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Biomass and Bioenergy 142 (2020) 105786

Contents lists available at ScienceDirect

Biomass and Bioenergy


journal homepage: http://www.elsevier.com/locate/biombioe

Treatment of chocolate-processing industry wastewater in a


low-temperature pilot-scale UASB: Reactor performance and in-situ biogas
use for bioenergy recovery
S. Alcaraz-Ibarra, M.A. Mier-Quiroga, M. Esparza-Soto *, M. Lucero-Chávez, C. Fall
Instituto Interamericano de Tecnología y Ciencias del Agua, Universidad Autónoma del Estado de México, Carretera Toluca-Atlacomulco km 14.5, Unidad San Cayetano,
Toluca, C.P, 50200, México

A R T I C L E I N F O A B S T R A C T

Keywords: The main objectives of this research were twofold: a) to evaluate the performance of a low-temperature pilot-
Low-temperature UASB reactor scale upflow anaerobic sludge blanket (UASB) reactor during the treatment of a chocolate-processing industry
Chocolate-processing industry wastewater wastewater (CIW) with high soluble chemical oxygen demand; and b) to evaluate the performance of two
Bioenergy recovery
thermal conditioning devices (TCDs) for bioenergy recovery through the in-situ biogas use. For 275 days, the
In-situ biogas use
Daily produced energy
UASB reactor was operated at low temperature (17–19 ◦ C), short hydraulic retention time (6.2 h) and variable
Energetic potential of wastewater total organic loading rate (OLRT) and soluble organic loading rate (OLRS) (10.3 ± 2.9 kg-CODΤ/m3/d and 7.9 ±
2.2 kg-CODS/m3/d, respectively). The produced biogas was burned in-situ with two TCDs, which mainly con­
sisted of an insulated combustion chamber, a heat exchanger and a Bunsen burner. The OLRT and OLRS removal
efficiencies were 59.5 ± 13.6% and 71.4 ± 13.2%, respectively, whereas the biogas production was in the range
of 119–834 L/d. In-situ burning of the produced biogas with the TCDs increased the influent temperature be­
tween 0.8 and 5.8 ◦ C, which improved the biogas production of the UASB reactor. The CIW energetic potential
was calculated based on the UASB reactor operational parameters, the calorific value of methane in biogas and
the daily CIW production (90 m3) of the studied factory. The estimated CIW energetic potential (13.59 MJ/
m3CIW) represents a sustainable source of energy, which could be enough to satisfy the power consumption of
25–42 households in Toluca Valley Metropolitan Area, Mexico.

1. Introduction be quite significant [4,5]. However, under low temperature conditions


(<20 ◦ C), the COD-RE and biogas production might significantly
Many wastewaters (WW) with low and medium organic matter decrease [6–8].
concentrations are discharged at low ambient temperatures, including Operating temperature has a great impact in the COD-RE of UASB
domestic WW and a large variety of industrial WW [1]. The anaerobic reactors. WW anaerobic treatment works better at mesophilic (35–37
on-site treatment is especially suitable for concentrated WW [2], such as ◦
C) and thermophilic (50–60 ◦ C) temperatures, mainly due to the
those from industrial activities. An appropriate option for the anaerobic improved environmental conditions for anaerobic microorganisms [9].
treatment of concentrated WW is the upflow anaerobic sludge blanket In tropical countries, anaerobic WW treatment has been applied suc­
reactor (UASB). As opposed to aeration-based treatments, such as acti­ cessfully at full-scale and at ambient temperature without requiring
vated sludge, which consume a lot of aeration energy, the UASB reactor heating [10–13]. However, under psychrophilic temperatures (<20 ◦ C),
yields energy through the produced biogas [3]. The produced biogas is a the biological and chemical reactions proceed much slower than under
mix of several gases, mainly methane and carbon dioxide. The methane mesophilic conditions, mainly due to a higher energy requirement for
has an added value because it can be burned to produce either electricity biodegradation of organic matter [1]. Long lag-phase periods (165 days)
or heat. If the influent chemical oxygen demand (COD) and the COD are required before biogas production begins during low-temperature
removal efficiency (COD-RE) of an UASB reactor are high (>2300 anaerobic treatment (15 ◦ C) [14]. However, Connaughton et al. [15]
mg-COD/L, 70%, respectively), the energy production from biogas could reported a start-up period of only 21 days during the low-temperature

* Corresponding author.
E-mail address: mesparzas@uaemex.mx (M. Esparza-Soto).

https://doi.org/10.1016/j.biombioe.2020.105786
Received 3 April 2020; Received in revised form 2 September 2020; Accepted 14 September 2020
Available online 28 September 2020
0961-9534/© 2020 Elsevier Ltd. All rights reserved.
S. Alcaraz-Ibarra et al. Biomass and Bioenergy 142 (2020) 105786

