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Water Problems Institute of Russian Academy of Sciences, Novo-Basmannaja str. 10, PO Box 524, 107078 Moscow, Russia
(Received 25 July 1994; revised version received 30 November 1994; accepted 5 December 1994)
where n = 1, 2 ..... 7 (methane, carbon dioxide, hydro- 8. The dependence of different model variables
gen sulfide, hydrogen, ammonia, water vapour, inert on such parameters as SRT, HRT and temperature
gas); Vg=gaseous phase volume; R=universal gas can be analysed for the steady-states of a continu-
constant; Tk=absolute temperature; q~=gas flux ous-flow reactor.
coming into the gaseous phase; PF,,=partial pressure 9. The model was realized in a form of a user-
of gas components in the influent wastewater; friendly computer program for IBM PC AT and it
Pv=total gas pressure in the gaseous phase; allows the user, in 1 min of computer time, to see
Q,,=mass exchange function between liquid and gas the complex dynamic behaviour of an anaerobic
for each gaseous component. The rate of mass system over many days.
exchange between the liquid and gaseous phases was 10. The procedure of visual model calibration is
described according to Andrews and Graef (1971). developed. The computer program includes a library
Detailed information about the model has of experimental data with different organic wastes
been reported (Vasiliev et al., 1993; Vavilin et al., being treated and corresponding values of constants
1994a) and the main features of the new version, and parameters. The model was able to provide a
(METHANE 2.2), are as follows. good comparison with data examined.
1. Hydrolysis, acidogenesis and methanogenesis 11. The current values of all variables can be dis-
are included. The total number of particulate, solu- played on the screen in text and in graphic forms
ble and gaseous variables of the model is about 30. and also printed out. Using these data it is easy to
Rates of changes in the biomass concentration (acid- analyse the input of particular processes like defined
ogens, syntrophs and methanogens) take into buffer systems used to keep a constant pH level.
account bacterial growth, death and mutual trans- 12. (METHANE 2.2) contains a ( H E L P ) proce-
formations. dure for a description of the program features in
2. Four versions of hydrolysis kinetics are con- text and in graphic forms.
sidered for suspended solids degradation, including
the simplest first-order kinetics.
RESULTS AND DISCUSSION
3. Dissolved and particulate organic matter is
supposed to be a mixture of carbohydrates, proteins Manure digestion: ammonia toxicity
and lipids which have limits to fermentation. Lysis To reduce ammonia concentration to a non-critical
and hydrolysis of cell biomass are taken into level, Kapp (1992) suggested raising the pressure in
account. a thermophilic sludge digester. Using a half-scale
4. The rate of the main limiting-substrate trans- pilot-plant he showed that at pressures from 2.5-3
formation by bacterial groups is presened as a bar the digestion succeeded. An increase in CO2
product of substrate limitation- and inhibition-func- partial pressure decreased the pH value, which low-
tions and temperature dependence. Inhibition ered the concentration of NH3.
effects of the molecular-hydrogen pressure, pH, con- We analysed Kapp's proposals in the case of
centration of non-ionized molecules of ammonia, of manure digestion using the ( M E T H A N E ) model. A
hydrogen sulfide and of propionate are considered. continuous-flow anaerobic system, fed on cattle
It is supposed that propionate represents the whole manure and adapted to a particular level of ammo-
spectrum of volatile fatty acids other than acetate. nia, was used by Angelidaki et al. (1993) to study the
Thus, the acetate or the propionate paths of fermen- effect of a step increase in the concentration of
tation carried out by acidogens A or acidogens P are ammonia in the influent water. High pH levels
included. The pathway of fermentation is dependent (7.6-8.1), together with high VFA concentrations,
on the hydrogen partial-pressure. were observed in the steady-state.
5. A physico-chemical reaction system of pH level For the model a manure composition was repre-
with ammonia, hydrogen sulfide, carbonic acid and sented by a mixture of soluble and insoluble
volatile fatty acid buffer systems is considered. The carbohydrates, proteins and lipids (70:29:1) to
buffer capacity of the system can be evaluated using obtain the suspended and dissolved solids composi-
bicarbonate alkalinity. The pH level can be fixed. tion and the level of ammonia equal to those in the
6. The flow-rate of biological solids through the cattle manure digestion mentioned above. The
reactor is considered to be independent of the flow- degradable part of the suspended solids was such as
rate of the bulk liquid phase. Thus, the model can to obtain the methane flow-rate required. The quasi-
be useful for analysis of high-rate digesters with sol- steady-state of the model was obtained under the
ids retention. conditions presented in Table 1. Some model coeffi-
7. Batch and continuous-flow reactors can be cients are shown in Table 2. Following this, after a
analysed using the first and the second forward-inte- sharp increase in influent ammonia concentration
gration methods with variable time-step. The user from 2.5 to 6.0 g N/I at 0 days the system adapted to
can change the integration accuracy. In continuous- the new conditions and reached a new steady-state
flow system the carbon balance is calculated to (Fig. 1). The graphs in Fig. 1 are the computer
check the integration accuracy. curves, thus the scales are rough. Only the maximum
Modelling of gas pressure effects on anaerobic digestion 27
Table 3. Computed values of some model variables for the manure continous-flow system at particular times after an
initial sharp increase in influent ammonia concentration a
methanogenesis is going on, but for the 1 bar case sulfate. When the input sulfate concentration was
the free-NH3 level inhibits the process substantially. increased from 200 mg S/1 to 625 mg S/I the system
3. When an NH3-inhibition process is excluded by did not fail, but under the input sulfate concentra-
an increase in the constants of NH3-inhibition func- tion of 1250 mg S/1 the high hydrogen sulfide
tions (see Table 2) the system dynamics change concentration inhibited methanogenesis organisms.
