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Solar Heated Food Waste Bioreactor for Enhanced Biogas Production and
Electricity Generation

Conference Paper · November 2021

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Solar Heated Food Waste Bioreactor for Enhanced Biogas Production and
Electricity Generation
Selebogo M. Khune1, Benton Otieno2, Peter Osifo3 and Aoyi Ochieng4
1
Vaal University of Technology, Private Bag X021, Andries Potgieter Blvd, Vanderbijlpark, South Africa; Phone: +27 725761634; E-mail:
[email protected]
2
Vaal University of Technology; E-mail: [email protected]
3
Vaal University of Technology; E-mail: [email protected]
4
Botswana International University of Science and Technology; E-mail: [email protected]

Abstract: Food waste generated in copious amounts in South Methane is 25 times more potent than carbon dioxide as a
Africa ends up in landfills creating environmental problems greenhouse gas while hydrogen sulphide produces bad and
such as the uncontrolled release of greenhouse gases. This unhealthy odour leading to serious environmental, economic,
study aimed to treat food waste through anaerobic digestion and and social problems [7]. The disposal of organic food waste to
generate electricity from the produced biogas. A Pilot-scale (1 landfills contributes 4.3% to South Africa’s greenhouse gas
m3) plant consisting of a complete-mix biodigester operated at emissions. Throughout the food supply chain from generation
mesophilic conditions (37 oC) with the aid of a solar geyser was to landfill, greenhouse gas emissions range between 2.8 and
used. A 1.5 kW biogas generator was used for electricity 4.14 tonnes CO2 per tonne of food waste [2]. The national
production. The biodigester was inoculated with cow dung and waste sector landfills contributed 18 773 Gg CO2 eq to the
operated at an optimum organic loading rate of 1.5 national methane emissions in 2010 [8].
kgVS/m3/day. The biodigester was effective owing to the
Controlled anaerobic digestion of food waste (and other organic
digester design and operation at mesophilic conditions
waste) has been studied and is considered a key element in
producing up to 1200 L (971 L/kgVS) of biogas per day. For
organic waste management due to its positive impact on the
every 1000 L of biogas produced, a maximum of 1.8 kW of
environment, economy, and energy [9,10]. It is found to have a
electricity was generated. The energy balance of the biodigester
net energy of 100-150 kWh/ton of waste [11]. This treatment
showed that only 10% of the energy generated was required to
method reduces the emissions of greenhouse gases into the
operate the plant, thus providing a net energy output of 90%.
atmosphere while producing carbon-neutral renewable energy
These results show that South Africa could have 475 GWh
and biofertiliser [12]. Anaerobic digestion is a biological
renewable energy potential based on the current food waste
degradation treatment of organic substrate undertaken by
generated annually, and it should be noted that effective
microorganisms in an aqueous environment in the absence of
digester design is critical in maximizing biogas production.
oxygen [13, 14]. The substrate must be sufficiently bloated with
Keywords: Anaerobic digestion; Electricity generation; Food at least 50% water [15]. The balanced methane fermentation
waste; Organic loading rate; Solar heating process is carried out by symbiotic fermentative bacteria such
as syntrophic acetogens, homoacetogens, hydrogenotrophic
1. Introduction methanogens, and acetoclastic methanogens [16].