anaerobic treatment of synthetic WW. It has also been reported that the carried out during the experimentation period (Table 1).
percentage of methane in biogas tends to decrease when operation
temperature drops from 24 to 14 ◦ C [16]. This behavior was also 2.2. Source of anaerobic biomass
observed by Masse et al. [17], who decreased the operation temperature
from 20 to 10 ◦ C during the treatment of swine manure in sequencing The anaerobic biomass used in this research was the preexisting
batch reactors. If the percentage of CH4 in biogas decreases, the power biomass that was inside the UASB reactor, which had been treating the
yield of the anaerobic treatment may decrease as well. same CIW for two years [33]. At the beginning of this research, the
Large amounts of heat are required to operate anaerobic reactors at anaerobic biomass was a well-settling mix of granular/flocculent sludge
mesophilic conditions in order to increase the COD-RE and the biogas with an initial total and volatile suspended solids (TSS and VSS,
production; but in some cases, the additional methane produced may not respectively) concentration of 13,681 and 9925 mg/L, respectively, and
be enough to offset the additional heating costs [18], resulting in a a VSS/TSS ratio of 0.73. The specific methanogenic activity (SMA) of
marginal or negative Net energy yield (NEY) [19]. This low NEY may this anaerobic sludge, which was measured with CIW as substrate at low
make the anaerobic treatment financially unfeasible [20]. Nevertheless, temperature (20 ◦ C), was 0.14 g-COD-CH4/g VSS∙d [34].
psychrophilic anaerobic WW treatment is a suitable option for raw WW
discharged at low ambient temperatures [1]. 2.3. UASB reactor operation
There are several modified versions of the UASB reactor, such as the
expanded granular sludge bed (EGSB) and EGSB-anaerobic filter (EGSB- A 244-L pilot-scale UASB reactor (0.30 × 0.35 × 2.33 m) was con­
AF) reactors. This type of reactors has been successfully used at low structed with 0.0125 m acrylic plates (Fig. 1). The UASB reactor was
temperatures (15–18 ◦ C) in the treatment of synthetic industrial WW insulated as previously described [35]. The UASB reactor was operated
[21–23] and raw industrial WW, such as brewery effluents [24]. How­ at short HRT (6.2 ± 0.3 h). The CIW was fed into the reactor with a
ever, these systems require recirculation of the effluent to increase the diaphragm pump (Cole Parmer, USA) to keep the flow rate (Q) constant
liquid upflow velocity inside the reactor (5–32 m/h), which represents a (0.66 ± 0.04 L/min). The biogas production was quantified by the water
substantial energy consumption for the recirculation pump, and there­ displacement method [36] using a 40-L glass container and a 4-L
fore the reduction of the NEY. Combined reactors with high energy inverted beaker (number 7, Fig. 1). Biogas composition was measured
input, such as continuous stirred-tank reactor (CSTR) and anaerobic on operation day 155 and 207. For practical purposes, the operating
baffled reactors (ABF), have been used to improve biogas production temperature of the UASB reactor was considered as the temperature
[25]. However, the use of CSTR implies mechanical mixing and in­ measured after the TCD (number 10, Fig. 1).
creases the energy requirements and power consumption, reducing the
NEY. If the raw biogas produced by an anaerobic reactor is burned
2.4. Thermal conditioning devices
in-situ, a significant amount of energy could be produced to heat the
reactor itself [26]. Increasing the operating temperature of a psychro­
Three temperatures were measured around the UASB reactor and
philic anaerobic reactor may improve its performance (COD-RE, biogas
TCDs: the storage temperature of the CIW (ST-T) gives an approximation
and methane production, etc.) and the NEY.
of the ambient temperature since the containers were not insulated
Over the past 10 years, the use of bioenergy in anaerobic reactors
(number 1, Fig. 1); the UASB influent temperature (In-T) was measured
during the treatment of different wastes (industrial and municipal
right after the TCD in the feeding line of the UASB reactor (number 10,
wastewater, municipal and agricultural solid wastes, etc.) has been
Fig. 1); the UASB effluent temperature (Eff-T) was measured at the top of
studied on theoretical scenarios [27–32]. In order to fill this techno­
UASB reactor (number 5, Fig. 1). The influent temperature rise, due to
logical gap on in-situ bioenergy use, a practical case study is presented
the TCD heating (ΔT), was calculated as the difference between In-T and
herein. The performance of a 244-L low-temperature pilot-scale UASB
ST-T.
reactor treating chocolate-processing industry wastewater (CIW) and
Two different TCDs (Fig. 2) and two operation stages (Table 2) were
the performance of two thermal conditioning devices (TCD) for the
tested in order to determine the best TCD in terms of heating efficiency.
in-situ use of biogas, were evaluated. This research was conducted at
The TCDs consisted mainly of an insulated combustion chamber, a heat
highly adverse conditions, such as low temperature, short hydraulic
exchanger and a Bunsen burner (Fig. 2).
retention time (HRT) and variable applied total and soluble organic
The daily produced energy (DPE) was calculated using equation (1):
loading rates (OLRTappl and OLRSappl, respectively), which are not rec­
ommended for anaerobic WW treatment. The key response variables DPE = CV × % CH4 × PB (1)
evaluated in the UASB reactor were the removal efficiency of total and
soluble organic loading rates (OLRT-RE and OLRS-RE, respectively) and where: DPE is the daily produced energy (kJ/d); CV is the theoretical
biogas production. The TCDs were evaluated in terms of daily utilized calorific value of methane at STP (35.75 kJ/L); % CH4 is the percentage
energy (DUE) and heating efficiency; the energetic potential of CIW of methane in produced biogas (84%); PB is the produced biogas
(EPCIW) was also evaluated. measured for each experimental stage at standard temperature and
This study seeks to contribute to the body knowledge regarding the
alternative and potential sources of sustainable energy, especially for Table 1
temperate climate regions such as Toluca Valley Metropolitan Area, | Physical-chemical characterization of CIW.
which is an important industrial and population area in México. CIW Parameter Units

pH 4.3 ± 0.6 (6)


2. Material and methods Discharge temperature (◦ C) 21.8 ± 1.5 (6)
CODT (mg/L) 7372.5 ± 3160.8 (6)
2.1. Chocolate-processing industry wastewater (CIW) CODS (mg/L) 5352.5 ± 2905.1 (6)
TSS (mg/L) 331.9 ± 359.2 (4)
VSS (mg/L) 296.4 ± 348.6 (4)
The WW used in this research was from a chocolate-processing in­ VFA (mg/L acetic acid) 381.4 ± 275.4 (4)
dustry located in Toluca Valley (Toluca, Estado de México, México). The Alkalinity (mg/L CaCO3) 821.8 ± 582.5 (4)
CIW was produced during the cleanup of production lines. The CIW was N–NH3 (mg/L) 4.2 (1)
received in 10-m3 water transportation trucks and stored in 1- and 5-m3 PTOT (mg/L) 177.2 (1)

containers at ambient temperature (11–19 ◦ C) for no more than 5 days. Average ± standard deviation. Number of samples (n) is shown between
Random physical-chemical characterization of CIW batches were parentheses.