substantially only at 1 bar total gas pressure (Fig. 6). The quasi-steady-state of the model was obtained
Thus, increasing total gas pressure leads to under the conditions shown in Table 4. After a step-
decreasing inhibition from non-ionized ammonia. wise increase in influent sulfate concentration from
200 mg S/I to 625 mg S/I at 0 days the system adap-
S y n t h e t i c substrate: sulfate effect ted to the new conditions, reaching a new
To reduce a hydrogen-sulfide concentration to non- steady-state where methanogenesis and sulfate-
critical levels, Olsson and Schleischer (1994) reduction were going on. However, at an influent
removed sulfide outside the reactor using the biogas. sulfate concentration of 1250 mg S/1 the system
The biogas was led to a gas washing system, where failed and both sulfate-reduction and methane-pro-
H2S was absorbed in a scrubber liquid containing duction shut down (Fig. 7).
iron. We analysed the idea of lowering the total gas This acetate/sulfate system was studied using the
pressure to reduce H2S-concentration toxicity. previous model of anaerobic digestion (Vavilin et al.,
A system of anaerobic microorganisms adapted to 1994b). The model was able to provide a good com-
a low sulfate-load was studied by Parkin et al. (1990) parison with data. Some model coefficients are
for a step increased concentration in the input of shown in Table 2.
Modelling of gas pressure effects on anaerobic digestion 29
1400
,.. Methanogens A, mg/I
~. ......................
0
3594 :. - Acetate, mgll
/
0 .~__-
2456 ............. Propionate, rag/l
z"
8.1 ~- ........................... pR
4
1033 -" ........................... Non-ionized N H 3, mgN/l
:
O L0
0
0.799 Methane \
flow rate, Ill*day
-, .............................
0 o 0.5
2.8 ~ Methane
partial pressure, bar t-
................................
0
0.680 / Carbon dioxide
; partial pressure, bar 0
400 800 1200 1600 2000
KII K I2
0
120 days Non-ionized ammonia concentration (mgN/l)
Fig. 2. Time-profiles of the main model variables (solid Fig. 3. Inhibition effect of non-ionized ammonia con-
line) on computer display for the reactor after a step-wise centrations on the growth rate of methanogens.
increase at 0 days in the influent ammonium concentra-
tion from 2.5 to 6.0 g N/1 and with a total gas pressure of
3 bar. Model dynamics presented in Fig. 1 are shown as
the control (dotted line).
(A)
(a)
1400 1400
.............. Methanogens A, mg/I x~......................... Methanogens A, mgll
\
0 0
12000 12000 -
A c e t a t e , mg/l _ Acetate, mall
0 0
3000,
/
3000 Propionate, mg/l Propionate. mg/I
0 0 ............................ ~
0.1 ........................... '.pH 0.I .............................. p H
4 4
1600 1600
....................... Non-ionized NH3, mgN/l ~ . ..................... Non-ionized N H 3, mgNll
0 0
0.840 Methane 0,290 Methane
~ i ...................... flow rate, I / l , d a y " .................... flow rate, ill*day
0 0
0.800 ........ Methane 2.8 Methane
partial pressure, bar partial pressure, bar
Fig. 4. Model dynamics (solid line) when the initial pH of 7.98 (see Table 3) was kept constant at a total gas pressure
of 1 bar (A) and of 3 bar (B). Model dynamics with a variable pH in the reactor (Figs 1 and 2) are shown as the control
(dotted line).
30 V A. Vavifin, V.B. Vasiliev, S. V Rytov
(A) (B)
1400 • 1400 "~"-"--*-,~
Methanogens A, mg/I Methanogens A, mg/I
0
3594 • 428
Acetate, mg/I
/ Acetate, m8/I
/
0 0
2456 - °- . . . . . . . . . . . 260
Propionate, mg/l Propionate, m8/I
t...,
0 0
8.0- pH 8.0 pH
4 4
735
Non-ionized NH3, mgN/I Non-ionized NH3, mgN/I
1.5 Methane
flow rate, l/l.day
oY
0.460 1
Methane
flow rate, Ill*day
'~. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
0 0
0.667 Methane Methane
partial pressure, bar 2.60 [" partial pressure, bar
0
0.430 Carbon dioxide 0.663 Carbon dioxide
partial pressure, bar partial pressure, bar
0 0 ,
0 120 days 0 120 days
Fig. 5. Model dynamics (solid line) when the pH was kept constant at a total gas pressure of 1 bar (pH=7.75:A) and
of 3 bar (pH=7.60: B). Model dynamics with a variable pH in the reactor (Figs 1 and 2) are shown as the control (dotted
line).