Throughout the world’s food supply chain, 1.3 billion tons of Methane is the main constituent and is considered a fuel
food is wasted yearly [1]. South Africa (SA) produces product. Methane has a calorific value of 36 MJ/m3 and thus
approximately 9 million tons of food waste annually [2]. SA’s biogas has a calorific value of 22 MJ/m3 at 60% methane
current methods of organic waste disposal are incineration, composition [17]. The calorific value of biogas can be
landfills, composting, and anaerobic digestion. Incineration and improved by biogas purification. Biogas can be used for
composting require energy to operate while landfilling has been cooking, generating electricity in combined heat and power
considered the most practical and cheapest disposal method. plants (CHP), and as a vehicular fuel. A cubic meter of biogas
However, landfills are filling up quickly and creating the need can produce 2.1 kW of electricity assuming a mechanical
for more sites farther away from waste generation, thus efficiency of 35% for the generator. The generation of
increasing costs. Another challenge to landfilling is that more electricity from biogas is seen as one of the most dominant
than 50% of the waste disposed of in landfills is organic with future renewable energy sources since the continuous power
high moisture content and rots under uncontrolled anaerobic generation from organic waste can be guaranteed [13].
conditions, releasing landfill gas into the atmosphere and Therefore, it has been shown through research studies that food
leaching into underground water [3,4,5]. Landfill gas, also waste has high biodegradability properties and is thus suitable
known as biogas, contains 55 – 70% methane, 30 – 45% carbon for anaerobic digestion for producing biogas energy [18].
dioxide, and trace amounts of hydrogen sulphide (0-2000 ppm), This study aimed to treat food waste through anaerobic
moisture (depending on temperature), and siloxanes [6]. digestion at a pilot scale. The biogas produced was used to
generate electricity and the energy balance of the pilot plant 2.3. Digester start-up and operation
was determined. The AD condition treatment was evaluated at Anaerobic digestion was initiated by introducing 200 kg of CD
a constant temperature, pH, and mixing while varying organic inoculum to the digester which contained 600 L of preheated
loading rate. The energy analysis was carried out to evaluate tap water to obtain a working volume of 800 L [19].
the efficiency of the plant and determine South Africa’s food Experiments were not conducted in triplicates due to time
waste electricity potential. constraints considering the design, construction, commissioning
and startup of the pilot plant. At the beginning of the startup
2. Materials and methods and after 24 hours of stabilization, biogas volume, biogas
composition, digestate pH, and temperature were monitored
2.1. Materials
daily. Inoculation was allowed to proceed until the produced
A pilot-scale biodigester operated at mesophilic conditions was biogas cumulative difference was less than 1%. At the end of
assembled at the Vaal University of Technology (VUT), South inoculation, the optimal OLR was determined by feeding the
Africa. A 1.5 kW biogas generator was purchased from Puxin digester batch-wise with different organic loads of 1, 2, 3, 5,
Technology, in China. A handheld biogas analyser was and 7 kgVS/m3. Food waste was collected, blended, and stored
purchased from China, Beijing Shi’An Technology Instrument in a shaded area in bulk batches of 60 - 100 L. Each load was
Co. LTD. Two Ritter biogas meters were donated by Devos added to the digester and allowed to digest until the biogas
Laboratory. Cow dung (CD) was sourced from a local farm in accumulative difference was less than 1%. At this point, a
Vanderbijlpark, while food waste (FW) was collected from the higher load was introduced. After determining the optimal
VUT Vanderbijlpark campus cafeteria and Stonehaven OLR, the digester was operated semi-continuously using the
Restaurant in Vanderbijlpark, South Africa. The FW comprised draw and fill method.
mainly of organic materials 60% included rice, raw dough, slap
chips, buns, bread, porridge; 30% vegetables and fruit and 10% 2.4. Biogas conversion to electricity
grease, chicken and meat. A biogas compressor pressurized biogas to 2 – 6 kPa and then
the generator engine was started. Devices and gadgets with a
2.2. Experimental setup
total power consumption of 1500 W were connected to the
The experimental setup consisted of a complete-mix anaerobic generator. A wattmeter was connected between the generator
biodigester (CMBD) operated at a controlled temperature of 37 and appliances to measure power output.
o
C. CMBD was constructed from a 1000 L vertical tank with a
working volume of 800 L. The biogas holder had a capacity of 2.5. Chemical and physical analysis
1000 L. Substrate was mixed using a submersible 180 W Samples of the blended feed and digestate were removed and
grinder pump. The digester was heated using a 100 L solar measured for total solids (TS) and volatile solids (VS) using the
heat-exchanger equipped with a temperature controller. A food standard method of analysis [20]. Alkalinity in the digester was
blender was used to reduce the particle size of the substrate. analyzed using a pH meter. The digester temperature was
Biogas quantity was measured with a biogas meter, with a flow measured using a digital STC-1000 temperature controller
rate ranging between 1 and 18 000 L per hour. An 18 W biogas connected to a thermocouple. Biogas composition was analysed
compressor was used to extract biogas from the biogas holder with an online natural diffusion hand-held biogas analyser to
to supply to downstream processes. A 1.5 kWh generator was measure CH4, CO2 and H2S. The biogas analyser could measure
used for electricity generation with a conversion efficiency of methane and carbon dioxide, each between 0 – 100 Vol% and
22%. The generator employed combustion, air-cooled, four- between 0 to 1000 ppm for H2S.
stroke single-cylinder engine. The experimental setup is
outlined in Fig. 1. 3. Results and discussion

