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Electrical conductivity as a state indicator for


the start-up period of anaerobic fixed-bed
reactors

Article in Water Science & Technology · February 2016

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Electrical conductivity as a state indicator for the start-up
period of anaerobic fixed-bed reactors

A. Robles1,2, E. Latrille2, J. Ribes3, N. Bernet2 and J.P. Steyer2


1
IIAMA, Institut Universitari d'Investigació d’Enginyeria de l’Aigua i Medi Ambient, Universitat Politècnica
de València, Camí de Vera s/n, 46022 Valencia, Spain
(E-mail: ngerobma@upv.es)
2
INRA, UR0050, Laboratoire de Biotechnologie de l’Environnement, Avenue des Etangs, F-11100
Narbonne, France
(E-mail: [eric.latrille; nicolas.bernet; jean-philippe.steyer]@supagro.inra.fr)
3
Departamentd’Enginyeria Química, EscolaTècnica Superior d’Enginyeria, Universitat de València,
Avinguda de la Universitat s/n, 46100 Burjassot, Valencia, Spain
(E-mail: josep.ribes@uv.es)

Abstract
The aim of this work was to analyse the applicability of electrical conductivity sensors for on-line
monitoring the start-up period of an anaerobic fixed-bed reactor. The evolution of bicarbonate
concentration and methane production rate was analysed. Strong linear relationships between
electrical conductivity and both bicarbonate concentration and methane production rate were
observed. On-line estimations of the studied parameters were carried out in a new start-up period
by applying simple linear regression models, which resulted in a good concordance between both
observed and predicted values. Electrical conductivity sensors were therefore identified as an
interesting method for monitoring the start-up period of anaerobic fixed-bed reactors due to its
reliability, robustness, easy operation, low cost, and minimum maintenance compared with the
currently used sensors.

Keywords
Anaerobic fixed-bed reactor; electrical conductivity; methane production; on-line monitoring;
start-up

1. INTRODUCTION
Methane production represents the main challenge for anaerobic digestion (AD) of waste.
Nowadays, high effort has been focussed on the study of high-rate systems that use self-
immobilised biomass (e.g. up-flow anaerobic sludge blanket (UASB), expanded granular sludge
blanket (EGSB) or fixed-bed bioreactors), where hydraulic retentions time (HRT) and solid
retention time (SRT) are uncoupled. However, anaerobic fixed-film reactors usually require of a
long start-up time, which is critical to reach successful process performance (Escudié et al., 2011).

The start-up stage of a fixed-film process could be defined as “the time necessary for selection and
proper spatial arrangement of the fittest bacterial strains of a consortium best tuned with each other
on the substratum” (Heppner et al., 1992). Optimising the start-up time is a key challenge in order
to maximise the economic benefits of an anaerobic process (Weiland and Rozzi, 1991). Hence, due
to the high complexity and instability of AD processes, it is necessary to develop suitable
monitoring systems enabling successfully starting-up, stabilising and optimising anaerobic fixed-
film reactors (von Sachs et al., 2003; Escudié et al., 2011).

Biogas composition and flow rate are commonly used as indicators for monitoring the performance
of AD processes. Moreover, the methane yield (YCH4), which is defined as the amount of methane
produced per unit of removed organic matter, can also be used as an indirect parameter for
evaluating the start-up period of an AD process (Michaud et al., 2002). Nevertheless, these
indicators can be insufficient to evaluate the overall process performance since they could indicate a
fault of the process when quick recovery is not possible anymore. On the other hand, the reliability
and efficiency of the volatile fatty acid (VFA) concentration as state indicator for monitoring the
performance of AD processes has been demonstrated (Boe et al., 2010). VFA concentration can be
reliably monitored, for instance, by means of a titrimetric sensor or a Fourier transform infrared
spectrometer (Steyer et al., 2002a,b).However, the ideal on-line technique for bioprocess
monitoring in full-scale applications should be robust, simple to maintain and to perform, and with
a long life-span and minimal investment cost (Aceves-Lara et al., 2012).

