Optimization For Biohydrogen Purification Process by Chemical Absorption Techniques
Optimization For Biohydrogen Purification Process by Chemical Absorption Techniques
Optimization For Biohydrogen Purification Process by Chemical Absorption Techniques
Sustainable Environment
Sustainable Environment Research (2023) 33:35
https://doi.org/10.1186/s42834-023-00196-5 Research
Abstract
Palm oil decanter cake and crude glycerol, which are characterized by their highly biodegradable organic content
and nutrient-rich composition, are attractive ingredients for biohydrogen production. In this experiment, we inves-
tigated (1) how to produce hydrogen more effectively by co-fermenting palm oil decanter cake and crude glycerol
and (2) how to improve the quality of the hydrogen gas produced via chemical absorption technology. This study
was divided into two parts. In the first part, the co-fermentation was conducted with a fixed decanter cake concen-
tration of 1% total solids (TS) w/v and variable crude glycerol concentrations (0.25–2.0% w/v). The results showed
that maximum biohydrogen production was achieved with 2.0% w/v crude glycerol, which had a hydrogen yield
of 131 L kg−1 TSadded and a hydrogen productivity of 1310 mL L−1 d−1. In the second part of the experiment, bio-
hydrogen purification was conducted using the chemical absorption technique by varying four different alkaline
solutions: mono ethanolamine (MEA), ammonia ( NH3), sodium hydroxide (NaOH), and potassium hydroxide (KOH).
The highest hydrogen purity of 98.9% v/v was reached with the MEA solution at a 5 M concentration and a 280 mL
min−1 feed mixed gas flow rate for an absorption time of 5 min. However, to achieve sustainable waste management
in palm oil mill plants, the feasibility of integrating the biohydrogen production process with palm oil mill effluent
from the biogas plants and applying a hydrogen gas quality improvement system need to be investigated further.
Keywords Absorption techniques, Biohydrogen production, Biohydrogen purification, Co-fermentation, Crude
glycerol, Palm oil decanter cake
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Chusut et al. Sustainable Environment Research (2023) 33:35 Page 2 of 10
transportation and thus increase the availability of low- Crude glycerol with 78.4% w/v glycerol purity was also
cost, clean energy [6, 7]. Furthermore, the combus- obtained from the Suksomboon palm oil industry in
tion of hydrogen does not release any pollutants into Chonburi, Thailand.
the atmosphere and generates heat energy up to 242 kJ Anaerobic sludge was obtained from biogas plants in
mol−1, as shown in the following reaction (Eq. (1)) [8]. the Suksomboon palm oil industry in Chonburi, Thai-
The combustion of pure hydrogen gas and oxygen gas land. The sample was heated at 100 °C for 30 min before
results in only steam (H2O) and heat. use. This pretreatment of anaerobic sludge is undertaken
to enrich the hydrogen producers and often relies on
the spore-forming characteristics of hydrogen produc-
1 f , gas
H2 + O2 → H2 0 (△HToo, H20 = 242 kj mol −1 ) (1) ers such as Clostridium, which are ubiquitous in anaero-
2 bic sludge and sediments. These organisms have a better
In biohydrogen production, the purification process is chance of survival under drastic anaerobic sludge pre-
considered a key issue as high-quality hydrogen can be treatment conditions than non-spore-forming bacteria,
utilized for power generation by fuel cell applications. such as methanogens, as the spores can germinate again
The enriched hydrogen within the gas blend formed under favorable conditions. Heat treatment of mixed cul-
during fermentation can be used to obtain fuel with an tures to enrich hydrogen producers is a simple, inexpen-
upgraded power value. This can be achieved by remov- sive, and effective method [15].
ing the major byproduct, specifically, CO2. Many tech- The characteristics of the raw materials are shown in
nologies have been applied in H2 purification, such as Table 1.
pressure swing adsorption, absorption, and membrane
technology [9, 10]. The process of biogas purification 2.2 Biohydrogen production process
through chemical absorption may offer a better alterna- The experimental biohydrogen production process was
tive. Because of the chemical absorption, this process conducted in a 20 L semi-continuous stirred tank reac-
can be operated at low pressure with a product stream tor (Fig. 1). The reactor had a working volume of 16 L
of high purity. The factors influencing the absorption of and was operated for a hydraulic retention time (HRT)
substances are (1) pH of the solvent, (2) concentrations, of 2 d. The process started with the co-fermentation of
and (3) temperatures of both the gas and solvent. Sol- 1% w/v total solids (TS) of palm oil decanter cake and
vents are considered economically attractive absorbents 0.25% w/v crude glycerol with 4 L of anaerobic sludge.
since they have low energy requirements and no environ- We subsequently adjusted the volume to 16 L using tap
mental impact and are easily renewable and cost-effective water. A new mixture of substrate (8 L) was fed into the
[10, 11]. According to ISO hydrogen fuel specifications, reactor daily, and a corresponding volume of digestate
biohydrogen must have a minimum hydrogen purity of was removed to keep the operating volume at 16 L. The
99.99% to be used as a fuel source [12, 13]. However, a concentration of glycerol was increased slightly by 0.25,
hydrogen supply gas with a purity of at least 98% may be
necessary for hydrogenation processes [14].