3.1. Characterization of the substrate


The biodegradability of a substance can be determined by its
physical and chemical characteristics, which influence the
performance of anaerobic digestion by affecting the methane
yield and process stability [18]. The biodegradability of the
food waste and cow dung as determined from the moisture
content (MC), total solids (TS), and volatile solids (VS)
percentage is presented in Table 1. A high amount of moisture
in a substance makes it suitable for anaerobic digestion [7]. In
this study food waste was found to contain 85% of MC and the
inoculum contained an average of 53%. The VS content in a
Fig. 1. Schematic representation of the pilot biogas plant substrate represents the biodegradable matter. The average VS
coupled to an electricity generator.
contents obtained for food waste and inoculum were 14 and 8
(b)

Digestate pH
16%, close to the 13% and 15% obtained by Kuczman et al.,
7,5
[21] and Dhamodharan et al. [22], respectively. The inoculum
used for the startup of the CM biodigester had a pH value of 7.3 7
which is suitable for methanogenic bacteria.
6,5
Table 1: Characteristics of CD and FW 20 25 30 35 40 45 50 55
Digestion time (Days)
Parameter Cow dung Food waste
Moisture content (%) 53 85 Fig. 2. (a) Biogas composition during CMBD startup and
Total solids (%) 47 15 (b) digestate pH
Volatile solids (%) 35 95
pH 7.3 4 3.3. Biodigester performance at different OLR
After the startup period of 55 days, CMBD performance at
Moreover, the VS/TS ratio is an indicator for evaluating the different OLR was monitored by evaluating pH, biogas
suitability of a substrate for biogas production; substrates with a composition, and biogas and methane yield. Biogas hourly
higher VS/TS ratio contain higher organic matter and thus are production rate and cumulative biogas production for the first
more suitable for biogas production [23]. In this study VS/TS 40 hours of FW digestion were monitored as well. From Fig.
for food waste was found to be 95%, an amount close to that of 3a, biogas production occurred in a series of peaks starting with
Zhang et al., [23] of 94 %. These high values indicated that the two main peaks, the second one being the highest. These peaks
food waste was rich in biodegradable matter and thus had an took place between hours 2 and 13, with the highest peak
excellent biomethane potential. Substrates with VS/TS higher occurring between hours 8 and 13. This was an illustration of
than 80% are considered great candidates to be anaerobic intense biogas production during the initial hours after digester
digestion feedstock [24, 25]. The VS/TS ratio for the inoculum feeding. A similar observation was found by Koch et al. [26]
was 35%, which demonstrated that there was a small fraction of who reported that the intense biogas production was an
organic matter to be digested, substances with values below indication of the presence of readily degradable compounds.
17.4 to 10 % are considered inorganic [21]. The highest biogas production rate was 131 L/hour for OLR 7
3.2. Biodigester start-up (see Fig. 3a). Lui et al. [27] obtained the highest peak of 0.8
L/day at an average OLR of 8.5 kgVS/m3, while El-Mashad
Cow dung was pre-incubated as inoculum in the prototype
and Zhang [28] obtained 59 L/kgVS/day at 2 kgVS/m3 within
biodigesters for 55 days to create a suitable environment for
the first day of digestion.
food waste digestion. The methane composition, which was
monitored from day 22 when significant activity was observed, Cumulative biogas production increased with an increase in
ranged between 42 and 59% and CO2 between 18 and 25% as loading, with OLR of 1, 2, 3, 5, and 7 kgVS/m3 producing 544,
shown in Fig. 2a, while H2S ranged from 0 to 49 ppm, Fig. 2b. 931, 1746, 2334, and 2796 L of biogas, respectively, as
The flammable biogas contained an average of 54% CH4 and depicted in Fig. 3b. The hourly production rate dropped
24% CO2 and 17 ppm of H2S. The unaccounted volume of gas significantly within 40 hours for OLR 1, 2, and 3 kgVS/m3.
by the biogas analyser could be ascribed to traces of different Whereas OLR 5 and 7 continued at significant production rates
gases (NH3, H2, N2, O2, CO). The pH remained stable averaging 20 and 50 L/hour, respectively. Approximately 80%
throughout the inoculation period and within the methanogenic of biogas was obtained within 40 hours of digestion time for
favorable range. The digestate pH level ranged between 7.2 and OLR 1, 2, and 3; whereas, up to 50% was obtained for OLR 5
7.5 over 55 days. This indicated that an excellent digestate and 7 within the same period. This indicated that continued
buffering capacity was introduced in the biodigesters. From daily organic loading at high rates might result in system
these results, it can be confirmed that methanogenic conditions overload due to organic compounds accumulation and thus
were successfully obtained during inoculation. lowering the microbial activity.
300 Methane production and accumulation are critical in evaluating
CH4 CO2 H2S (a)
60 methanogenesis during digestion. Similar to the biogas
CH4 & CO2 (%)