2
S. Alcaraz-Ibarra et al. Biomass and Bioenergy 142 (2020) 105786

the DPE.
Additionally, the energetic potential of the CIW (EPCIW) was calcu­
lated using equation (5) [37]:
PB × % CH4
EPCIW = × CODS × CODS − RE × CV (5)
OLRSrem × VR

where: EPCIW is the energetic potential of the CIW (kJ/m3CIW); OLRSrem


is the removed soluble organic loading rate (kg-CODS/m3/d); VR is the
reactor volume (m3); CODS is the reactor influent CODS (g-CODS/LCIW)
and CODS-RE is the soluble COD removal efficiency (%). The other
variables are described in equation (1).

2.5. UASB reactor monitoring

Influent and effluent samples were collected six times a week for
Fig. 1. | Schematic diagram of the 244-L pilot-scale UASB reactor: 1. CIW determination of CODS and three times a week for (CODT). The collected
storage containers (5 and 1 m3); 2. Submersible centrifuge pump; 3. Influent
samples were filtered with glass-fiber filters (GF/C, Whatman, USA).
diaphragm pump; 4. Pilot-scale UASB reactor; 5. Gas – liquid – solid separator
The filtrates were collected in 40-mL amber-glass vials [38] and were
device; 6. CO2 trap (empty for this investigation); 7. Biogas measurement and
hydraulic seal; 8. Humidity trap (empty for this investigation); 9. Flow control processed the same day of sampling. Alkalinity and volatile fatty acids
valve; 10. Thermal conditioning device (TCD); 11. External lamelas settler. (VFA) were measured once a month; ST-T, In-T, Eff-T, Q, biogas pro­
duction, influent and effluent pH were measured once a day, six days a
week.
pressure conditions (STP) of 273 K and 1 atm, respectively (L/d).
The daily utilized energy (DUE) by each TCD was calculated using 2.6. Analysis
equation (2):
CODS and CODT were measured with a commercial COD Hach Kit
DUE = CP × ΔT × Q (2)
(method 435, high range COD, Hach, Co, USA); VFA and alkalinity were
measured according to the standard methods 5560 C and 2320 B,
where: DUE is the daily utilized energy from in-situ combustion of
respectively [39]; Temperature and pH were determined using a
biogas in each TCD (kJ/d); CP is the specific heat capacity of water
potentiometer (YSI 63-10 FT, YSI, Yellow Springs, OH, USA). Biogas
corrected for WW (90% of water CP) (3.8 kJ/L ◦ C); ΔT is the temperature
composition was measured with a combined gas warning and measuring
rise of the UASB influent due to the TCD heating (◦ C); and Q is the
device (Multitec® 560, Sewerin, Gütersloh, Germany). SST and SSV
average flow rate of the UASB reactor for each experimental stage (L/d)
were measured according to the standard methods 2540 D and 2540 E,
(Table 5).
respectively [39].
The heating efficiency of each TCD was calculated with equation (3):

Heating Efficiency =
DUE
× 100 (3) 3. Results and discussion
DPE
The heating efficiency (%) is an approximation of how much energy 3.1. CIW characterization
from the combustion of raw biogas was used in each TCD.
The NEY (kJ/d) for each stage was calculated by subtracting all the Table 1 shows the physical-chemical characterization of the CIW.
energy outputs from the DPE, with equation (4): The average CODS of the CIW was high (5352.5 ± 2905.1 mg/L) and
ranged from 2000 to 10,000 mg/L; the average CODS/CODT ratio was
NEY = DPE − DUE (4) 72.6%, which indicated that most of the organic matter was soluble. The
In this context, for S-1, the energy used to run the 0.1 HP peristaltic CIW had low concentration of TSS and VSS (331.9 ± 359.2 and 296.4 ±
pump was considered as an extra energy output and was subtracted from 348.6 mg/L, respectively), which facilitated its treatment without a
primary sedimentation stage. The suspended solids were mostly

Fig. 2. |Thermal conditioning devices (TCDs) used to burn the produced biogas in-situ: a) warm water recirculation system; b) polystyrene-insulated wood com­
bustion chamber.