Electrical conductivity is defined as the ability of a solution to conduct electrical current and it is
directly proportional to ion concentration. Moreover, it can be easily monitored: a cell formed by
two electrodes is placed in the sample and the current between both electrodes is measured by
means of the application of alternative potentials (Colombiéet al., 2007).Therefore, conductivity
measurements could be of great interest for monitoring and control AD processes, where ion
concentration is mainly affected by both VFA and bicarbonate concentrations(Hawkes et al., 1994):
two of the most reliable indicators of AD process performance (Olsson et al., 2005).

Several studies have been published where the feasibility of electrical conductivity sensors for
bioprocess monitoring has been evaluated (see, for instance, Hoffmann et al., 2000, Varley et al.,
2004, Aguado et al., 2006, Ellison et al., 2007). However, there is still a lack of knowledge
regarding its applicability to AD processes. The main objective of this work was to analyse the
applicability of electrical conductivity sensors for on-line monitoring the start-up period of an
anaerobic fixed-bed reactor which was fed with winery wastewater. Bicarbonate concentration and
methane production were analysed, and strong linear relationships between these parameters and
electrical conductivity were observed. Theoretical calculations of both bicarbonate concentration
and methane production from the on-line electrical conductivity measurements were conducted in a
new start-up period, assessing the feasibility of electrical conductivity sensors for monitoring the
start-up period of the evaluated AD process.

2. MATERIAL AND METHODS


2.1. Pilot plant description and operation
Figure 1 shows the flow diagram and the instrumentation of the continuous anaerobic fixed-bed
reactor used in this study. This plant has a total volume of 0.358 m3. The support media (Cloisonyl:
180 m2·m-3 specific surface) fills 0.034 m3, leaving the resting 0.324 m3 of effective volume. In
order to control the temperature when necessary, the anaerobic reactor is jacketed and connected to
a water heating system. The reactor includes a pH-controller that feeds NaOH (30%) when
necessary.

Figure 1. Flow diagram of the plant, including instrumentation. (Nomenclature: FIT: Flow-Indicator-Transmitter; PIT:
Pressure-Indicator-Transmitter; pH: pH-Transmitter; CT: Conductivity-Transmitter; T: Temperature sensor; PLC:
Programmable Logic Controller).

The plant was fed with raw winery wastewater from local cellars located in the area of Narbonne,
France. Table 1 shows the main characteristics of the raw winery wastewater used in this study. The
wastewater was stored in a feed tank (27 m3) that was connected to a dilution system of 0.2 m3.
Hence, different organic loading rates (OLR) were tested. The HRT was maintained at 2.7 days
approximately. In the reactor, a portion of the liquid was recycled from the bottom to the top for
both improving the mixing conditions and favouring the stripping of the produced gases from the
liquid phase. The recycling flow rate during the experimental period was set to 550 L·h-1. The fresh
substrate was mixed with the recycled liquid, and then introduced at the top of the reactor. The plant
was operated at a controlled temperature of 35 ºC. The pH set point was set to 7.2.

Table 1. Average characteristics of the raw winery wastewater.


Parameter Unit Mean ± SD
-1
COD g COD·L 21.5 ± 0.8
Acetate g COD·L-1 3.7 ± 0.4
Propionate g COD·L-1 4.6 ± 0.8
Butyrate g COD·L-1 2.8 ± 0.3
Valerate g COD·L-1 1.5 ± 0.7

2.2. On-line monitoring


The on-line equipment used in this work consists of: a conductivity-temperature transmitter located
in the recycling pipe; a flow-rate indicator transmitters for the winery wastewater fed-pump; an on-
line titrimetric sensor (Anaerobic Control Analyser AnaSense®, AppliTek S.L.) for the
measurements of total VFA and bicarbonate; and a gas flow-rate indicator transmitter
(electromagnetic floater-based sensor KROHNE DK37E) and an on-line CH4 sensor (Bluesense
BCP-CH4bio), both located in the biogas discharging pipeline. All gas measurements were
normalised to standard conditions of temperature and pressure (STP).