200 production profile shown in Fig. 3a, the methane production


H2S (ppm)

40 profile comprised of a series of peaks as given in Fig. 3c. Koch


100 et al., [26] observed a similar trend in their first 100 hours of
20
co-digestion of food waste with municipal wastewater. There
was an increase in methane production with an increase in
0 0
20 25 30 35 40 45 50 organic load to a limit, which was OLR 3 kgVS/m3. OLR 5 and
Digestion time (Days) 7 kgVS/m3 showed no clear trend in methane production as
shown in Fig. 3c. The lack of a clear trend indicated instability
of the anaerobic digester at high OLR. Fig. 3d shows that OLR
3, 5, and 7 produced almost similar cumulative methane within 3000
1 2 3
the first 40 hours of digester feeding. These results show

Cumulative biogas
5 7
methane inhibition beyond OLR 3, which confirms digester 2000

(L/hour)
overload, thereby hindering microbial activity [27]. (b)
1000
Methane production for the OLR of 1, 2, and 3 kgVS/m3 was
highest at 18, 29, 42 L/hour on hours 4, 16, and 10,
respectively, which was reduced to 5 L/hour by day 39. OLR 5 0
0 5 10 15 20 25 30 35 40
and 7 kgVS/m3 had the highest methane production rate of 47.5 Digestion time (Hours)
and 43.5 L/hour by day 10 and 6, respectively, by day 40 the
methane production was still significantly exceeding 15 L/hour. (c) 1 2 3

Methane production
Furthermore, after day 28, OLR 7 kgVS/m3 methane production 40 5 7

rate (LCH4/hour)
increased from 18.6 to 30.4 L/hour by day 40. This trend
indicated the reduction in initial overload leading to enhanced
20
microbial activity and therefore improved methane production.
Koch et al. [26] obtained the highest peak of 13.7
LCH4/kgVS/hour within the first 10 hours of digestion. 0
0 5 10 15 20 25 30 35 40
3.4. Biogas yield and composition at different OLR Digestion time (Hours)
1200
The specific biogas and methane yield of food waste after 40 1 2 3 5 7
hours at the various organic loads are represented in Fig. 3. The Cumulative methane 900
(LCH4/day) (d)
graph shows a clear decrease in biogas and methane yield
600
beyond OLR 3. Organic loads 1 and 3 kgVS/m3 obtained the
highest biogas and methane yields of 655 and 709 L/kgVS, and 300
411 and 409 LCH4/kgVS/m3, respectively. OLR 7 obtained the
0
lowest specific biogas and methane yield of 492 L/kgVS/m3 0 5 10 15 20 25 30 35 40
and 195 LCH4/kgVS/m3, respectively. OLR 3 gave the highest Digestion time (Hours)
conversion of biogas from food waste and thus was chosen to
Fig. 3. (a) Biogas production hourly rate and (b) cumulative
be the optimal organic load as per specific biogas and methane
biogas production (c) hourly methane rate and (d)
yield. Consequently, the OLR of 3 kgVS/m3 produced higher
cumulative methane production during anaerobic digestion
cumulative biogas and methane than OLR 1. OLR 3 produced
of food waste at different organic loadings.
three times more biogas and methane than OLR 1 in the same
period, thus making it a desirable operating parameter. Babaee The composition of biogas produced shows the methanogenic
and Shayegan, [28] obtained the optimal organic load to be 1.4 bacteria performance as depicted in Fig. 4d. It was observed
kgVS/m3/day which yielded 250 LCH4/kgVSadded. El-Mashad that an increase in organic load resulted in a decrease in
and Zhang, [29] obtained 657 L/kgVS from waste food after 30 methane content and an increase in carbon dioxide content at
days of digestion 79.1% of which was produced after 20 days the early stages of digestion. Hydrogen sulphide content
of digestion. Also, after 20 days of digestion, the methane yield showed no significant response to organic load increase. The
accounted for 72.5% of 353 L/kgVS obtained after 30 days highest H2S average content was 39 ppm. According to
[29]. Pipatmanomai et al. [30], H2S content below 50 ppm is below
toxicity levels and thus safe to be used in combustion electricity
120
1 2 3 generators and biogas stoves.
5 7
At high OLR methane content dropped and carbon dioxide
Biogas production rate