(A) (B)
1400 . . . . . . I . . . . . . . . . . . . . . . . . . . . . .
1400 T'" Methanogens A, m8/I Methanogens A, mgll
~-.~. . . . . . . . . . . . . . . . . . . . . . .
/
0/ 0
, .- ................... i 420
3594 ] Acetate, mg/I Acetate, m8/I
0
pn 8.1 pH
4
1200 735
f ....................... Non-ionized NH3, mgN/I ....................... Non-ionized NH3, mgN/l
1,°
i 0
0.420 : Methane
Methane
k. . flow rate, l/l.day flow rate, Ill*day
0
0.680 Methane 2.8 Methane
partial pressure, bar partial pressure, bar
0 0
0.310 0.760 ........................... Carbon dioxide
.............................. Carbon dioxide
partial pressure, bar partial pressure, bar
Fig. 6. Model dynamics (solid line) without free ammonia inhibition at 1 bar (A) and at 3 bar (B) total gas pressures.
Model dynamics with an ammonia inhibition (Figs 1 and 2) are shown as the control (dotted line).
Modelling of gas pressure effects on anaerobic digestion 31
500
Methanogens A. mg/I Methanotgens A, mg/I
ol \ Sulfate-red. A. mg/l
0
17 Sulfate-red. A. mg/I
o X,~. 0
1300" 1249 Sulfate. mgS/l
Sulfate, mgS/I
0 0
0.400' Biogas 0.410 - Biogas
flow rate. Ill*day flow rate. Ill,day
0 0
13000 12470:
Acetate, mg/l Acetate, mg/I
[
0 OI ". . . . . . . . . . . . . . .
Non-ionized H2S. mgS/l 41 ~ ~ ' ~ ' ~ , ................. Non-ionized H2S, mgS/I
o ~
6.4 " - - ~ pH 6.4 [ . . . . . . . . pH
4 4
/ ,
'\
~ i
0 200 days 0 200 days
Fig. 7. System failure after the step-wise increase at day Fig. 8. Simulation of system recovery (solid line) after a
0 in the influent sulfate concentration from 200 to 1250 large step-wise increase at day 0 in the influent sulfate
mg S/! and with a total gas pressure of 1 bar. Symbols: concentration from 200 to 1250 mg S/I and with a total
experimental data (Parkin et al., 1990); lines: model pre- gas pressure of 0"65 bar. Model dynamics at 1 bar pres-
dictions. sure (Fig. 7) are shown as the control (dotted line).
obic Digestion, Cape Town, 23-27 January 1994, RSA Vasiliev, V. B., Vavilin, V. A., Rytov, S. V. & Ponomarev,
Litho (Pty), pp. 2-11. A. V. (1993). Simulation model of anaerobic digestion
Kapp, H. (1992). The effect of higher pressures on the of organic matter by a microorganism consortium: basic
mesophilic and the thermophilic anaerobic sludge diges- equations. Water Res., 20, 633-43.
tion. In Proc. Int. Symp. on Anaerobic Digestion of Solid Vavilin, V. A., Vasiliev, V. B., Ponomarev, A. V. & Rytov,
Waste, Venice, 14-17 April 1992, 85-94. S. V. (1994a). Simulation model (Methane) as a tool of
McCarty, P. L. & Mosey, F. E. (1991). Modelling of effective biogas production during anaerobic conversion
anaerobic digestion process (a discussion of concepts). of complex organic matter. Biores. Technol., 48, 1-8.
Water Sci. Technol., 24, 17-33. Vavilin, V. A., Vasiliev, V. B., Rytov, S. V. & Ponomarev,
Olsson, L. E. & Schleicher, O. (1994). Anaerobic-aerobic A. V. (1994b). Self-oscillating coexistence of methano-
treatment of black liquor from an NSSC pulp mill gens and sulfate-reducers under hydrogen sulfide
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Syrnp. on Anaerobic Digestion, Cape Town, 23-27 Jan- 49, 105-19.
uary 1994, RSA Litho (Pty), pp. 170-9. Vavilin, V. A., Vasiliev, V. B., Rytov, S. V. & Ponomarev,
Parkin, C. F., Lynch, N. A., Kuo, W. C., Van Keuren, E. A. V. (1995). Modelling ammonia and hydrogen sulfide
L. & Bhattacharya, S. K. (1990). Interaction between inhibition in anaerobic digestion. Water Res., 29, 827-35.
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