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BIOHYDROGEN

1

Presented by:
Mr.Darshan Gowda
BTL(H)007
Contents


Introduction



Hydrogen properties



Hydrogen production methods



Bio hydrogen & its
History
production methods

Economics


Conclusion



Reference

2
Why we need alternative fuel.?

3

Fossil fuel resources
are


Limited



green house gases
4
Understanding the hydrogen5


Hydrogen is the first element on the periodic
table, making it the lightest element on earth.



0.00005% in air



It rises in the atmosphere and is therefore rarely
found.



pure hydrogen gas, burning in air, producing
water and heat.



Combustion heat enables hydrogen to act as a
fuel.
Hydrogen properties


Colorless and odorless



Extremely reactive with oxygen and other
oxidizers.



Low ignition energy.



High flame temperature.



Invisible flame in daylight conditions.



Small molecular size promotes leaks and diffusion.



The cryogenic liquid at 20K is even colder than
frozen nitrogen, oxygen or argon.

6
Key facts about Hydrogen as
a fuel

7

Highly combustible and can be used as a fuel.
1g of combustion provides 30000 cals as compared to gasoline
that

gives only 11000 cals.

Can be produced from water using Biological agents.

Biologically produced hydrogen is known as Biohydrogen.
Hydrogen Production
1. Electrolysis.
2. Steam-methane reforming process.

3. Biological process(bio-hydrogen).


Hydrogen production always requires more
energy than can be retrieved from the gas as
a fuel later on when they are produced by above
two process.

8
Simple setup for demonstration
of electrolysis of water.

9
Biological production

10



Biological hydrogen production stands out as
an environmentally harmless process carried
out under mild operating conditions, using
renewable resources.



Several types of microorganisms such as the
photosynthetic bacteria, cyano bacteria, algae
or fermentative bacteria are commonly utilized
for biological hydrogen production.
Milestones

11

discovered that algae can switch
between producing O2 and H2.



1939 Hans Gaffron



1997 prof. Anastasios Malis discovered



2006

that deprivation of
sulphur will cause the algae to switch from producing
H2.He found that enzyme hydrozenase responsible
for the reaction.
Researcher from the University of Bielfeld have
genetically changed the single cell Chlamydomonas
reinhardtiiin in such a way that it produces an large
amount of hydrogen.
12



2007 It was discovered that if cupper is added to
block O2 generation in algae.



2007 prof. Anastasios Malis studying solar to chemical
energy conversion efficiency in tax X mutants of
Chlamydomonas reinhardtiiin , achieved 15% efficiency .
Methods of Bio hydrogen
Production
1.Dark Fermentation
2.Photo Fermentation
3.Combined Fermentation
4.Direct Photolysis (algae)
5.Indirect Photolysis (cynobacteria)

13
1. Dark Fermentation

14

Fermentative conversion of organic substrate to
biohydrogen.
This method doesn’t require light energy.
The Gram+ve bacteria of Clostridium genus is of
great potential in biohydrogen production.
Require wet carbohydrate rich biomass as a
substrate.
Produces fermentation end product as organic
acids, Co2 along with biohydrogen.
C6H12O6 + 2H2O

2CO2

2CH3COOH + 4H2 +
15

Glu

pyruvate

acetylcoA

fd

H2


Carbohydrate mainly glucose is preffered.



Pyruvate the product of glucose catabolism is oxidized to
acetyl-coA requires ferrodoxin reduction.



Reduced ferrodoxin is oxidized by hydrogenase which
generates ferrodoxin and release electron as a molecular
hydrogen.
Advantages

16



It produces valuable metabolites as a butyric acid,
propionic acid.



It is an anaerobic process so no oxygen limitation.



It can produce carbon during day and night.



Variety of carbon sources can be used as a substrate.
Drawbacks

17



Relatively lower achievable yield of H2, as a portion
of substrate is used to produce organic acids.



Anaerobes are incapable of further breakdown of
acids.



Accumulation of this acids cause a sharp drop of
culture pH and subsequent inhibition of bacterial
hydrogen production.



Product gas mixture contains Co2 which has to be
separated.
Approaches to overcome

18



Metabolic shift of biochemical pathway to
arrest the formation of acid and alcohol.



To improve the techniques for the seperation of
the gases.
2.Photo Fermentation

19

Purple non sulphur bacteria genus rhodobacter
holds significant promise for production of
hydrogen.

Photo fermentation where light is required as a
source of energy for the production of hydrogen
by photosynthetic bacteria.