(a)
80
content increased as shown in Fig. 4a and b. The biogas quality
(L/hour)

for OLR 5 and 7 improved after hour 32 where methane and


40
carbon dioxide contents were within the usable range for
0 energy conversion. Besides, this is characteristic of the primary
0 5 10 15 20 25 30 35 40 stages of AD, hydrolysis, acidogenesis, and acetogenesis,
Digestion time (Hours) producing CO2. These stages have a higher growth rate than the
methanogenesis stage [16]. Thus, it is critical to maintain a
loading rate that promotes methanogenic bacteria growth rate
and prevents excessive acids and CO2 build-up that could
inhibit the hydrogenotrophic methanogens [16].
900 average composition of biogas at different organic loads for
(a) Biogas yield
food waste in Fig. 4c showed that an increase in organic load
Yield (L/kgVS)

700 Methane yield


resulted in a decrease of methane content and an increase in
500 carbon dioxide composition. Higher organic loads resulted in
300 poor-quality biogas that cannot be used as fuel. The average
methane and carbon dioxide contents for OLR of 1, 2, 3, 5 and
100 7 kgVS/m3 were 63, 60, 58, 50 and 43 %, and 14, 26, 30, 32
0 1 2 3 4 5 6 7 8
Organic Load (kgVS/m3) and 33 %, respectively.

3.5. Operation of the anaerobic digester at optimal


60 conditions
CH4 (%)

The CMBD anaerobic digester was operated at the optimal


40 organic loading rate of 1.5 kgVS/m3/day for 35 days to monitor
the daily operation of the biogas pilot plant and to determine
1 2 3
(b) 5 7 the daily biogas production. The optimum OLR of 3 kgVS/m3
20
0 5 10 15 20 25 30 35 40
took 48 hours to completely digester therefore to run the
digester daily the OLR was halved so as not to overfeed the
Digestion time (Hours)
digester. Biogas and methane daily production rate increased
1 2 gradually over the digestion period, this was due to the
50 (c) 3 5
7 presence of residual substrate from previous feeds which
increases with additional feed (Fig. 5.a). On the first day, 341 L
CO2 (%)

30 (276 L/kgVS/day) of biogas and 187 L (151 L/kgVS/day) of


methane were produced and increased daily to a maximum
average of 1319 (1068) and 791 (641) L/day (L/kgVS/day),
10 respectively, on day 91. Additionally, the graph consists of a
0 5 10 15 20 25 30 35 40
series of peaks occurring on days 61, 69, 83, and 91; the
Digestion time (Hours)
80 45 reduction in biogas production post-peak was due to the fresh
food waste introduced to the digester after the prepared bulk
CH4 & CO2 (%)

CH4 CO2 H2S


60
H2S (ppm)

30 batch had been depleted. This was because feeding fermented


40
food makes volatile fatty acids readily available to the
15
20 microorganism in the digester; hence fermented food is more
(d) favourable than fresh food waste and improves biogas
0 0
0 1 2 3 4 5 6 7 8 production [31].
Organic Load (kgVS/m3)
Biogas showed to be rich in methane throughout the digestion
Fig. 4. (a) Specific biogas and methane yields, (b) hourly period with an average of 60% and a low concentration of CO2
methane and (c) carbon dioxide contents, and (d) overall at an average of 29 % and 94 ppm for H2S. The highest
composition of cumulative biogas produced during methane concentration obtained was 68% on day 65, and the
anaerobic digestion of food waste at different organic lowest carbon dioxide was 24% and 44 ppm for H2S (Fig. 5.b).
loading rates. The graph shows that digestion conditions were stable and
favorable for methanogenesis. This can further be seen in the
After hour 13, there was a gradual decrease in carbon dioxide digestate pH levels in Fig. 5.c. The pH was stable and ranged
production as they were converted into methane. Consequently, between 7.3 and 7.8 with no adjustment required. This was an
methane content increased gradually after hour 13. OLR of 2 indication of a high buffering capacity, attributed to inoculum,
and 3 kgVS/m3 followed a similar trend as did OLR 5 and 7 and optimum OLR.
kgVS/m3; biogas composition for the OLR of 2 and 3 kgVS/m3
remained within favourable range throughout the digestion Biogas Methane
Biogas production rate

1200,0
period whereas for OLR 5 and 7 kgVS/m3 the composition was (a)
compromised. The results for OLR of 1 kgVS/m3 showed the
(L/Day)