3
S. Alcaraz-Ibarra et al. Biomass and Bioenergy 142 (2020) 105786

particulate organics (average VSS/TSS ratio = 89.3%). Table 3


The COD:N:P ratio of the CIW was 30:0.02:1, whereas the COD:N:P | Average operational parameters of the UASB reactor during overall experi­
ratio recommended by Metcalf & Eddy [5] to ensure the anaerobic mental run.
biomass activity is 250:5:1. Following this conservative criteria, the Parameter Overall experimental run
PTOT was enough to satisfy the biomass requirements of this nutrient, but Total period (d) 0–275
the N–NH3 was not. Despite of the nitrogen deficiency, the CIW was not Influent temperature (In-T) (◦ C) 18.5 ± 2.9 (223)
amended with external nutrients. However, chocolate may contain an Effluent temperature (Eff-T) (◦ C) 17.6 ± 2.2 (223)
average of 2.5% of total nitrogen as proteins [40]. The deamination of Q (L/min) 0.7 ± 0.1 (223)
HRT (h) 6.2 ± 0.3 (223)
proteins occurs during the hydrolysis stage of anaerobic digestion,
Upflow velocity (m/h) 0.4 ± 0.1 (223)
liberating the amino group of the molecule, which transforms itself into pH influent 6.7 ± 0.2 (223)
ammonia or ion ammonium, necessary for the synthesis of new bacteria pH effluent 6.9 ± 0.2 (223)
[41]. The biomass concentration inside the reactor increased from 9925 CODT influent (mg/L) 2616.3 ± 708.1 (108)
to 11,308 mg-VSS/L (data not shown), supporting the decision of no CODT effluent (mg/L) 1092.8 ± 531.5 (108)
OLRTappl (kg-CODT/m3/d) 10.3 ± 2.9 (108)
external nutrient addition. OLRTrem (kg-CODT/m3/d) 6.0 ± 1.9 (108)
The pH of the raw CIW was lower (4.3 ± 0.6) than the optimum OLRT-RE, % 59.5 ± 13.6 (108)
recommended for anaerobic treatment (6.5–7.6) [42]. Therefore, the pH CODS influent (mg/L) 2026.5 ± 554.5 (216)
of CIW was increased to 6.7 ± 0.2 (Table 3) before entering the UASB CODS effluent (mg/L) 613.2 ± 375.7 (216)
OLRSappl (kg-CODS/m3/d) 7.9 ± 2.2 (216)
reactor by adding a sodium hydroxide solution (0.4–1 L of 33% w/w
OLRSrem (kg-CODS/m3/d) 5.5 ± 1.5 (216)
NaOH). Alkalinity was added as sodium bicarbonate to a concentration OLRS-RE (%) 71.4 ± 13.2 (216)
of 1.5–2.5 g/L. Biogas production @ STP (L/d) 432.3 ± 137.6 (223)
The CIW was fed into the reactor as it was received, except in two Methane content in biogas (%) 83 - 85 (2)
periods of time: during the first period of time (day 58–106), the CIW Alkalinity (mg/L as CaCO3) 2249.4 ± 336.1 (8)
VFA (mg/L as acetic acid) 220.9 ± 125.5 (8)
was diluted because it had a high CODS (>7000 mg/L) and a lot of re­
agents were being used to increase its pH to 7. During the second period Average ± standard deviation. Number of samples (n) is shown between
(day 198–229), the CIW was also diluted because the operating tem­ parenthesis.
perature decreased (11–13 ◦ C) during winter and it had a negative
impact on the UASB reactor performance. In both cases, the CIW was larger HRT (>5 d) during the anaerobic digestion of potato leachate in a
diluted with tap water to an average CODS of 2000 mg/L and a minimum two-stage mixed-UASB system. Therefore, the HRT of 6 h selected for
of 1000 mg/L. this research was a suitable operational setting for the system.
Comparable HRTs have been used in the same UASB reactor during
3.2. Reactor temperature and HRT the treatment of cereal-processing industry WW and CIW, achieving an
OLRS-RE of 92 and 79% for HRT of 5.2 and 6.5 h, respectively [35,38].
The average operational parameters of the pilot-scale UASB reactor Connaughton et al. [15] has reported a similar OLRS-RE (82.7%) at short
are shown in Table 3. The reactor was operated at low temperature and HRT (4.9 h) and high OLRSappl (24.6 kg-COD/m3/d). This OLRSappl is
short HRT. The reactor Eff-T (17.6 ± 2.2 ◦ C) was always lower than the threefold the OLRSappl of our investigation (7.9 ± 2.2 kg-CODS/m3/d)
In-T (18.5 ± 2.9 ◦ C) due to heat losses along the reactor column, despite because a high recirculation rate and a high upflow velocity were used.
that the reactor was insulated with glass fiber and polystyrene plates. The higher OLRS-RE obtained by Connaughton et al. [15] could also be
Nevertheless, the temperature difference between In-T and Eff-T was in explained by the type of WW treated (synthetic, VFA-based,
average less than 1 ◦ C. nutrients-supplemented WW), which gave the optimal growth condi­
The average HRT (6.2 ± 0.3 h) remained stable for the 275 days of tions to the anaerobic biomass.
the experimental run. Although the HRT was shorter than that recom­
mended (10–14 h) for low-temperature WW treatment in UASB reactors 3.3. Soluble applied and removed organic loading rates
[5], the OLRS-RE (71.4 ± 13.2%) was within the range of OLRS-RE of
UASB reactors operated at similar HRT. This HRT was selected to The average OLRSappl (7.9 ± 2.2 kg-CODS/m3/d) (Table 3) had a high
demonstrate that anaerobic treatment of CIW was feasible under low standard deviation because the CIW was mostly fed to the reactor as it
operation temperature (18.5 ± 2.9 ◦ C) and short HRT; this HRT was also was received. The time series of the OLRSappl, the removed OLRS
selected in order to treat a large volume of CIW (Q = 950.4 ± 57.6 L/d) (OLRSrem) and the OLRS-RE are shown in Fig. 3, whereas the linear
with the 244-L UASB reactor. Kamyab et al. [43] reported that methane correlation between OLRSrem and OLRSappl is shown in Fig. 4. During the
yield (MY) was higher in short HRT conditions (1–5 d of HRT) than for 275 days of operation, the CIW quality in terms of CODS concentration

Table 2
|Operation stages of TCDs.
Stage Total period Description
(d)

S-1 0–109 A small combustion chamber (0.25 × 0.25 × 0.35-m) was built with 0.0125-m thick plywood and it was insulated with glass fiber (0.05-m) (TCDa) (
Fig. 2a).
Inside, a 1-L Erlenmeyer flask filled with tap water was heated with a Bunsen burner, which was continuously burning the produced biogas.
The warm tap water inside the Erlenmeyer flask was pumped with a 0.1 HP peristaltic pump (Cole Palmer, USA) through a 9-m copper long copper coil
(0.006-m diameter), which was inside a 70-L plastic container.
The 70-L insulated plastic container was filled with CIW, which was continuously flowing to the reactor inlet.

S-2 110–275 A second combustion chamber was built with 0.0125-m thick plywood (0.3 x 0.3 × 0.4 m) and it was insulated with 0.05-m polystyrene plates (TCDb) (
Fig. 2b).
An 8-L aluminum container was filled with tap water, insulated with polyester fiber and placed inside the combustion chamber.
An 8-m long copper coil (0.006-m diameter) was installed as heat exchanger inside the aluminum container.
The reactor influent was pumped through the copper coil.
The produced biogas was continuously burned with a Bunsen burner to heat the water in the aluminum container.