2.3. Sampling and off-line measurements


Besides the on-line monitoring, biogas composition (CH4, CO2, O2, H2S and N2) was determined
off-line using a gas chromatograph equipped with a thermic conductivity detector (GC-TCD, Perkin
Elmer®, Clarus 480 GC). VFA composition (i.e., acetate (C2), propionate (C3), iso-butyrate and
butyrate (iC4 and C4), and iso-valerate and valerate (iC5 and C5))was determined by gas
chromatography (Perkin Elmer®, Clarus 580 GC).COD was determined by the spectrophotometric
micro-method (Tube Test MR, AQUALYTIC®), according to Standard Methods (2005).

3. RESULTS AND DISCUSSIONS


3.1. Process performance evaluation
Figure 2a shows the evolution of OLR during the experimental period. As this figure shows, OLR
was progressively increased from 0 to 4 g COD L-1 d-1 in order to minimise possible disturbances
on the biofilm formation. Moreover, the effluent VFA concentration was used as state indicator of
the process performance in order to avoid biomass-growth inhibitions due to possible overloads of
the reactor. Thus, when effluent acetate concentrations higher than 1600 mgCOD·L-1 were reached,
a reduction in the OLR was conducted in order to avoid inhibition of propionic-reducing bacteria
(see period from days 20 to 25).
a b
Figure 2. Evolution throughout the operational period of: (a) OLR; and (b) reactor head-space pressure and methane
production rate.

Figure 2b shows the evolution of the head-space pressure in the anaerobic reactor and the methane
production rate throughout the experimental period. It is important to note that outflow of biogas
from the reactor was not detected until the head-space pressure reached the minimum value for
biogas discharge. As Figure 2b shows, although the head-space pressure started increasing around
day 5 (mainly due to carbon dioxide formation), it was observed that no methane production was
monitored until day 20. Important to note is that the methane composition in the biogas started
being noticeable around day 5, and reached a steady-state value around day 20 (up to 90% v/v).
This increase in the biogas methane composition resulted in a consequent decrease in the biogas
carbon dioxide composition, thus modifying the alkalinity of the liquid phase (pH was controlled at
7.2). Hence, non-stationary bicarbonate concentrations were observed throughout this initial stage
(i.e. until reaching steady-state conditions around day 20 of the operational period).

a b
Figure 3.Evolution throughout the operational period of: (a) COD removal efficiency (total COD removed and COD
removed for methane production); and (b) methane yield.

Figure 3 shows the evolution throughout the operational period of the COD removal efficiency
(Figure 3a) and methane yield (Figure 3b). From day 0 to 20, the COD removed in the system was
attributed to the anabolism of anaerobic biomass (i.e. initial growth, fixation, and adaptation of the
biomass to the new environmental conditions) (Michaud et al., 2002). During this initial period,
high COD removal efficiencies were observed mainly due to the low OLR levels applied. From day
25 to 30, a decrease in the COD removal efficiency was observed. This behaviour was related to the
previously-commented VFA accumulation in the reactor. Nonetheless, an increasing COD removal
efficiency associated with the catabolism of methanogenic archaea was observed after day 30. On
the other hand, a decrease in the methane yield from around 0.32 to 0.10 LCH4 STP·g-1CODREMOVED
was observed from day 25 to 30 (see Figure 3b). In accordance with Michaud et al. (2002), this
behaviour was attributed to possible process disturbances during the initial contact between the
microorganism and the fixed support media, mainly related to attachment constraints during the
biofilm formation and consolidation. Therefore, a minimum time of 20 days was required to reach a
functional anaerobic biomass consortium, whilst a minimum time of 35 days was required for
achieving a functional anaerobic biofilm. After day 35, a quite stable COD removal efficiency (up
to 85%) was achieved, which resulted in a continuous increase in the methane yield throughout
time. This behaviour highlighted the development and maturing of a stable biofilm.

3.2. Monitoring system development


Similarities between the evolution of electrical conductivity and both bicarbonate concentration and
methane production rate were observed during the previously-analysed operating period. Hence, the
evolution of electrical conductivity, bicarbonate concentration and methane production rate was
analysed, resulting in linear relationships between these parameters. Since ion conductivity is
sensitive to temperature, electrical conductivity was corrected to 25ºC (G25) as proposed by
Colombié et al. (2007). Moreover, in order to account for possible variations in methane production
due to variations in temperature and pressure, methane flow rate was expressed at standard
conditions of temperature and pressure (STP). As commented before, increasing OLRs were applied
during the start-up period of the anaerobic fixed-bed reactor, and the evolution of G25, bicarbonate
concentration and methane production rate was evaluated.