800,0
most stable methane and carbon dioxide content throughout the
digestion period. Methane content for OLR of 1, 2, and 3 400,0
kgVS/m3 ranged between 53 and 66%, whereas OLR of 5 and 7
kgVS/m3 ranged between 20 and 60%. The carbon dioxide 0,0
58 63 68 73 78 83 88
content for OLR of 1, 2, and 3 kgVS/m3 ranged between 10 and
Digestion time (Days)
42%, and 15 and 64% for OLR of 5 and 7 kgVS/m3. The
80 pilot scale.
CH4 CO2 H2S (b) 800
60 Table 2: Power consumption of equipment used in biogas
CH4 & CO2 (%)

600 production and biogas use

H2S (ppm)
40
400 Component Rating (W) Usage (W)
Digestate circulation pump 180 45
20 200 Hot water circulation pump 8 1
Solar geyser temperature controller 5 5
0 0
58 63 68 73 78 83 88 Hot water circulation controller 3 3
Digestion time (Days) Food grinder 373 90
Biogas blower 16 16
8,1 Total 585 160
(c)
Digestate pH

7,6
4. Conclusion
7,1
The successful construction and operation of the pilot plant
6,6 indicated that biogas technology is within reach to South
58 63 68 73 78 83 88 Africans; all the parts used for the construction of the digesters
Digestion time (Days) were sourced locally except for the generator engine. The
Fig. 5. Daily (a) biogas and methane production (b) biogas digester temperature test work results showed that a 1 m3
composition and (c) digestate pH during anaerobic digester can be well heated using a 100 L solar heated geyser
digestion of food waste at optimum OLR of food waste. without electrical backup. The digester was heated up from
24.1 oC to 37.3 oC in 10 days and was well maintained at that
3.6. Biogas conversion to electricity and energy balance temperature with sufficient insulation. Also, it was found that
A maximum of 1.8 kWh of electricity was generated from 1000 when the solar geyser water was at temperatures between 80
L of biogas with an overall conversion efficiency of 22%. The and 100 oC the digester could be heated from 24 to 38 oC in 2
biogas consumption of the generator was 650 L/hour. On a days. Cow dung proved to be suitable for inoculation as it
national scale, this amount of electricity can light up to three provided a healthy environment for digesting FW. For digesting
hundred 6 W energy saver light bulbs for an hour. In a rural highly acidic food substrate, CD provided a high buffering
setting where there is no electricity, this biogas pilot plant can capacity to the system. pH levels remained stable throughout
provide electricity and allow the users to perform short-term the digestion periods with no irreversible acidification typically
energy-requiring tasks. experienced in the treatment of FW. The optimal OLR of 1.5
kgVS/m3/day, which made up 7 kg of waste food at a food-to-
The energy balance considers the energy input to run the biogas
water ratio of 3:2, was able to produce 1400 L/day (1134
pilot plant and compares it with the total energy output. The
L/kgVS/day) of biogas. At the end of 35 days of digestion a
temperature controllers used in this plant were operated
total of 31 535 (25 534) and 19282 (15 612) L (L/kgVS) of
continuously throughout the day and consumed a total of 8 W
biogas and methane, respectively, was produced. From 1000 L
per hour, these are the lowest energy-consuming component of
of biogas 1.8 kWh of electricity was produced equivalent to
the plant. The two highest energy-consuming components of
powering three hundred 6 W light bulbs for 1 hour. The energy
the plant were the food blender and digestate circulation pump.
balance over the pilot plant showed that the system required
The food blender had the highest power rating however it was
10% energy of its energy output to produce 1.8 kW. Based on
used only for 15 minutes a day consuming 90 W. The digestate
these results it can be concluded that the pilot plant is effective
circulation pump was operated for 15 minutes per hour daily,
and a viable technology in South Africa.
thus it consumed 45 W. The hot water circulation pump ran
continuously at startup for 2 days and then it would turn off
Acknowledgments
when the set digester temperature was reached and then it runs
for approximately 3 hours in the morning. On average the hot We acknowledge Financial Support from the Water Research
water circulation pump used 1.3 W per hour daily. When Commission (WRC, Project no. C2020/2021-00426), South
running the generator, the biogas blower was used to pressurize Africa, and Postdoctoral Funding from the German Academic
the biogas and it consumes 16 W per hour. In total, the energy Exchange Service (DAAD).
input to run the entire biogas pilot plant per hour was 160 W
(see Table 2). In comparison to a power output of 1800 Wh, the References
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Synergistic effect of functionalised Zn-FeTiO2 and Cu-ZnFeTiO2 on
biostimulated methanation process