In this study, we focused on enhancing the efficiency
of biohydrogen production via the co-digestion of crude Table 1 Characteristics of palm oil decanter cake, crude glycerol,
and anaerobic sludge
glycerol from the biodiesel production process with palm
oil decanter cake and optimizing the chemical absorption Parameter Decanter cake Crude glycerol Anaerobic
process to improve the purity of the produced hydro- sludge
gen. This process could be integrated with those at palm Total solids (TS) 27.4% w/v n.d. 31,700 mg L−1
oil mill plants to ensure the sustainable management of Total volatile n.d. n.d. 14,900 mg L−1
waste from these plants in the future. solids
Total COD 937,000 mg k g−1 1,080,000 mg L−1 18,200 mg L−1
Soluble COD n.d. n.d. 5,300 mg L−1
2 Materials and methods pH n.d. 6.53 9.3
2.1 Raw materials Total carbona n.d. n.d. 47.4% w/w
Palm oil decanter cake, a feedstock for biohydrogen Total nitrogena n.d. n.d. 4.3% w/w
production, was collected from a palm oil mill plant in Cellulosea n.d. n.d. 50.1% w/w
the Suksomboon palm oil industry in Chonburi, Thai- Hemicellulosea n.d. n.d. 30.7% w/w
land. The sample was stored at 4 °C before use to reduce Lignina n.d. n.d. 10.4% w/w
microbial activity and reduce the physical and chemical n.d. not determined
changes. a
Additional information from previous co-authors [16]
Chusut et al. Sustainable Environment Research (2023) 33:35 Page 3 of 10
0.50, 1.00, and 2.00% w/v crude glycerol, respectively, Table 2 Parameters for absorption technology adapted from
and the decanter cake was fixed at 1% TS w/v through- Rohani et al. [19]
out the fermentation process. The pH of the substrate Parameter Parameter range
was adjusted to 5.5 with 85% phosphoric acid ( H3PO4)
−1
as a pretreatment before use. H 3PO4 is known to be a Inlet gas flow rate (mL min ) 280
weak acid and therefore does not affect systemic micro- Inlet gas composition ( H2:CO2) (%, v/v) 60:40
organisms. It can break down lignocellulose biomass Types of alkaline solutions KOH, NaOH, NH3, and MEA
and improve cellulose digestibility. Because H3PO4 is Alkaline solution concentration (M) 1, 2 and 5
environmentally friendly, the solid residue can be used Alkaline solution temperature (°C) Room temperature (20–25)
as fertilizer. In addition, the lack of oxidizing power of Data recorded times (min) 5, 15, 30, 60 and 90
H3PO4 makes it more beneficial in the treatment of lig- Size of the reactor (mm) Diameter 86 and height 181
nocellulose biomass [17, 18]. The reactor was operated Alkaline solution volume (mL) 500
under thermophilic conditions (55 °C) with agitation at
100 rpm.
Fig. 2 Parameter changes under the co-fermentation of palm oil decanter cake with crude glycerol (a) Hydrogen production, and hydrogen
content; (b) pHs; (c) butyric acid and acetic acid; (d) ethanol, and propionic acid
Chusut et al. Sustainable Environment Research (2023) 33:35 Page 5 of 10
The biohydrogen production trend measured by the gas. Theoretically, if acetic acid were the only constitu-
percentage of hydrogen gas and the volume of hydrogen ent in the fermentation process, hydrogen gas would be
produced increased with the increasing crude glycerol obtained as a product at 4 mol mol−1 glucose as a sub-
concentration. The crude glycerol was added in increas- strate, as shown in Eq. (3) [15, 21].
ing volumes as a co-substrate to help decompose organic
matter. Although the pH in the fermentation system was
C6 H12 O6 + 2H2 O → 2CH3 CH2 COOH + 2CO2 + 4H2
maintained, we found that the increase in crude glyc- (3)
erol decreased the pH in the semi-continuous hydrogen
Conversely, if butyric acid were the only component
fermentation system (Fig. 2b). Because nutrients with a
in the fermentation process, hydrogen gas would be
simple molecular structure were continuously fed into
obtained as a product at 2 mol mol−1 glucose as a sub-
the system, it allowed the microorganisms in the fer-
strate, as shown in Eq. (4) [15, 21].