For an established G25 operating range (0.5 mS·cm-1 < G25 < 4 mS·cm-1), a linear regression (R2
coefficient of 0.97) between both bicarbonate concentration and G25 was observed (see Figure 4a
and Equation 1). Deviations between calibration and experimental data (see Figure 4a, 1.1 mS·cm-1
< G25 < 2.3 mS·cm-1) were mainly related to the previously-commented accumulation of VFAs
observed during the star-up period of the plant.

(∆𝐵𝑖𝑐)𝑒𝑠𝑡 = 𝛼𝐵𝑖𝑐/𝐺 · (∆𝐺)25 (Equation1)


where (ΔBic)est is the estimated change in the bicarbonate concentration(mmol·L-1); (ΔG)25 is the
measured change in G25 (mS·cm-1); and αBic/G is the regression coefficient including the confidence
interval at 95% (37.01 ± 0.04 mmol·cm·L-1·mS-1).

Equation 1 highlights the possibility of using electrical conductivity sensors for on-line monitoring
the bicarbonate concentration during the start-up period of an anaerobic fixed-bed reactor.
Nevertheless, the use of these sensors could be enhanced by accounting for possible variations in
other parameters such as VFA concentration since electrical conductivity is proportional to the total
ion concentration (Aceves-Lara et al., 2012).

For an established Bic operating range (20 mmol·L-1 < Bic < 60 mmol·L-1), a linear regression (R2
coefficient of 0.89) between both bicarbonate concentration and methane production rate was also
observed (see Figure 4b and Equation 2).

(Δ𝑄𝐶𝐻4 )𝑒𝑠𝑡 = 𝛼𝑄𝐶𝐻4 /𝐵𝑖𝑐 · (∆𝐵𝑖𝑐) (Equation 2)


where (ΔQCH4)est is the estimated change in the specific methane production from the measured
bicarbonate concentration (LCH4 STP·d-1·L-1); (ΔBic) is the change in the bicarbonate concentration
(mmol·L-1); and αQCH4/Bic is the regression coefficient including the confidence interval at 95%
(0.0152 ± 0.0002 LCH4 STP·mmol-1·d-1).

The linear dependence shown in Equation 2 states the importance of bicarbonate concentration for
starting-up an anaerobic fixed-bed reactor. On the other hand, an increasing dispersion of the
monitored methane production rate was observed for bicarbonate concentrations higher than 60
mmol·L-1. Above this value it was assumed that the process was completely started-up, thus
methane production depended on different operating conditions.

Equation 3 is obtained by combining Equations 1 and 2, which illustrates that for an established G 25
operating range (1.2 mS·cm-1 < G25 < 2.2 mS·cm-1), a nearly linear regression (R2 coefficient of
0.82) between both G25 and methane production is observed (see Figure 4c). Deviations between
experimental and predicted values shown in Figure 4c (R2 coefficient was 0.82) could be related to
variations in other operating variables (e.g. VFA concentration).

(Δ𝑄𝐶𝐻4 )𝑒𝑠𝑡 = 𝛼𝑄𝐶𝐻4 /𝐺 · (∆𝐺)25 (Equation 3)


where αQCH4/G is the regression coefficient including the confidence interval at 95% (0.446 ± 0.005
LCH4 STP·cm·d-1·L-1·mS-1).