E Kweinor Tetteh*, G Amo-Duodu and S Rathilal


The Faculty of Engineering and the Built Environment, Green Engineering and Sustainability Research Group,
Department of Chemical Engineering, Durban University of Technology, Steve Biko Campus (S4 Level 1) Box 1334,
Durban 4000, South Africa ; [email protected] (GAD), [email protected] (SR)
Correspondant email : [email protected] / [email protected] (EKT)

Abstract: With the rapid shift of nanotechnology from In wastewater treatment settings, CO2 methanation is a potential
laboratory to large-scale industrial applications, the release of option for mitigating anthropogenic gas emissions [1, 2]. In
nanomaterials into the environment is unavoidable. In fact, essence, valorisation of CO2 from biogas produced via anaerobic
wastewater treatment settings (biosolids) being the major digestion (AD) of high strength organics is a viable route to meet
receptor of these nanomaterials needs to be improved to curb this wastewater treatment energy inputs. Consequentially,
environmental concern. In this study, magnetised nanoparticles application of nanomaterials is gaining momentum in the
(MNPs) such as Zn-FeTiO2 and Cu-ZnFeTiO2 were synthesised wastewater settings, whereby their end of life and recoverability
using the co-precipitation method and characterised using possess environmental challenges [1, 3]. Therefore, employing
Fourier-transform infrared spectroscopy (FTIR), X-ray powder magnetic nanoparticles (MNPs), which is easily separated with
diffraction (XRD) and scanning electron microscopy/energy external magnetic field, represents a promising solution in
dispersive X-Ray spectroscopy (SEM/EDS) techniques. Their curbing some of these concerns including cost of discharging
synergistic effect on biogas production (methanation) and sludge and landfills complexity with heavy metals [4, 5, 6].
metabolic activity was investigated by adding 1.5 g of MNPs to Additionally, MNPs have been reported to have the potential as
anaerobic digestion of municipality wastewater and comparing a biostimulant for biogas enhancement in AD processes [7].
the performance to a control reactor (with no additives). After 30
Generally, treating wastewater with an AD process to generate
days of incubation at mesophilic temperature (35℃), the daily
biogas has been a slow process [8, 9]. Other researchers have
biogas production was collected by downward water
reported on the use of MNPs in biostimulated methanation
displacement (inverted cylinder). The subsequent cumulative
processes for the enhancement of AD process performance with
biogas volume calculated followed a modified Gompertz kinetic
respect to methane yield and water quality treatability
model (P < 0.005). Cumulative biogas production of 200 mL and
performance [3, 7, 10, 11, 12]. Manzoor el at. [11] investigated
105 mL with methanations enhancement of 100% CH4 and
the effect of photocatalytic MNPs, such as ZnFe2O4/TiO2 and
96.7% CH4 upon the addition of Cu-ZnFeTiO2 and Zn-FeTiO2
ZnFe2O4 for CO2 methanation. These catalysts were chosen
were respectively recorded. This was compared to the control
because they are stable, have resistance towards corrosion, and
reactor performance of 52.5 mL and 65.7% CH4. Using the
is cheap. Also, additive metals such as iron, zinc, copper, and
biogas production as a metric over time, the rate constant
nickel have nutritional value in the AD phase and their inclusion
obtained were 0.2605 d-1 > 0.183 d-1 > 0.118 d-1 for the system
can significantly stimulate microbial activities, thereby affecting
with Cu-ZnFeTiO2, Zn-FeTiO2 and control, respectively. Results
both methane and biogas yields [11, 13, 14]. Due to efficacy and
of these findings exemplify the possibility of intensifying the use
physiochemical properties of MNPs, which includes being
of MNPs to improve anaerobic digestion processes in the
superparamagnetic, having large surface area, its nanosize,
wastewater treatment settings.
resistance to corrosion, chemical and thermal stability, their
hybridized form with a photocatalyst has proven to be more
suitable [2, 11, 15]. However, to the best of our knowledge, the
Keywords: Biogas; bioenergy; biostimulation; magnetic
applicability of magnetised photocatalyst and its mechanism in
nanoparticles; methanation; kinetics
AD processes is still limited. Therefore, this study seeks to
understand the synergistic effect of Cu-ZnFeTiO2 and Zn-
1. Introduction
FeTiO2 on a biostimulated methanation process for local South by Pope et al. [17].