Organic acids are preferred as a substrate.
The

light energy required in this process is
upto the range of 400nm.
Mechanism

20

CH3COOH + 2H2 + Light  4H2 + 2Co2

Production of hydrogen by photosynthetic
bacteria takes place under illumination and in
the presence of inert and anaerobic atmosphere
for the breakdown of organic substrate to
produce hydrogen molecules.
Advantages




Relatively higher achievable yield of H2, as a
portion of substrate is used to produce organic
acids.
Anaerobes are capable of further breakdown of
acids in to biohydrogen.

Drawbacks
 It can produce carbon during day only.

21
Combined fermentation

22



The combination of dark and photo fermentation
provides an integrating system for maximization of an
hydrogen yield.



The idea of combined fermentation takes into an
consideration the very fact of relatively lower achievable
yield of H2 in dark fermentation.



The non utilization
fermentation.

of

acid

produced

in

dark
Mechanism

23

Stage 1 :- Dark fermentation: Anaerobic
fermentation
of
carbohydrate
produces intermediates such as low molecular
weight organic acids and Co2 along with
hydrogen.
Stage 2:- Light fermentation


The low mol wt organic acid in stage 1 are converted to hydrogen
by photosynthetic bacteria.



2CH3COOH + 4H2o

 CH3COOH + 2Co2 + 4H2

24
Advantages

25

Two stage fermentation can improve the
overall yield of hydrogen and overcomes the
major limitation of dark fermentation.

Drawbacks:Relatively new approach techno economic
feasibility is yet to studied
4.Direct Photolysis

26



Certain green algae produces H2 under anaerobic
condition.



Under deprived of S green algae Chlamydomonas reinhardtiiin

become anaerobic in light & commence to synthesis of
hydrogen.
27

Direct Photolysis
Molecular aspects

28

Light Absorption by Photo system II (PSII) Initiates the
Photosynthetic Pathway.

PSII is a large molecular complex that contains several
proteins and light-absorbing pigment molecules like
carotenoids, chlorophylls and phycobilins.

The

reaction center strips electrons from two water
molecules, releasing four protons and an oxygen (O2)
molecule into the thylakoid space.
29

The

electron carrier from PSII passes through the
thylakoid membrane and transfers its electrons to the
cytochrome complex, which consists of several
subunits including cytochrome f and cytochrome b6.

A

series of redox reactions within the complex
ultimately transfer the electrons to a second electron
carrier i.e. photo system I (PSI).

As

electrons are transported through the complex,
protons (H+) outside the thylakoid are carried to the
inner thylakoid space.
30

Light Absorption by PSI Excites Electrons and Facilitates

Electron Transfer to an Electron Acceptor Outside the
Thylakoid Membrane.

Light

absorbed by the PSI reaction center energizes an
electron that is transferred to ferredoxin (Fd), a molecule
that carries electrons to other reaction pathways outside the
thylakoid.

The

reaction center replaces the electron transferred to
ferredoxin by accepting an electron from the electron-carrier
molecule that moves between the cytochrome and the PS1
31

Under

Certain Conditions, Ferredoxin can
Carry Electrons to Hydrogenase.

Normally,

ferredoxin shuttles electrons to an
enzyme that reduces NADP+ to NADPH, an
important source of electrons needed to convert
CO2 to carbohydrates in the carbon-fixing
reactions.

Under anaerobic conditions, hydrogenase can
accept electrons from reduced ferredoxin
molecules and use them to reduce protons to
molecular hydrogen (H2).
4H+ + ferredoxin(oxi) ――› ferredoxin(reduced)
H

co2 o2

Sunlight
Algae
production
Bioreactor
(Light
Aerobic)

Algae
Concentra
tor and
adapter
(DarkAnaerobic
)

A
L
G
A
E

32

Sunlight
H2

Photobioreactor
(light anerobic)

H2
H2

Nutrient
recycle
Algae Recycle
Fig:- Schematic of Hydrogenase mediated Biophotolysis process
Economics


The US department of energy has targeted a selling price
of $2.60/kg as goal for making renewable hydrogen
economically viable.



1kg is approximately the energy equivalent to a gallon of
gasoline.



To achieve this , the efficiency of light to hydrogen
conversion must reach 10% while current efficiency is only
1% and selling price is estimated at 13.53/kg.

33
Reference


Hand book of bioenergy and biofuels – V K mutha



Journal on Bio hydrogen production aspotential
energy resources by Kaushik & D Das.



Bio biohydrogen – Microbiological production of
hydrogen fuel by P C Hallebeck & J R Bennemen

34
Conclusion

35



Bio hydrogen is fuel of future



Areas of research to increase efficiency include developing
of oxygen tolerant hydrogenase and increased hydrogen
production rates.



