Environmental Engineering Reference
In-Depth Information
the reduction of molecular nitrogen to ammonium by consuming reducing power
(e
-
mediated by ferredoxin, NAD
+
etc.) and ATP. Nitrogenase catalyzes H
+
reduc-
tion in the absence of nitrogen gas. Even in nitrogen atmosphere, H
2
production is
catalyzed by nitrogenase as a side reaction at a rate of one-third to one-fourth that
of nitrogen-fixation. Nitrogen-fixing cyanobacteria are potential candidates for H
2
production by nitrogenase but it is an energy-consuming process due to breakdown
of many ATP molecules.
2.2 Soluble Metabolic Acid Intermediates
The soluble acid metabolites or volatile fatty acids (VFA) formed during the aci-
dogenic process help in understanding the metabolic pathway [18]. The following
equations show variable soluble acid metabolites generation during acidogenic
fermentation.
C
6
H
12
O
6
+2H
2
0
→
2CH
3
·
COOH + 2CO
2
+4H
2
[Acetic acid]
C
6
H
12
O
6
→
CH
3
·
CH
2
·
CH
2
·
COOH + 2CO
2
+2H
2
[Butyric acid]
C
6
H
12
O
6
+2H
2
→
2CH
3
·
CH
2
·
COOH + 2H
2
O
[Propoinic acid]
C
6
H
12
O
6
+2H
2
→
COOH
·
CH
2
·
CH
2
O
·
COOH + CO
2
[Malic acid]
→
CH
3
·
C
6
H
12
O
6
CH
2
OH + CO
2
[Ethanol]
Depending on the pathway used by the microorganism and the corresponding
end-products, H
2
yields are variable. Products formed from pyruvate such as acetate,
butyrate, butanol, acetone, lactate or ethanol determine the theoretical yield of H
2
[3]. In obligate anaerobes, pyruvate is converted to H
2
from the reduced Fd by the
action of hydrogenase resulting in maximum yield of 2 mol H
2
/mole glucose. Two
additional moles of H
2
can be produced from NADH produced during glycoly-
sis, where NADH is oxidized by Fd reduction by NADH:ferredoxin oxidoreductase
(NFOR) [3]. Further, H
2
can be produced from the reduced Fd by hydrogenase. The
highest theoretical yield of 4 mol H
2
/mole glucose can be obtained when acetate
or acetone is the fermentation end-product. Two molecules of formate are produced
from two pyruvate molecules where a theoretical maximum yield of 2 mol H
2
/mole
of glucose can be obtained. In the case of butyrate as the fermentation end-product,
the maximum theoretical yield is 2 mol H
2
/mole glucose. When alcohols are the
end-products, lower yields of H
2
are obtained as alcohols contain additional H
2
atoms that have not been converted to H
2
gas [3]. The presence of higher concentra-
tions of propionic acid or solventogenesis is generally not considered to be feasible
for H
2
production.
3
Waste and Wastewater as Substrates for H
2
Production
One of the sustainable ways to reduce the cost of waste or wastewater treatment is to
generate bio-energy, such as H
2
gas, from the organic matter present. Waste biomass
contains enough energy to meet a significant fraction of the world's entire energy
demand, if it could be efficiently converted to useful energy forms [19]. According
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