Africa Sugar refinery wastewater treatment via the water quality
and methane yield. 2.3. Kinetics of biostimulated system
Using the cumulative biogas yield for 30 days, each
2. Materials and Methods biostimulated system was modelled using the first order (1) and
modified Gompertz (2) kinetic models to estimate their
With the protocols adapted from APHA [16], the wastewater respectively kinetic variables [19].
obtained from a local South Africa Sugar refinery wastewater
treatment plant in the KwaZulu Natal Province was characterised Y(m) = ym [1 − exp( − kt)]
to constitute chemical oxygen demand (1340 mg COD/L), (1)
turbidity (200 NTU), Color (3570 Pt.Co), total suspended solids
(95 mgTSS/L) and volatile suspended solids (49 mgVSS/L). Y(m) = ym. exp �− exp
R ax.e
[λ − t] + 1
ym
2.1. Synthesis and characterization (2)
Synthesis of the magnetic nanoparticle (MNPs) was done using
Where;
the co-precipitation method adapted from Maaz et al., [15].
Using a 2 L beaker, the mixture of the precursors in volume ratio Y(m) is cumulative of specific biogas yield (mL/g COD), ym is
of volume ratio of 3:2:1:1 (429 mL Fe3+: 286 mL Fe2+: 143 mL maximum biogas production (mL/g COD), λ is the lag phase
TiO2: 143 mL Cu or Zn) was stirred and heated at temperature period or minimum time to produce biogas (days), t is
of 70°C for 2 hours, whereby 3 mL oleic acid was added for cumulative time for biogas production (days) and e is a
homogeneity. At a pH of 12, about 250 mL of NaOH was added mathematical constant (2.718282), K = Rmax.e/ym is the
dropwise until a thick black precipitated was formed. Prior to maximum specific substrate uptake rate per maximum biogas
calcination (at 550°C for 1 hour), the resultant powder was production (mL/g COD. day) and k is a first-order rate constant
washed (distilled water and ethanol) and dried at 100°C for 12 (1/d).
hours. MNPs were then characterized using scanning electron
microscopy and energy dispersive X-ray (SEM/EDX), Fourier 3. Results and discussion
Transform Infrared (FTIR) spectrometer (Shimadzu FTIR 8400)
3.1. Characterization of MNPs
and X-ray diffractometer equipment (Bruker AXS, D8
Advance). Sigma Aldrich in South Africa provided all the The physicochemical properties of the modified TiO2 were
chemicals and reagents used. studied, where the morphological appearance of the Zn-FeTiO2
(Fig 1a) and Cu-ZnFeTiO2 (Fig 1b) were compared. The SEM
2.2. Biostimulated methanation process and analysis images (Fig 1) illustrated the presence of the metal dopants in
In an anaerobic digestion process using a biochemical methane the TiO2 photocatalyst [20]. The nonspherical shapes and
potential (BMP) test, a working volume of 800 mL with a fragmented structures of the agglomerated metals (Zn and Fe)
headspace of 200 mL was used for the analysis. A biochemical and TiO2 photocatalyst are observed in the Zn-FeTiO2
methane potential (BMP) test was carried out in three bioreactors nanocomposite (Fig 1a). Compatibly, the angular structures and
(1 L Duran schott bottles) with working volume of 800 mL and self-agglomerated nanocrystalline particles of the Cu, Zn, Fe and
a headspace of 200 mL. They were air-tight with Teflon caps the TiO2 resulted in conglomeration of the Cu-ZnFeTiO2
connected with tubes and cylinders. After being filled with nanocomposite (Fig 1b). There were no major variations in size
wastewater (500 mL), inoculum (300 mL), and MNPs (1.5g), between the dopant metals and the TiO2 photocatalysts in
each bioreactor was purged with nitrogen for 2 minutes. The agglomeration sizes ranging from 1 to 5 μm. This showed
bioreactors were then submerged in a 30°C water bath, with the monodispersed uniform particles with a surface area of 4.15 μm
caps' tubes connected to a cylinder via a downward displacement at a width distance (WD) of 5.58 mm (Fig 1a) and 5.34 mm (Fig
method for gas collection. BMP system was operated for 30 days 1b) on a microscale of 1 μm, with magnification of 50 kx and
hydraulic retention time with daily monitoring of the biogas landing energy power of 5 keV.
produced. At the end of the 30 day digestion period, the gas was
characterized using gas chromatography (GC-2014 Schimadzu,
Japan) for each set-up. The supernatant liquid in each bioreactor
was characterized to determine COD, color and turbidity using
the APHA [16] standards. The remaining sludge was also
characterised to determine the TSS and VSS as per the protocol

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