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Monitoring of digesters in
biogas plants
Renewable sources of energy are gaining steadily in importance. Leading Authors
Jürgen Wiese, EnerCess GmbH,
the way is the use of methane gas obtained from fermentation processes in Bad Oeynhausen, Germany
biogas plants. Overloading such plants with excessive biomass may have Ralf König, HACH LANGE GmbH,
drastic economic consequences and may even inactivate the biomass, Düsseldorf
➀
Co-substrates ➁ ➁
Stirrer Stirrer Fermentation
residue storage
Co-substrates
➂
Heat
Stirrer Block CHP unit Electricity
Biogas
Mixing pit
Engine Generator
Condensate Connection to
Buyer: thermal energy separator grid
Heat
Fig. 1: Design of a typical biogas plant (CHP = combined heat and power)
➀ Eluate analysis: Ntot, COD, NH4, heavy metals
➁ Digester analysis: NH4, org. acids, COD, acid capacity
➂ Online process analysis: pH, temperature, redox and TS
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Fig. 3: Central pumping station of a biogas plant in Lelbach with online sensors (front)
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COD ensure the trouble free operation of a prevented and dilution of the electrolytes is
The chemical oxygen demand is the biogas plant. avoided.
amount of oxygen required to oxidise Figure 4 shows examples of time-course
the oxidisable components of the Process monitoring in practice curves obtained from pH and redox
fermentation substrate. All oxidisable The suitability of the process probes was measurements. Through appropriate
organic compounds are totally tested in a biogas plant in north Hesse, positioning in the control zone of a pump
chemically oxidised to CO2 and H2O. Germany. The parameters temperature, station, the conditions in the digester
COD is a reliable indicator of the energy total solids, pH and redox were or post-digester can be accurately
potential of a fermentation substrate. measured [7]. determined and monitored. During the
test period (8 months), the pH readings
Organic acids/Fatty acids pH/Redox measurement remained in the range from 6.9 to 7.4. In
Low molecular fatty acids, in particular The digital pHD electrode used to measure the post-digester the average was 7.38,
acetic acid, propionic acid and butyric pH and redox is fully encapsulated so with a minimum of 7.20 and a maximum of
acid are formed during the first and that it does not come into contact with 7.50. These results confirm that the pH in
second steps of the fermentation the fluid being measured. A special, a digester is not constant, but undergoes
process. If the fermentation process soil resistant salt bridge forms the fluctuations. A similar result was obtained
is proceeding efficiently, the values for direct contact to the fluid to enable the from the readings of the redox potential.
these compounds, expressed as an measurements to be made. In contrast The average value was -392 mV, with
equivalent amount of acetic acid, lie to conventional membrane based fluctuations between -250 and -476 mV.
between 500 and 3,000 mg/l. In this electrodes, this electrode can be used These values show that fermentation
case, the processes in the digester, the for very long periods even in fluids with processes must be properly understood
production of acid by hydrolysis and the a high particulate content, e.g. digester and closely monitored to ensure optimal
degradation of acid by methanisation are water. The intervals between cleaning and therefore profitable operation of a
in equilibrium. If the acid concentration are especially long. Electrode poisoning, biogas plant.
rises above 10,000 mg/l, the pH e.g. by any H2S that may be present, is
usually falls below 7. According to
Bischofsberger [6], a drop in pH to
6.4, at an acetic acid concentration
of 1,000 mg/l, reduces the methane Online measurement of pH and redox potential
concentration by half. Acetic acid Redox [mV] pH
concentrations below 1,000 mg/l should
be determined by the titrimetric VOA/ — Redox potential
TAC method. — pH
Ammonium
During the fermentative degradation
of protein rich substrates in particular,
e.g. grass silage or chicken droppings,
high concentrations of ammonium ions
may be generated. Ammonium exists
in a pH dependent equilibrium with
ammonia, which is toxic to the bacteria.
If the pH increases the equilibrium shifts,
favouring ammonia. Regular checks of
the ammonium content of the digester
Fig. 4: Measurements from the pressure pipe line of a biogas plant digester in north Hesse,
Germany
6 BIOGAS_PROCESS MONITORING
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For the comparability of the results of the Dilution series for LCK 365 Organic acids
two methods it was especially important
Acetic acid equivalents [mg/l]
that the period between on-site analysis
(using the cuvette test) and laboratory
analysis (using the standard method
was as short as possible). Besides
the samples from the co-fermentation
biogas plant, numerous samples
from the mechanical-biological waste
treatment plant were analysed.
In addition, the concentrations of the
organic acids in digester samples from
various biogas plants were analysed
using ion chromatography (IC) and the
fast photometric test. The sum of the
Dilution
individual components determined using
Fig. 7: Dilution series for checking the plausibility of the measurements of organic acids in a post
IC was compared with the total organic
digester sample
acids determined with the photometric
test.
