projections for solar gasification of
carbonaceous materials such as agricultural
waste to produce syn gas for producing H
2
.
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Biomass Derived Synthesis Gas
(Syn Gas) Conversion
Sponge Iron and related processes

• Steam Iron processes is one of the oldest processes for
producing H
2
from syngas. (developed as early as 1910).
Fe
3
O
4
+ 4CO 3Fe + 4CO
2
3Fe + 4H
2
O Fe
3
O
4
+ 4H
2

• Recently sponge Iron process has been extended to FeO
3FeO + H
2
O H
2
+ Fe
3
O
4

• Metal hydrides (e.g. LaNi5, and La Ni4.7 Al0.3) has also
been investigated for continuous hydrogen recovery from
biomass gasification mixtures lean mixtures.
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KEY PROCESS STEPS IN BIOMASS TO METHANOL AND H
2
Methanol
Biomass
Pretreatment, drying, chipping
Gasifier
Gas Cleaning
Reformer for higher
hydrocarbons
Shift to adjust CO/H
2
ratio
Methanol Production
H
2
Production
Gas Turbine/boiler
)
Steam Turbine
Purge gas
Hydrogen
Electricity
Electricity
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ABE
Acetone Butanol Ethanol fermentation
Acetate formation
C6H12O6 + 2H2O ------- 2CH3COOH + 2CO2 +4H2
Butyrate formation
C6H12O6 -----CH3CH2CH2COOH + 2CO2 +2H2
Propionate formation
C6H12O6 +2H2O --- 2CH3CH2COOH + 2H2
Acetate + Ethanol production
C6H12O6 + 2H2O → CH3CH2OH + CH3COOH + 2H2
+ 2CO2
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Acetone–butanol–ethanol (ABE) fermentation is a process that
uses bacterial fermentation to produce acetone, n-Butanol,
and ethanol from starch.

The process is anaerobic (done in the absence of oxygen),
similar to how yeast ferments sugars to produce ethanol for
wine, beer, or fuel.

The process produces these solvents in a ratio of 3-6-1, or 3
parts acetone, 6 parts butanol and 1 part ethanol.

It usually uses a strain of bacteria from the Clostridia Class
(Clostridium Family). Clostridium acetobutylicum is the most
well-known strain, although Clostridium beijerinckii has also
been used for this process with good results.
Background Information
Acetic Acid
MW: 60.05
bp: 117-118
°
C
Butyric Acid
MW: 88.11
bp: 162
°
C
Butanol
MW: 74.12
bp: 116 – 118
°
C
Butanol is produced as a fermentation product by bacteria;
known as, solventogenic Clostridia, when cultured on glucose-
rich media containing acetic acid and butyric acid.
-Recently, butanol has been gaining attention as a possible
alternative to petroleum-based gasoline. Much effort is
currently being made to reduce production costs to make
butanol an economically viable option.

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Acetone is the organic compound with the
formula OC(CH3)2.

This colorless, mobile, flammable liquid is
the simplest example of the ketones.

Acetone is miscible with water, and virtually
all organic solvents
More than 3 billion kilograms are produced
annually, mainly as a precursor to polymers.
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Chemically, Acetone is produced by cumene
process,
benzene is alkylated with propene and the
resulting cumene (isopropylbenzene) is oxidized
to give phenol and acetone:
C6H5CH(CH3)2 + O2 → C6H5OH + OC(CH3)2
Acetone is also produced by the direct oxidation
of propene with a Pd(II)/Cu(II) catalysts,
Vegetable oil


Plant with sugar
(sugarcane)

Plant with starch
(maize, potato,
cassava)
Plant with ligno-
cellulose

PURIFIED OIL
Synthetic
catalysis
Gasification Hydrolysis
treatment
Dehydration
Esterification
BIODIESEL
BIOMETHANOL BIOETHANOL
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Fuel Type
Specific Energy Density
(MJ/kg)
Solid Fuels
Bagasse (Cane Stalks) 9.6
Chaff (Seed Casings) 14.6
Animal Dung/Manure 10- 15
Dried plants (C
6
H
10
O
5
)
n
10 – 16
Wood fuel (C
6
H
10
O
5
)
n
16 – 21
Charcoal 30
3.6MJ=1KWh
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Liquid Fuels
Fuel Specific Energy Density
Pyrolysis oil 17.5
Methanol (CH
3
-OH) 19.9 – 22.7
Ethanol (CH
3
-CH
2
-OH) 23.4 – 26.8
Ecalene 28.4
Butanol(CH
3
-(CH
2
)
3
-OH) 36
Fat 37.656
Biodiesel 37.8
Sunflower oil (C
18
H
32
O
2
) 39.49
Castor oil (C
18
H
34
O
3
) 39.5
Olive oil (C
18
H
34
O
2
) 39.25 - 39.82
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Gaseous Fuels
Fuel Specific Energy Density
Methane (CH
4
) 55 – 55.7
Hydrogen (H
2
) 120 – 142
Fossil Fuels (comparison)
Coal 29.3 – 33.5
Crude Oil 41.868
Gasoline 45 – 48.3
Diesel 48.1
Natural Gas 38 – 50
Ethane (CH
3
-CH
3
) 51.9
• http://www.syntecbiofuel.com/butanol.php
powermin.nic.in/whats_new/pdf/IIP
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