Research on cost effective production of bio hydrogen for
commercialization is required.
Thank you

t

36

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Biohydrogen Production Methods and Potential

  • 2. Contents  Introduction  Hydrogen properties  Hydrogen production methods  Bio hydrogen & its History production methods Economics  Conclusion  Reference 2
  • 3. Why we need alternative fuel.? 3 Fossil fuel resources are  Limited  green house gases
  • 4. 4
  • 5. Understanding the hydrogen5  Hydrogen is the first element on the periodic table, making it the lightest element on earth.  0.00005% in air  It rises in the atmosphere and is therefore rarely found.  pure hydrogen gas, burning in air, producing water and heat.  Combustion heat enables hydrogen to act as a fuel.
  • 6. Hydrogen properties  Colorless and odorless  Extremely reactive with oxygen and other oxidizers.  Low ignition energy.  High flame temperature.  Invisible flame in daylight conditions.  Small molecular size promotes leaks and diffusion.  The cryogenic liquid at 20K is even colder than frozen nitrogen, oxygen or argon. 6
  • 7. Key facts about Hydrogen as a fuel 7 Highly combustible and can be used as a fuel. 1g of combustion provides 30000 cals as compared to gasoline that gives only 11000 cals. Can be produced from water using Biological agents. Biologically produced hydrogen is known as Biohydrogen.
  • 8. Hydrogen Production 1. Electrolysis. 2. Steam-methane reforming process. 3. Biological process(bio-hydrogen).  Hydrogen production always requires more energy than can be retrieved from the gas as a fuel later on when they are produced by above two process. 8
  • 9. Simple setup for demonstration of electrolysis of water. 9
  • 10. Biological production 10  Biological hydrogen production stands out as an environmentally harmless process carried out under mild operating conditions, using renewable resources.  Several types of microorganisms such as the photosynthetic bacteria, cyano bacteria, algae or fermentative bacteria are commonly utilized for biological hydrogen production.
  • 11. Milestones 11 discovered that algae can switch between producing O2 and H2.  1939 Hans Gaffron  1997 prof. Anastasios Malis discovered  2006 that deprivation of sulphur will cause the algae to switch from producing H2.He found that enzyme hydrozenase responsible for the reaction. Researcher from the University of Bielfeld have genetically changed the single cell Chlamydomonas reinhardtiiin in such a way that it produces an large amount of hydrogen.
  • 12. 12  2007 It was discovered that if cupper is added to block O2 generation in algae.  2007 prof. Anastasios Malis studying solar to chemical energy conversion efficiency in tax X mutants of Chlamydomonas reinhardtiiin , achieved 15% efficiency .
  • 13. Methods of Bio hydrogen Production 1.Dark Fermentation 2.Photo Fermentation 3.Combined Fermentation 4.Direct Photolysis (algae) 5.Indirect Photolysis (cynobacteria) 13
  • 14. 1. Dark Fermentation 14 Fermentative conversion of organic substrate to biohydrogen. This method doesn’t require light energy. The Gram+ve bacteria of Clostridium genus is of great potential in biohydrogen production. Require wet carbohydrate rich biomass as a substrate. Produces fermentation end product as organic acids, Co2 along with biohydrogen. C6H12O6 + 2H2O 2CO2 2CH3COOH + 4H2 +
  • 15. 15 Glu pyruvate acetylcoA fd H2  Carbohydrate mainly glucose is preffered.  Pyruvate the product of glucose catabolism is oxidized to acetyl-coA requires ferrodoxin reduction.  Reduced ferrodoxin is oxidized by hydrogenase which generates ferrodoxin and release electron as a molecular hydrogen.
  • 16. Advantages 16  It produces valuable metabolites as a butyric acid, propionic acid.  It is an anaerobic process so no oxygen limitation.  It can produce carbon during day and night.  Variety of carbon sources can be used as a substrate.
  • 17. Drawbacks 17  Relatively lower achievable yield of H2, as a portion of substrate is used to produce organic acids.  Anaerobes are incapable of further breakdown of acids.  Accumulation of this acids cause a sharp drop of culture pH and subsequent inhibition of bacterial hydrogen production.  Product gas mixture contains Co2 which has to be separated.
  • 18. Approaches to overcome 18  Metabolic shift of biochemical pathway to arrest the formation of acid and alcohol.  To improve the techniques for the seperation of the gases.
  • 19. 2.Photo Fermentation 19 Purple non sulphur bacteria genus rhodobacter holds significant promise for production of hydrogen. Photo fermentation where light is required as a source of energy for the production of hydrogen by photosynthetic bacteria. Organic acids are preferred as a substrate. The light energy required in this process is upto the range of 400nm.