4
S. Alcaraz-Ibarra et al. Biomass and Bioenergy 142 (2020) 105786

24 100 Amini et al. [47] during the treatment of dairy WW with an upflow
OLRSappl & OLRSrem (kg-CODS/m3/d)

21 aerobic-anaerobic sludge blanket (UAASB) at 25–30 ◦ C, but at low


80 OLRSappl (1.9–3.4 kg-CODS/m3/d). Sumino et al. [48] treated municipal
18
sewage in a UASB reactor coupled to an aerated fixed-bed reactor at
15 ambient temperature (9.7–27.1 ◦ C), low OLRSappl (0.3–0.4

OLRS-RE (%)
60
12 kg-CODS/m3/d) and the UASB reactor removed 51–68% of the OLRSappl.
9 40 Gouveia et al. [49] obtained an OLRS-RE between 72.9 and 90.1%
during the treatment of municipal WW in a UASB reactor with an ul­
6
20 trafiltration membrane at low temperature (18 ± 2 ◦ C) and low OLRSappl
3 (0.8–4.7 kg-CODS/m3/d). As it can be seen, just a few investigations
0 0 have treated industrial WW at low temperature and medium OLRSappl in
0 25 50 75 100 125 150 175 200 225 250 275 UASB reactors.
Operation time (d)
OLRSappl OLRSrem OLRS-RE

3.4. Total applied and removed organic loading rates


Fig. 3. |Time series of the UASB reactor performance for OLRSappl, OLRSrem and
OLRS-RE. The period between vertical discontinuous lines (days 58–105 and
The OLRTappl and removed OLRT (OLRTrem) were calculated in terms
198–229) show the entrance of CIW diluted with tap water due to its high CODS
and winter season, respectively. of CODT (Table 3). Fig. 5 shows the linear correlation between OLRTrem
and OLRTappl. The OLRTrem and OLRTappl from other investigations car­
ried out in UASB, EGSB and AnMBR reactors operated at low tempera­
12 ture are shown in Table 4. These values were also graphed in Fig. 5. The
slope of the linear regression indicated an OLRT-RE of 61.11% was ob­
OLRSrem (kg-CODS/m3/d)

10 y = 0.7216x tained for this research (Fig. 5). This OLRT-RE is similar to 59.5%, which
R² = 0.7263 was mathematically calculated with the influent and effluent CODT data
8 (Table 3). The OLRT-RE calculated for the literature data was higher
(63.99%). However, the OLRTappl in this research were significantly
6 higher (4.1–16.9 kg-CODT/m3/d) than those found in literature
(0.6–6.4 kg-CODT/m3/d). This evidences that the 244-L pilot-scale
4
UASB reactor operated at higher OLRTappl than those reported in liter­
ature, but obtained similar OLRT-RE. On the other hand, the tempera­
2
ture range and the HRT applied in this investigation (17.6–18.5 ◦ C and
0 6.2 h, respectively) were within the ranges reported in the literature
0 2 4 6 8 10 12 14 (Table 4) (10–30 ◦ C and 3–16 h, respectively). However, the main
OLRSappl (kg-CODS/m3/d) achievement of this research was that despite the high OLRTappl, the
UASB reactor was stable and no inhibition or failure was observed for
Fig. 4. |Correlation between the OLRSrem and OLRSappl; the slope of the linear 275 days.
regression indicates the average OLRS-RE (72.16%).

3.5. Biogas production and methane yield


was highly variable. The OLRSappl ranged from 2.6 to 12.9 kg-CODS/m3/
d during the experimental run. Dilution with tap water was needed on The biogas production was corrected from the environmental con­
days 58 and 79 (Fig. 3), because a CIW batch with high CODs was ditions of Toluca Valley (average Eff-T = 17.6 ± 2.2 ◦ C and atmospheric
received. This dilution allowed to minimize the addition of NaOH and pressure = 0.74 atm at an altitude of 2650 m above the mean sea level)
NaHCO3 necessary to increase the pH up to 7. The pH dropped to 6.7 on to STP (273 K and 1 atm). The biogas production @ STP varied in the
these days, but even when most authors have recommended an optimum range of 119–834 L/d and showed a similar behavior as the OLRSrem: the
pH range between 7.0 and 7.5 [44], there was not a significant impact in biogas production increased and decreased as the OLRSrem did (Fig. 6a).
the reactor performance and the biogas production. Also, as shown in The correlation between biogas production @ STP and OLRSrem is shown
Table 3, there was no VFA accumulation in the UASB reactor effluent as in Fig. 6b. The linear regression showed a high R2 coefficient (0.8036).
alkalinity remained within an optimal range [5].
The average OLRS-RE of the experimental run (day 0–275) was 71.4
12
± 13.2%. This value is similar to the slope of the linear regression of the
correlation between OLRSrem and OLRSappl (72.16%) (Fig. 4). Despite the 10 y = 0.6111x
R2 coefficient of the linear regression was low (0.7263), the RE obtained R² = 0.575
OLRTrem (kg-CODT/m3/d)

with the OLR correlation was similar to that obtained mathematically 8


using the influent and effluent CODs data. The OLRS-RE is like that
obtained in the same reactor during other investigations (75–80%) 6
[33–35,38]. However, during those investigations, the OLRSappl were y = 0.6399x
not as high as the ones applied in this investigation (7.9 ± 2.2 4 R² = 0.776
kg-CODS/m3/d). Also, the authors worked with constant OLRSappl,
which were gradually increased in each experimental run. In this 2

research, the OLRSappl changed over short periods of time to see the
0
reaction capacity of the UASB reactor at continuously variable influent 0 3 6 9 12 15 18
CODS. This might explain the lower OLRS-RE obtained in this research. OLRTappl (kg-CODT/m3/d)
Other authors have reported higher COD and OLRS-RE (>86%) at Literature This research
low temperature (10–20 ◦ C), but those results can be attributed to the
use of synthetic WW and the application of low OLRSappl coupled with Fig. 5. |Linear correlation between OLR rem and OLRTappl for: ■ Results found
T

in literature for low temperature UASB, AnMBR, HUASB and EGSB reactors;
long HRT [26,45,46]. A similar OLRS-RE (71.27%) was obtained by
and ○ Results obtained in this research.