mentation tank to function unimpeded. In addition, the
crude glycerol contained a high chemical oxygen demand
(COD) and a pH of 6.53. It was not only utilized as a co- C6 H12 O6 → CH3 CH2 CH2 COOH + 2CO2 + 2H2 (4)
substrate for the hydrogen production, but also as an
alternative pH-adjusting substance to keep the pH value In practice, the fermentation pathways occur in paral-
within the reactor up, thereby resulting in semi-continu- lel with both the acetic and butyric acid pathways. This
ous hydrogen production. is especially true in fermentation processes with mixed
Butyric acid and acetic acid were the primary volatile cultures, such as in this experiment. As a result, both ace-
fatty acids detected in the liquid samples throughout the tic and butyric acid were often found in the fermentation
fermentation process (Fig. 2c). It could be concluded that process, and the yield of hydrogen was consistently lower
this hydrogen fermentation process occurred according than theoretical value [11].
to the butyric acid-producing pathway, with butyric acid In the fourth phase of fermentation, butyric and ace-
and acetic acid as the main products accumulated in the tic acid were primarily generated in the reactor. Ethanol
liquid sample. The results showed that during the first was also accumulated at a high level compared to in the
fermentation phase (days 1–41), not only were these the other fermentation phases (Fig. 2d). The high accumu-
predominant acids produced within the reactor, but pro- lation of undissociated acid above 19 mM proved to be
pionic acid was also highly accumulated compared to the a factor that inhibited acidogenesis and was a threshold
other phases (Fig. 2d). Theoretically, 2 mol H 2 would be concentration for a decrease in hydrogen yield and the
consumed from the propionic acid producing pathway. In onset of solventogenesis [16, 22]. Ethanol is an indicator
Fig. 2d, propionic acid remained high from day 7–37, and of a solventogenesis reaction in a reactor. This reaction
the trend until day 63 was consistent with the H2 con- can occur when there is a proton imbalance and during
tent in Fig. 2b. Many studies have shown were reported detoxification into the bacterial cell. Within the acidity
that the H 2 is consumed by propionic acid producing condition, the non-dissociated acid form may infiltrate
and homoacetogenesis pathways when using organic through the cells, and protons will be discharged into the
waste in the dark fermentation. If high levels of propi- cells, which leads to harmful conditions. Subsequently,
onic acid were to have been found, the yield of hydrogen solventogenesis will be generated to maintain a neutral
would have been reduced. Bacteria with propionic acid condition for a normal metabolic process.
fermentation pathways may also have been evident. This With respect to waste reduction under co-fermenta-
describes propionic acid-type fermentation in which this tion using 1% w/v TS palm oil decanter cake with differ-
group of bacteria uses a mixture of hydrogen gas to pro- ent concentrations of crude glycerol, our results showed
duce propionic acid, as in Eq. (2) [20], which results in a that maximum soluble COD removal was achieved with
decrease in the yield of hydrogen. 0.25% w/v crude glycerol waste and TS removal with
0.50% w/v crude glycerol waste (Tables 3 and 4). They
further revealed the low removal efficiency of both solu-
C6 H12 O6 + 2H2 → 2CH3 CH2 COOH + 2H2 O ble COD and TS because the hydrogen production pro-
(2) cess was a part of the anaerobic fermentation process.
When comparing the third and fourth phase fermen- Organic matter is degraded from large organic molecules
tation, the percentage of hydrogen was similar, but the to smaller molecules resulting in the accumulation of
volume of hydrogen was different because of the increas- various volatile organic compounds.
ing number of acidogenic bacteria in the fourth phase. In terms of the hydrogen gas yield and productivity,
Increasing the acetic acid pathway in the fermentation the maximum hydrogen gas yield and productivity were
process resulted in an increased amount of hydrogen observed at 2% w/v crude glycerol waste (Table 5). When
Chusut et al. Sustainable Environment Research (2023) 33:35 Page 6 of 10
Table 3 Soluble chemical oxygen demand removal in the comparing the hydrogen yields obtained in the present
biogas production from co-fermentation of palm oil decanter study with other studies, the hydrogen yields from the
cake with crude glycerol co-fermentation of decanter cake and crude glycerol
Crude glycerol SCOD influent SCOD effluent SCOD removal were higher than those from other raw materials such
(% w/v) (mg L−1) (mg L−1) (%) as rice straw, potato waste, and raw wet steam-exploded
cornstalk (Table 6). We noted that the type of substrate
0.25 7,100 ± 700 6,400 ± 700 9.2 ± 3.3
used for co-fermentation and different operating condi-
0.50 10,100 ± 1,100 9,000 ± 600 8.5 ± 3.9
tions affected the rate of hydrogen production. Due to
1.00 17,300 ± 1,900 15,300 ± 1,200 8.6 ± 3.0
the varying chemical compositions of the substrates, the
2.00 33,400 ± 1,500 30,600 ± 2,100 7.4 ± 2.4
difficulties with hydrolysis and the substrate transforma-
tion to hydrogen gas were different.