  • 20. Mechanism 20 CH3COOH + 2H2 + Light  4H2 + 2Co2 Production of hydrogen by photosynthetic bacteria takes place under illumination and in the presence of inert and anaerobic atmosphere for the breakdown of organic substrate to produce hydrogen molecules.
  • 21. Advantages   Relatively higher achievable yield of H2, as a portion of substrate is used to produce organic acids. Anaerobes are capable of further breakdown of acids in to biohydrogen. Drawbacks  It can produce carbon during day only. 21
  • 22. Combined fermentation 22  The combination of dark and photo fermentation provides an integrating system for maximization of an hydrogen yield.  The idea of combined fermentation takes into an consideration the very fact of relatively lower achievable yield of H2 in dark fermentation.  The non utilization fermentation. of acid produced in dark
  • 23. Mechanism 23 Stage 1 :- Dark fermentation: Anaerobic fermentation of carbohydrate produces intermediates such as low molecular weight organic acids and Co2 along with hydrogen.
  • 24. Stage 2:- Light fermentation  The low mol wt organic acid in stage 1 are converted to hydrogen by photosynthetic bacteria.  2CH3COOH + 4H2o  CH3COOH + 2Co2 + 4H2 24
  • 25. Advantages 25 Two stage fermentation can improve the overall yield of hydrogen and overcomes the major limitation of dark fermentation. Drawbacks:Relatively new approach techno economic feasibility is yet to studied
  • 26. 4.Direct Photolysis 26  Certain green algae produces H2 under anaerobic condition.  Under deprived of S green algae Chlamydomonas reinhardtiiin become anaerobic in light & commence to synthesis of hydrogen.
  • 28. Molecular aspects 28 Light Absorption by Photo system II (PSII) Initiates the Photosynthetic Pathway. PSII is a large molecular complex that contains several proteins and light-absorbing pigment molecules like carotenoids, chlorophylls and phycobilins. The reaction center strips electrons from two water molecules, releasing four protons and an oxygen (O2) molecule into the thylakoid space.
  • 29. 29 The electron carrier from PSII passes through the thylakoid membrane and transfers its electrons to the cytochrome complex, which consists of several subunits including cytochrome f and cytochrome b6. A series of redox reactions within the complex ultimately transfer the electrons to a second electron carrier i.e. photo system I (PSI). As electrons are transported through the complex, protons (H+) outside the thylakoid are carried to the inner thylakoid space.
  • 30. 30 Light Absorption by PSI Excites Electrons and Facilitates Electron Transfer to an Electron Acceptor Outside the Thylakoid Membrane. Light absorbed by the PSI reaction center energizes an electron that is transferred to ferredoxin (Fd), a molecule that carries electrons to other reaction pathways outside the thylakoid. The reaction center replaces the electron transferred to ferredoxin by accepting an electron from the electron-carrier molecule that moves between the cytochrome and the PS1
  • 31. 31 Under Certain Conditions, Ferredoxin can Carry Electrons to Hydrogenase. Normally, ferredoxin shuttles electrons to an enzyme that reduces NADP+ to NADPH, an important source of electrons needed to convert CO2 to carbohydrates in the carbon-fixing reactions. Under anaerobic conditions, hydrogenase can accept electrons from reduced ferredoxin molecules and use them to reduce protons to molecular hydrogen (H2). 4H+ + ferredoxin(oxi) ――› ferredoxin(reduced)
  • 32. H co2 o2 Sunlight Algae production Bioreactor (Light Aerobic) Algae Concentra tor and adapter (DarkAnaerobic ) A L G A E 32 Sunlight H2 Photobioreactor (light anerobic) H2 H2 Nutrient recycle Algae Recycle Fig:- Schematic of Hydrogenase mediated Biophotolysis process
  • 33. Economics  The US department of energy has targeted a selling price of $2.60/kg as goal for making renewable hydrogen economically viable.  1kg is approximately the energy equivalent to a gallon of gasoline.  To achieve this , the efficiency of light to hydrogen conversion must reach 10% while current efficiency is only 1% and selling price is estimated at 13.53/kg. 33
  • 34. Reference  Hand book of bioenergy and biofuels – V K mutha  Journal on Bio hydrogen production aspotential energy resources by Kaushik & D Das.  Bio biohydrogen – Microbiological production of hydrogen fuel by P C Hallebeck & J R Bennemen 34
  • 35. Conclusion 35  Bio hydrogen is fuel of future  Areas of research to increase efficiency include developing of oxygen tolerant hydrogenase and increased hydrogen production rates.  Research on cost effective production of bio hydrogen for commercialization is required.