5
S. Alcaraz-Ibarra et al. Biomass and Bioenergy 142 (2020) 105786

Table 4
|OLRT-RE and MY reported for low temperature UASB reactors found in literature.
Reactor type WW type Temperature (◦ C) HRT (h) OLRTappl OLRTrem OLRT-RE (%) MY Reference
(kg-CODT/m3/d) (kg-CODT/m3/d) (L-CH4/kg-CODrem)

ASB DWW 12.5 8.1 1.8 0.9 48.0 23.2 [50]


12.5 6.0 2.4 1.2 52.0 19.6
12.5 4.0 4.4 1.6 37.0 16.0
UASB DWW 20 6.0 2.5 1.5 60.0 97.1 [51]
17.5 6.0 2.6 1.6 60.0 127.9
15 6.0 2.4 1.5 60.0 118.1
12.5 6.0 2.0 1.2 60.0 102.9
10 6.0 3.1 1.6 51.5 93.4
UASB MWW 17 10.0 1.5 0.9 60.0 126.0 [52]
19 10.0 1.5 1.0 64.0 129.0
19 8.0 1.9 1.2 65.0 117.0
19 6.0 2.5 1.6 61.0 120.0
UASB DS 25–30 12.0 0.9 0.6 65.5 91.0 [53]
UASB SCV 22 20–800 0.5–32.4 0.4–28.4 87.5 299 [54]
UASB DWW Ambient 8.0 0.6 0.3 53.4 NR [55]
8.0 1.1 0.7 62.9 NR
8.0 1.9 1.3 69.9 NR
8.0 3.3 2.8 85.6 NR
8.0 6.4 5.1 80.0 NR
UASB DS 15 6.0 2.5 0.8 31.8 192.5 [56]
15 6.0 2.5 0.8 32.2 269.5
15 6.0 2.7 1.0 37.1 322.0
UASB MWW 20 3.0 3.8 2.8 72.6 NR [57]
20 6.0 1.9 1.5 78.4 NR
20 9.0 1.3 1.0 81.7 NR
AnMBR DWW 15 16.0 0.7 0.6 92.0 181.2 [58]
HUASB SWW 12 12.0 1.0 0.7 74.0 352.3* [59]
12 12.0 1.0 0.8 77.0 352.5*
12 8.0 1.5 1.1 70.0 340.1*
EGSB SWW 10 18.0 1.3 1.2 90.0 38.0 [60]
10 12.0 2.0 1.7 86.0 57.0
10 12.0 2.0 1.5 74.0 122.9
10 12.0 2.0 1.7 84.0 66.6

DWW: domestic wastewater; MWW: municipal wastewater; DS: domestic sewage; SCV: sugar cane vinasse; SWW: synthetic wastewater NR – Not reported * Theoretical
values|.

The slope of the linear regression indicated that 78.8 L of biogas were
produced for each kg-CODS/m3 removed. This value was corrected by
the volume of the UASB reactor (0.244 m3) and the biogas yield was 900 30
obtained (322.95 L-biogas/kg-CODrem). The percentage of CH4 in biogas 800
Biogas production @ STP (L/d)

25

OLRSrem (kg-CODS/m3/d)
was 83 and 85%, on operation days 155 and 207, respectively (Table 3). 700
Therefore, the MY was 271.3 STP L-CH4/kg-CODrem. This calculated MY 600 20
was within the range reported in literature (16.0–352.5 STP L-CH4/kg- 500
15
CODrem) (Table 4). However, the calculated MY only represents the 400
77.5% of the theoretical MY @ STP (350 L-CH4/kg-COD), which is quite 300 10
similar to a MY recovery of 76.4% reported by Del Nery et al. [54]. The 200
5
calculated MY may have been lower than the theoretical MY due to the 100
loss of dissolved methane in the effluent [45] as the methane solubility 0 0
0 25 50 75 100 125 150 175 200 225 250 275
Operation time (d)
a) Biogas production @ STP OLRrem
Table 5 1000
| Average operational parameters of TCD’s for each experimental stage. 900
Biogas Production @ STP (L/d)

Parameter S-1 S-2 800


Total period (d) 0–109 110–275 700
OLRSappl (kg-CODS/m3/d) 7.7 ± 1.3 8.1 ± 2.6 600
Biogas production @ STP (L/d) 465.3 ± 66.8 459.6 ± 132.9 500
Q (L/d) 985.0 ± 57.9 937.4 ± 61.3
400
ST-T (◦ C) 17.0 ± 0.7 13.9 ± 1.7
300 y = 78.80x
In-T (◦ C) 19.3 ± 1.2 17.2 ± 2.2 R² = 0.8036
ΔT (◦ C) 2.3 ± 0.8 3.2 ± 0.9 200
Eff-T (◦ C) 19.1 ± 1.0 17.0 ± 2.1 100
DPE (kJ/d) 13,971.7 ± 2005.9 13,800.3 ± 3991.5 0
DUE (kJ/d) 8562.0 ± 2853.6 11,527.8 ± 3166.5 0 2 4 6 8 10
Heating efficiency (%) 61.4 ± 18.4 84.7 ± 12.4 b) OLRSrem (kg-CODS/m3/d)
Energy consumption of the 0.1-HP 6445.4 –
peristaltic pump (kJ/d)
Fig. 6. |a) Time series of the UASB performance for OLRSrem and biogas pro­
NEY (kJ/d) − 1035.8 2272.5
duction @ STP; b) Correlation between the biogas production @ STP and
the OLRSrem.

