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BIOINFORMATICS
DOI: 10.5504/bbeq.2012.0061
ABSTRACT
The anaerobic conversion of glycerol by the bacterium Klebsiella sp. is a well-known process. According to its metabolism
glycerol is converted into different products, e.g. 2,3-butanediol, 1,3-propanediol, acetic acid, formic acid, lactic acid and
biogas. The latter is produced by two competitive ways: decarboxylation of acetic acid or self-reduction of carbon dioxide by
hydrogen, acetic acid, carbon dioxide and hydrogen being intermediate products of one of the competitive metabolic routes.
Which of these compounds is a desired final product depends on the purpose of the fermentation.
In the present work a non-structured mathematical model is developed to describe these competitive processes. The model
consists of nine ordinary non-linear differential equations for the kinetics of some selected more important reactions from the
metabolic pathway. The model takes into account the microbial growth, the pH drop caused by the organic acid formation and
the resulting inhibition of the methanogenic microbial activity. The pH-optima of the enzymes are approximated by Gaussian
distribution. The enzyme sensitivity toward pH-variations is presented by the half-width of the Gaussian curve.
A large set of experimental data for glycerol anaerobic digestion by Klebsiella sp. in a baffled multistage reactor was used for
verification of the model. The comparison of the experimental data with the model results revealed the number of reactor stages,
sufficient for complete methanization and to determine the optimum conditions for 2,3-butanediol or methane production.
Biotechnol. & Biotechnol. Eq. 2012, 26(5), 3244-3248
Keywords: biogas production, glycerol, enzyme activity,
mathematical modeling
Notations: Ac: concentration of acetic acid; BD: concentration
of 2,3-butanediol; bi: enzyme activity dependence on
pH; CH4: concentration of methane; CO2: concentration
of carbon dioxide; F: concentration of formic acid; Km:
saturation constant; Kx: biomass decay constant; ki: rate
constants of intermediate and final processes; pH: pH value;
Pv: concentration of piruvate; S: concentration of glycerol; t:
time; X: concentration of biomass; YX/S: yield coefficient of
micobial production
Greek symbols: : rate constant of substrate conversion; :
specific growth rate; max: maximum specific growth rate; s2:
width of the Gaussian curve at its semi-height
Subscripts: ac: acetic acid; Ac1: acetic acid decarboxylation;
BD: 2,3-butanediol; bd1: degradation rate constant for
2,3-butandiol; CH4: methane; CO2: carbon dioxide; F: formic
acid; Pv: piruvate; S: glycerol; 0: initial values
Introduction
Crude glycerol is the main waste product from biodiesel
manufacturing. Its amount is equivalent to the methanol used
for the trans-esterification and exceeds the traditional market
demands. On the other hand, this waste product contains about
20 % water and it is contaminated by the catalyst and some
methanol. Since there is market demand only for pure glycerol
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and its price is not high, the purification of the waste product is
not economically feasible.
There are many chemical compounds produced from
glycerol by microbial methods. Different bacteria (from the
genera Klebsiella, Clostridium, Enterobacter, etc.) are capable
of metabolizing glycerol, leading to main basic products
with some differences in the metabolic by-products (4). The
metabolic scheme for glycerol conversion by the bacteria
Klebsiella sp. is shown in Fig.1 (11). Another way for waste
glycerol utilization is to produce energy in the form of biogas
(4, 9).
This biogas could be used for partial energy supply of
the main biodiesel plant. Methanogenic bacteria can produce
methane from the metabolic products of the other bacteria
listed above. Methane can be produced either after acetic acid
decarboxylation or carbon dioxide reduction by hydrogen:
CH3COOH CH4 + CO2
(Eq. 1)
(Eq. 2)
(Eq. 3)
(Eq. 4)
TABLE 3
Comparison of evaluated parameters for the first two
compartments of the bioreactors (experimental data from
different run)
1
7
5
4
2 8
Fig. 4. Time profiles and comparison with experimental data as HPLC peak
area for compartment 1 at s2 = 0.25. Line 1 (): glycerol; line 2 (o): acetic
acid; line3 (o): 2,3-butanediol; line4 (): pH; line5: methane volume; line6:
piruvate; line 7: enzyme activity, (bCH4) of methane formation from formic
acid; line8: biomass concentration.
Parameter
mmax, h-1
kF, h-1
kBD, h-1
kBD1, h-1
kAc, h-1
kAc1, h-1
Pvo, peak area
Compartment 1
0.274
1.370
0.820
0.084
0.078
0.063
18.4
Compartment 2
0.242
1.450
0.340
0.075
0.085
0.062
39.7
s2 = 0.25
0.274
0.656
0.948
0.105
0.107
0.154
19.54
s2 = 0.45
0.275
0.521
1.004
0.118
0.099
0.272
19.98
1
4
2
3
Conclusions
Acknowledgements
REFERENCES
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