Professional Documents
Culture Documents
Monitoring The Anaerobic Digestion Process: by Harry Michael Falk
Monitoring The Anaerobic Digestion Process: by Harry Michael Falk
Monitoring The Anaerobic Digestion Process: by Harry Michael Falk
Acidogenesis
The second phase of the first stage is the acidogenesis, named after the formation
of volatile fatty acids. Monomers, the end products of the hydrolysis step, are taken up
by di"erent facultative and obligatorily anaerobic bacteria such as Bifidobacterium spp.
Selenomonas spp. and Flavobacterium spp. and further degraded to acetic acid,
propionic acid, butyric acid, alcohols, hydrogen and carbon dioxide. The formation of
the end products is related with the partial hydrogen pressure; if the H 2 partial pressure
is increasing, fewer reduced compounds like acetate are formed [33].
The monomers formed in the hydrolytic phase are taken up by different facultativeand obligatorily
anaerobic bacteria and are degraded in the second, the acidogenic phase, to short- chain organic acids,
C1 C5 molecules (e.g., butyric acid, propionic acid, acetate, acetic acid), alcohols, hydrogen, and carbon
dioxide. The concentration of the intermediately formed hydrogen ions affects the kind of the
products of fermentation. The higher the partial pressure of the hydrogen, the fewer reduced
compounds, like acetate, are formed.
The pathways of degradation are as follows:
a.
Carbohydrates:
Formation of propionic acid by propioni bacterium via the succinate pathway and the acrylic
pathway
Formation of butyric acid (butyric acid pathway) above all by clostridium
Acetic acid 2-hydroxy butyrate trans-2-butenic acid butyric acid butanol (Figure 2.4 )
b. Fatty acids:
These are degraded e.g. from acetobacter by - oxidation. Therefore the fatty acid is bound on
Coenzyme A and then oxidizes stepwise, as with each step two C atoms are separated, which are
set free as acetate.
b. Amino acids:
These are degraded by the Stickland reaction by Clostridium botulinum taking two amino acids at
the same time one as hydrogen donor, the other as acceptor in coupling to acetate, ammonia, and
CO2. During splitting of cysteine, hydrogen sulfide is released.
Acetogenesis
In this step long chain fatty acids are reduced to acetic acid (C 2) and hydrogen (H2)
by acid-forming bacteria like Acetobacterium spp., Sporomusa spp. and Ruminococcus
spp. Under standard conditions, these biochemical reaction are endergonic (see table
1.2). For the degradation propionic acid, !G 0!= 76.2 kJ/mol are needed. At very low
concentrations of H2, however, the acetate formation by oxidation of the long chain
fatty acids is thermodynamically possible. The problem, that acetogenic bacteria are
obligatory H2 producers on the other hand is solved by living with the methanogenic
bacteria syntrophically, a process termed "interspecies hydrogen transfer" [24].
The methanogenic bacteria remove the H 2, which is formed by the acetogenic
bacteria and therefore lowering the hydrogen partial pressure [33]. Figure 1.5 presents
the influence of the hydrogen partial pressure on the free energy the bacteria can gain
in the acetogenesis and methane formation from carbon dioxide and hydrogen. Clearly,
all thereactions are thermodynamically favorable only in a small window
The products from the acidogenic phase serve as substrate for other bacteria, those of the
acetogenic phase. The acetogenic reactions (Table 2.1 ) are endergonic. With the degradation of
propionic acid are needed Gf= + 76.11 kJ mol 1, and with the degradation of ethanol Gf= + 9.6 kJ mol
1.4
In the acetogenic phase, homoacetogenic microorganisms constantly reduce exergonic H 2 and CO2 to
acetic acid.
Acetogenic bacteria are obligatory H2 producers. The acetate formation by oxidation of long- chain
fatty acids (e.g., propionic or butyric acid) runs on its own and is thus thermodynamically possible only
with very low hydrogen partial pressure. Acetogenic bacteria can get the energy necessary for their
survival and growth, therefore, only at very low H2 concentration.
Acetogenic and methane- producing microorganisms must therefore live in symbiosis. Methanogenic
organisms can survive only with higher hydrogen partial pressure. They constantly remove the products
of metabolism of the acetogenic bacteria from the substrate and so keep the hydrogen partial
pressure, pH2, at a low level suitable for the acetogenic bacteria.
When the hydrogen partial pressure is low, H 2, CO2, and acetate are predominantly formed by the
acetogenic bacteria. When the hydrogen partial pressure is higher, predominantly butyric, capronic,
propionic, and valeric acids and ethanol are formed. From these products, the methanogenic
microorganisms can process only acetate, H2, and CO2.
About 30% of the entire CH 4 production in the anaerobic sludge can be attributed to the reduction
of CO2 by H2, but only 5 6% of the entire methane formation can be attributed to the dissolved
hydrogen. This is to be explained by the interspecies hydrogen transfer by which the hydrogen moves
directly from the acetogenic microorganisms to the methanogenics, without being dissolved in the
substrate.
The anaerobic conversion of fatty acids and alcohols goes energetically at the expense of the
methanogenics, where these, however, in return, receive the substrates (H 2, CO2, acetic acid) needed
for growth from the acetogenic bacteria.
The acetogenic phase limits the rate of degradation in the final stage. From the quantity and the
composition of the biogas, a conclusion can be drawn about the activity of the acetogenic bacteria.
At the same time, organic nitrogen and sulfur compounds can be mineralized to hydrogenic sulfur
by producing ammonia. The reduction of sulfate follows for example the stoichiometric equations below
Sulfate - reducing bacteria such as Desulfovibrio, Desulfuromonas, Desulfobulbus, Desulfobacter,
Desulfococcus, Desulfosarcina, Desulfonema and Desulfotomaculum participate in the process, which
uses the energy released by the exergonic reaction.
1.4.4. Methanogenesis
The final step of reducing the organic intermediates to methane is the methanogenesis,
an exergonic reaction, which only takes place under strictly anaerobic conditions. The
responsible bacteria all belong to the archaea family, such as Methanococci spp.,
Methanobacteria spp. and Methanomicrobia spp. Central to the anaerobic fermentation
and methane generation this methanogenic bacteria are very sensitive to all sort of
process disturbances, especially pH-fluctuations and oxygen. Due to their very low
growth rate, the whole process of anaerobic digestion is optimized for these bacteria.
Not all methanogenic species can use all available substrates. These can be divided
into three major groups and their methane forming reactions can be found in table 1.3:
CO2 type: CO2, HCOO Methyl-type: CH3OH, CH3NH3, (CH3)2NH2+,(CH3)3NH+, CH3SH, (CH3)2S
carbon dioxide percentage in the biogas can be an indicator for a process disturbance
[33]. A second system, the ammonia-ammonium bu"er inhibits a too weak acidification
(pKa = 9.25):
NH3 + H2O NH4+ + OH
NH3 + H+ NH4+
Although these bu"er systems equilibrate the pH, both can still be overloaded with e.g.
a too high organic load of easy degradable carbohydrates (starch powder, potato
wastewater), which can lead to a rapid increase of the volatile fatty acids.