6
S. Alcaraz-Ibarra et al. Biomass and Bioenergy 142 (2020) 105786

increases as the temperature decreases (18.3 mg-CH4/L at 17.6 ± 2.2 ◦ C power consumption of 1.8 kW-h/d. The estimated cost of electrical
and 0.74 atm). power consumed was $ 2.24 USD per month ($ USD = 0.075 kW-h × 24
h/d × 30.416 d/month × $0.814 MXN/kW-h × $ 1 USD/$ 19.74 MXN)
or $ 27.09 USD per year (calculated for year 2019). Therefore, this
3.6. TCDs performance
electrical power consumption may reduce the NEY of the UASB reactor,
so the peristaltic pump was eliminated for the following experimental
Fig. 7 shows the UASB reactor temperature (In-T, Eff-T and ST-T) and
stage with TCDb.
the TCDs ΔT during the 275 days of operation. Unconventional high ΔT
The average ST-T during S-2 (day 110–275) was 13.9 ± 1.7 ◦ C. This
values were observed between days 25 and 60 due to water stratification
low temperature coincided with the transition from autumn to winter in
inside the 70-L container (Fig. 2a), where the heat exchanger was
Toluca Valley, leading to cooler ambient temperatures. The average STP
installed, which affected the measurement of the real temperature. In
biogas production during S-2 was 459.6 ± 132.9 L/d and it was slightly
order to decrease the experimental error of the collected data, such ΔT
lower, but not significant, than that during S-1 (465.3 ± 66.8 L/d). This
values were not considered in the final calculations. The ST-T began to
behavior was probably caused by the low In-T during S-2 (17.2 ± 2.2
decrease after day 142 due to the start of the autumn and winter season ◦
C). Despite these conditions (lower In-T and lower biogas production
in Toluca Valley (October to March) (Fig. 7). The lowest ST-T was
during S-2 than during S-1), the combustion of biogas allowed to obtain
reached on day 194 (11.1 ◦ C). Therefore, a 50-W electrical resistance
a ΔT of 3.2 ± 0.9 ◦ C. This ΔT was higher than that from S-1, leading to
was installed in the TCD to heat the UASB reactor influent. On day 214,
an increase in the heating efficiency of the TCD from 61.4 ± 18.4% (S-1)
the electrical resistance was withdrawn from the TCD. For the evalua­
to 84.7 ± 12.4% (S-2). This was probably due to lower heat losses in the
tion of the TCDs performance, the temperature data from day 194–214
TCD, because of a more effective insulation, even when the peristaltic
were not considered to avoid the interference of the 50-W electrical
pump was removed from the TCD.
resistance.
Unfortunately, these heating efficiencies cannot be compared with
The ΔT is an approximation of the heating capacity of the TCD as it
literature TCDs because they were homemade. As can be seen in Fig. 7,
burned biogas and heated the reactor influent. The TCDs ΔT varied from
ΔT showed the most stable behavior during the 165 days of S-2, despite
0.8 to 5.8 ◦ C (Fig. 7). Basically, the heat transfer occurred instantly as
a significant drop in ST-T (down to 12 ◦ C), which was observed on day
soon as the CIW entered the TCDs. The contact time between the reactor
259. This sudden drop in ST-T was attributed to the entrance of a cold
influent (through the copper coil) and the heated water (inside the
front to Toluca Valley, which caused a significant environmental tem­
aluminum container) was 51.5 s as the influent Q and the copper coil
perature drop.
length were kept constant.
The NEY for S-1 was negative (− 1035.8 kJ/d), whereas the NEY for
The average and standard deviation of In-T, Eff-T, ST-T, ΔT, Q,
S-2 was positive (2272.5 kJ/d). The TCDb from S-2 not only proved to be
OLRSappl and biogas production, as well as DPE, DUE and heating effi­
more efficient in terms of heating efficiency, but it also conducted to a
ciency for each experimental stage with the TCDs are shown in Table 5.
positive NEY. The NEY of 2272.5 kJ/d in S-2, represented almost the
The average DPE was always higher than the average DUE for both
16.5% of the DPE from the UASB reactor (13,800.3 kJ/d). For a UASB
TCDs. This was probably due to heat losses in each TCD. It was also
reactor operated in a low temperature region such as Toluca Valley
observed that the lower DUE, the higher the heat losses.
Metropolitan Area, a TCD has proved to be a useful system for bioenergy
As can be seen in Fig. 7 and Table 5, during S-1 (day 0–109), the ST-T
recovery and use in the reactor itself. TCDb increased the NEY by
had an average temperature of 17.0 ± 0.7 ◦ C and remained stable along
eliminating the peristaltic pump of the heating system.
the complete stage. S-1 was performed during summertime (July–Oc­
tober). The average ambient temperature in Toluca Valley during
summertime was temperate (21 ◦ C) due to rain season. ST-T was always 100
lower than the average ambient temperature because the CIW storage 90
containers, as well as the pilot-scale UASB reactor, were inside a hy­ 80
draulics laboratory, which had 15-m high ceiling and it did not have any 70
OLRS-RE (%)

heating. During S-1, the TCDa increased the In-T to 19.3 ± 1.2 ◦ C and 60
had a ΔT of 2.3 ± 0.8 ◦ C (Table 5). However, one of the main disad­ 50 y = 0.6162x + 70.175
vantages of the TCDa (Fig. 2a) was that it used of a peristaltic pump (1/ 40 R² = 0.0044
10 HP = 6445.4 kJ/d = 0.075 kW-h), which had an estimated electrical 30
20
25 15 10
0
20 12 0 1 2 3 4 5 6 7
a) ∆T (°C)
Temperature (°C)

15 9
900
ΔT (°C)

Biogas production @ STP (L/d)

10 6 800
700
5 3 600
500
0 0
0 25 50 75 100 125 150 175 200 225 250 275 400
y = 71.47x + 245.21
Operation time (d) 300 R² = 0.4476
In-T Eff-T ST-T ΔT 200

Fig. 7. Time series of UASB temperatures during the experimental run (275 100
days) for: In-T (influent temperature after TCD at the inlet of UASB reactor); Eff- 0
T (effluent temperature of the UASB reactor); ST-T (storage temperature of the 0 1 2 3 4 5 6 7
CIW before TCD) and ΔT (the temperature rise of the UASB influent due to the b) ∆T (°C)
TCD heating was calculated as the difference between In-T and ST-T). The
vertical discontinuous line separates the two operation stages with the Fig. 8. | Correlation between: a) ΔT (◦ C) and the OLRS-RE (%); and b) ΔT (◦ C)
different TCDs. and the biogas production @ STP (L/d).