(∆𝐵𝑖𝑐)𝑒𝑠𝑡 = 𝛼𝐵𝑖𝑐⁄𝐺 · (∆𝐺)25 (∆𝑄𝐶𝐻4 )𝑒𝑠𝑡 = 𝛼𝑄𝐶𝐻4 ⁄𝐵𝑖𝑐 · (∆𝐵𝑖𝑐)


𝛼𝐵𝑖𝑐⁄𝐺 = 37.01 ± 0.04 𝛼𝑄𝐶𝐻4 ⁄𝐵𝑖𝑐 = 0.0152 ± 0.0002
𝑚𝑚𝑜𝑙 · 𝑐𝑚 · 𝐿−1 · 𝑚𝑆 −1 𝐿𝐶𝐻4 𝑆𝑇𝑃 · 𝑚𝑚𝑜𝑙 −1 · 𝑑 −1

a b
(∆𝑄𝐶𝐻4)𝑒𝑠𝑡 = 𝛼𝑄𝐶𝐻4 ⁄𝐵𝑖𝑐 · (∆𝐺)25
𝛼𝑄𝐶𝐻4 ⁄𝐺25 = 0.446 ± 0.005
𝐿𝐶𝐻4 𝑆𝑇𝑃 · 𝑐𝑚 · 𝑑 −1 · 𝐿−1 · 𝑚𝑆 −1

c
Figure 4. Linear regressions obtained between: (a) bicarbonate concentration and electrical conductivity; (b) methane
production rate and bicarbonate concentration; and (c) methane production rate and electrical conductivity.

In this study, suitable anaerobic biofilm stability for methane production was observed when the
system conductivity achieved values around 1.2 mS·cm-1. This value established the minimum
starting-up time (20 days in our work, see Figure 2b and Figure 3) required to develop a functional
and stable anaerobic biomass consortium. In this respect, a minimum G25 value of around 1 mS·cm-
1
was identified as the minimum value that predicted a suitable bicarbonate concentration to achieve
a proper performance of anaerobic biomass consortia.
Finally, in order to validate the applicability of electrical conductivity sensors for monitoring the
start-up period of this AD process, the obtained simple regression models were used to estimate
both bicarbonate concentration and methane production rate in a new start-up period. Figure 5a
shows the evolution of G25, the experimentally measured bicarbonate concentration, and the
estimated bicarbonate concentration. Figure 5b shows the evolution of G25, the experimentally
measured methane production rate, and the estimated methane production rate. These figures show
the data evolution during the calibration period and the new start-up period. Around day 16 in
Figure 5, a failure in the pH-control system caused an increase of pH in the system up to values
around 10. Subsequently, the reactor was partially cleaned with water and the process was re-started
up (a considerable amount of biomass was lost due to the disturbance). As can be observed in
Figure 5, linear regression models were enough to successfully predict the bicarbonate
concentration (R2 coefficient of 0.91) and the methane production rate (R2 coefficient of 0.81) from
the measured electrical conductivity.

a b
Figure 5. Validation results of the linear regression models to estimate both (a) bicarbonate concentration and (b)
methane production rate.

The results shown in this work point to electrical conductivity as a possible state indicator for the
start-up period of an anaerobic fixed-bed reactor. It is important to highlight that, apart from their
low acquisition cost, on-line electrical conductivity sensors are reliable, simple and require low
maintenance for day-to-day monitoring and control (Vanrolleghem and Lee, 2002). Although
methane production rate is one of the most adequate state indicators for monitoring an AD process,
measuring methane composition is commonly expensive (i.e. on-line and off-line methane analysers
are much more costly and difficult to maintain than electrical conductivity sensors). Moreover,
measuring bicarbonate concentration is not easy. Hence, as commented above, this work provides
insights into the use of electrical conductivity as a possible state indicator for AD processes (e.g.
electrical conductivity could help rapidly identifying possible process disturbances). Hence, the use
of these low-cost industrially feasible on-line sensors would help engineers to handle day-to-day
tasks in full-scale AD systems.

4. CONCLUSIONS
Linear relationships between electric conductivity and both bicarbonate concentration and methane
production rate were observed. The obtained linear relationships successfully predicted both
bicarbonate concentration and methane production rate from on-line electrical conductivity
measurements. This highlighted the possibility of using electrical conductivity sensors as a cheap
and simple method for on-line monitoring the start-up period of an anaerobic fixed-bed reactor.

Acknowledgement
This research work has been supported by the EU (FP7-SME-2008-1 call, project ADD CONTROL
232302) and the Spanish Research Foundation (MICINN FPI grant BES-2009-023712), which are
gratefully acknowledged.

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