Sample preparation Plausibility of the measurements the spiked samples, (corrected to take
Colourless, clear solutions are required There are two relatively simple methods account of the dilution factor), should
for photometric tests. For this reason of determining the plausibility of the correlate to the known concentration of
it is important that the preparation of results: dilution and spiking [8]. For the added standard.
the digester samples, which have a first of these, a dilution series is prepared Figure 7 shows the results obtained
high particulate content, is carried out from the measured original sample. If from a dilution series prepared from a post
carefully and in line with good practice. any interference is present in the original digester sample from a biogas plant during
The samples from the digester and sample, its effect is weakened as the the course of long-term comparative
post-fermentation tank were diluted in level of dilution of the sample increases. measurements. Except for the result
the ratio 1:20. To do this, the tip of a The concentration of the original sample from the 1:10 dilution, all the results are
single-use pipette tip was cut off and can be calculated from the measurement within the range of tolerance, which is
the appropriate volume was added step results obtained from the dilutions. The higher for samples with a high particulate
by step (25 ml, 5 x 5 ml) to a 500 ml presence of any interference is revealed content than for samples that contain no
round flask. The diluted sample was then by a significant deviation between the particles. This is a consequence of the
split up and passed through a 0.45 μm concentration of the undiluted original unavoidable dilution error. The cause of the
polycarbonate membrane filter under sample and the concentrations calculated low result obtained from the 1:10 dilution
a pressure of 6 bar in the reference from the measurements of the dilution is unknown, but may be associated with
laboratory. The standard analyses were series. If there is virtually no deviation, no the above mentioned uncertainty of the
carried out on the filtrate. For each sample specific interference is present. volume reduction. The presence of any
photometric cuvette test, 20 ml of the The spiking method requires steadily interference can be excluded, as the
filtered sample was centrifuged in a table increasing concentrations of a standard to following dilution steps did not confirm this
centrifuge for 10 minutes at 13,500 be added to the measured sample. The trend.
rpm, providing approximately 20 ml concentration determined by measuring
clear and almost colourless centrifugate,
with which the cuvette tests were then
carried out.
8 BIOGAS_COMPARATIVE MEASUREMENTS
Comparative measurements
Spiking test with acetic acid standard method DEV H44 and the
LANGE cuvette test LCK 514 [11]. The
Expected value on basis of dilution/spiking
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Ion chromatography (IC) Comparative measurements – cuvette test and standard analysis
measurements [mg/l]
The cuvette test for organic acids
and the standard method (steam
distillation and titration of the acetic acid COD
equivalents) both determine the sum
of the individual substances. They do
not give the concentrations individual
substances, e.g. propionic acid, butyric
acid or acetic acid. In order to obtain NH4-N
the concentrations of these substances
and to clarify whether the sum of their
concentrations correlates with the
results obtained using the cuvette test Org. acids
and steam distillation, a number of
digester samples were also subjected
to ion chromatography and the results
were compared with those of the fast Fig. 9: Comparative measurements photometric cuvette test (red) and standard method (blue)
photometric test. – post digester sample from a biogas plant
In view of the lower total solids
content of the samples (clearly below
10 %), sample preparation was much
easier than for the previous comparative
measurements. Simple filtration through Ion chromatographic analysis
a folded filter usually sufficed.
The measurements were carried out
by Ingenieurbüro Stahmer, Bremen. It
analyses up to 100 digester samples
each week for ammonium nitrogen,
COD and organic acids. The ion
chromatogram for sample I shows a total
of four individual organic substances in
the digester sample: acetate, lactate,
propionate and n-butyrate. The sum
of the individual concentrations is
2,234.73 mg/l organic acids (Tab. 2).
The photometric test gave a sum of
2,530 mg/l. The difference in the results
for this sample is therefore 13 %. Given
the already mentioned dilution error
associated with substances containing
a high level of solids, this is a very good
Fig. 10: Ion chromatogram of a digester sample showing the individual components acetate,
value. The following ion chromatographic
lactate, propionate and N-butyrate
analyses gave much smaller differences.
10 BIOGAS_MEASUREMENT TECHNOLOGY
These results demonstrate that the fermentation product that can be readily
results obtained using the cuvette test used for agricultural purposes can
for the determination of organic acids only be obtained if the plant process is
correlate well with the results of the IC controlled.
standard method and that the sum of The described online measurement
the individual substances determined technology for metering pH, redox,
using the IC method also correlates very total solids and temperature, together
well with the result of the photometric with the photometric cuvette tests used
test and the steam distillation. in operations laboratories, allow cost
effective, precise, real time monitoring of
Summary the fermentation process so that biogas
The degradation processes in plants can be efficiently controlled. The
commercially operated biogas plants required investment is relatively low,
pHD sc sensor for pH or redox measurement take place in a sensitive microbiological compared with the risks associated with
system. High, profitable gas yields and a an uncontrolled fermentation process.
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Literature
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DOC 040.52.00447.May07
Automatic titrator for the volumetric Cuvette test LCK 114 for the determination
determination of organic acids of COD