7
S. Alcaraz-Ibarra et al. Biomass and Bioenergy 142 (2020) 105786

In order to evaluate if the TCDs (through the ΔT) improved the 4. Conclusions
performance of the UASB reactor, ΔT and OLRS-RE were correlated
(Fig. 8a) as well as ΔT and the biogas production @ STP (Fig. 8b). The 244 L pilot-scale UASB reactor, operated at low temperature
With a nearly horizontal slope and a low correlation coefficient (R2 conditions and short HRT, removed 52–91% of the OLRSappl and 39–84%
= 0.0044), the linear regression of ΔT vs OLRS-RE (Fig. 8a) showed no of the OLRTappl. The biogas production varied between 119 and 834 L/
influence of ΔT on the OLRS-RE of the UASB reactor. This was not the d STP. The biogas had 84% of methane. The OLRS-RE and the OLRT-RE
case for the linear regression of ΔT vs biogas production @ STP (Fig. 8b) were similar to those reported in literature for anaerobic reactors
in which the slope showed a positive linear correlation and a higher operated at low temperature and short HRT. In addition, the OLRSappl
determination coefficient (R2 = 0.4476). Also, the slope of the linear and the OLRTappl in this research were significantly higher than those
correlation was positive, indicating that the reactor influent heating parameters used in other investigations conducted at similar operational
improved the performance of the UASB reactor in terms of biogas pro­ conditions. Therefore, it demonstrated that the anaerobic treatment of
duction. Despite the increase of the In-T, the reactor temperatures (In-T CIW is feasible under these settings.
and Eff-T) remained in the psychrophilic range in this investigation The bioenergy recovery during the in-situ use of biogas allowed
(15–25 ◦ C). It has been observed that the performance of UASB reactors increasing the reactor influent temperature between 0.8 and 5.8 ◦ C,
can be enhanced with the increase of the operational temperature [57]. which led to increasing the performance of the UASB reactor in terms of
However, this temperature increase was done with an external heat biogas production. The polystyrene-insulated wood combustion cham­
source (electric heater), increasing the power consumption and prob­ ber (TCDb) had the highest heating efficiency. The average EPCIW was
ably reducing the NEY [57]. Therefore, the in-situ use of the produced 13.59 MJ/m3CIW, which is a sustainable potential source of energy
biogas reduced the power consumption and increased the NEY, for the which could lead to satisfy the electricity requirements of several
pilot-scale anaerobic reactor operated at low ambient temperature used households in Toluca Valley Metropolitan Area. For a country like
in this investigation. Mexico, where the cost of electricity production is high, the sustainable
production of energy from biogas should be further studied.
3.7. Energetic potential of CIW (EPCIW) The DPE from biogas of the UASB reactor proved to be useful for
heating the reactor influent. This research allows to establish the design
EPCIW was calculated considering the operational parameters of the bases for these systems on a larger scale. However, it must be taken into
UASB reactor during overall experimental run (Table 3). The average consideration that on a larger scale, the materials and design of the TCD
EPCIW was 13,597.3 ± 3706.0 kJ/m3CIW, (13.59 ± 3.70 MJ/m3CIW) with must be adapted to the needs of the system, so it is necessary to carry out
a maximum and a minimum of 27,609.2 and 3701.8 kJ/m3CIW, further research.
respectively. The maximum and minimum EPCIW corresponded to the
highest and lowest BP of 834.1 and 118.9 L/d, respectively. The average Acknowledgements
EPCIW of 13.59 MJ/m3CIW was calculated for the operational conditions
of low temperature (17–18 ◦ C) and medium OLRSappl (7.9 ± 2.2 kg- The authors would like to acknowledge the Consejo Mexiquense de
CODS/m3/d). The EPCIW obtained in this investigation was significantly Ciencia y Tecnología (Student Scholarship Number 17EA0005) and the
lower than the EP of sugarcane vinasse (144.0–187.2 MJ/m3) reported Consejo Nacional de Ciencia y Tecnología (Research Project Number
by Fuess et al. [37]. However, the EP of sugarcane vinasse was calcu­ 182696) for the financial support.
lated without considering the energy losses of the biogas conversion
systems (e.g., reciprocating engines, electrical generators, boilers and References
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AF: Anaerobic filter
AnMBR: Anaerobic membrane bioreactor

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S. Alcaraz-Ibarra et al. Biomass and Bioenergy 142 (2020) 105786

CIW: Chocolate-processing industry wastewater OLRTappl: Applied total organic loading rate
COD: Chemical oxygen demand OLRTrem: Removed organic loading rate
COD-RE: Removal efficiency of the chemical oxygen demand OLRT-RE: Removal efficiency of the total organic loading rate
DPE: Daily produced energy Q: Flow rate
DUE: Daily utilized energy SMA: Specific methanogenic activity
Eff-T: Effluent temperature of UASB reactor STP: Standard temperature and pressure conditions (273 K and 1 atm)
EGSB: Expanded granular sludge bed reactor ST-T: Storage temperature of CIW
HRT: Hydraulic retention time ΔT: Temperature rise of the reactor influent
In-T: Influent temperature of UASB reactor TCD: Thermal conditioning device
MY: Methane yield TSS: Total suspended solids
NEY: Net energy yield UAASB: Upflow aerobic-anaerobic sludge blanket reactor
OLRS: Soluble organic loading rate UASB: Upflow Anaerobic sludge blanket reactor
OLRSappl: Applied soluble organic loading rate VFA: Volatile fatty acids
OLRSrem: Removed soluble organic loading rate VSS: Volatile suspended solids
OLRS-RE: Removal efficiency of the soluble organic loading rate WW: Wastewater
OLRT: Total organic loading rate

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