Table 6 Comparison of the hydrogen gas from the palm oil decanter cake and crude glycerol with previous research
Feedstocks Operation mode pH Temp. (°C) Yield (L k
g−1 TSadded) References
Fig. 3 H2 content via absorption technique with different alkaline solutions (a) MEA, (b) NH3, (c) KOH, and (d) NaOH
Chusut et al. Sustainable Environment Research (2023) 33:35 Page 8 of 10
percentage of hydrogen than the other alkaline solu- had an impact on the hydrogen percentage rate. The
tions because 1 mol of MEA would react in equilibrium absorbents must have a high quenching capacity for
with 1 mol CO2, as demonstrated in Eq. (6) [11, 28, 29]. CO2, be moisture-tolerant, and exhibit a strong prefer-
Meanwhile, the use of more NaOH and KOH at 2 mol ence for CO2 over other gases. The absorption process
would react in equilibrium with 1 mol CO2, as shown in can be more effective if the gaseous pollutants (CO2)
Eqs. (7)–(8) [11, 30]. Moreover, a previous study revealed are more soluble in an absorbent than in biogas [33].
that a higher absorbent concentration may release more The concentration of the sorbent is crucial in chemi-
free ionic species, which would provide a more notewor- cal absorption. As the viscosity of the solution and the
thy CO2 response within the absorption process. How- produced biogas intake rate are increased, the diffu-
ever, the trend of reduced gas purity showed the presence sion coefficient and absorption rate will decline. The
of a CO2 saturation stage during absorption [31]. amount of CO2 in the gas stream and the surface of
the sorbent have an impact on the rate of absorption
[29, 34]. The pH of the solvent has a major impact on
RNH2 + CO2 + H2 0 → RNH3+ + HCO3− (6) both the rate of absorption and the overall absorption
process, with the rate of absorption decreasing with
increasing acid or base in the process. While amine
2NaOH + CO2 → Na2 CO3 + H2 O (7) and NH3 perform best in the pH range of 11.5–12, the
optimal pH values for KOH and NaOH are 13 and 12.9,
respectively [29, 35, 36]. Regeneration, requires a very
2KOH + CO2 → K2 CO3 + H2 O (8) small amount of energy. The heat of absorption varies
between − 25 and − 50 kJ mol−1 for physical absorp-
In theory, MEA is less effective in absorbing C O2 tion and between − 60 and − 90 kJ mol−1 for chemical
than NaOH. It has been shown that 1.39 t of MEA and absorption. The ability to use regenerate energy in a
0.9 t of NaOH are theoretically needed to produce 1 t of reasonable way is a benefit of the absorber [29, 37]. In
CO2, respectively [29, 32]. The main drawbacks of this the process of chemical absorption, the choice of the
approach have been reported in a previous study and proper solvent is crucial. To increase the efficiency and
include the substantial solvent energy needed to regen- effectiveness of absorption, several more aspects must
erate the chemical solution, the initial cost of the amine be considered in addition to those listed above. These
solvents, and the solvents that are lost through evapora- include accessibility, affordability, volatility, gas solu-
tion. Alkali salt is therefore attractive because it is less bility, innocuous qualities, and toxicity to both humans
expensive and more accessible [29]. and the environment [29].
When considering the C O2 removal efficiency in this
work compared with that in previous studies (Table 7),
it was evident that the type of alkaline solution used for 4 Conclusions
absorption and the various operating circumstances In this experiment, we aimed to enhance the efficiency
of hydrogen production through co-fermentation using
decanter cake and crude glycerol. The experiment was
lab-scale and focused on the inclusion of the appropri-
Table 7 Compare the CO2 removal efficiency from this research ate crude glycerol concentration for the hydrogen pro-
compared with previous research duction process. We studied methods to improve the
quality of hydrogen gas after the production process
Initial Type of Concentration Removal References
concentration alkaline of solution (M) efficiency via absorption technology. Maximum biohydrogen pro-
CO2 (%, v/v) solution (%) duction was observed at 2.0% w/v crude glycerol with
a hydrogen yield of 131 L k g−1 TSadded and a hydrogen
46 NaOH 3.0 66 [30]
40 MEA 1.6 75 [38]
production rate of 1.3 L L −1 d−1. However, to achieve
45 KOH 9.5 93 [39]
sustainable waste management at palm oil mill plants,
47 NaOH 0.1 93 [40] the feasibility of using wastewater from biogas plants
40 NaOH 2.9 85 [41] for dilution instead of tap water should be studied by
46 NH3 11.8 65 [42] controlling the concentration of organic matter before
40 MEA 5.0 97 This study use. We performed biohydrogen purification using the
40 NH3 5.0 85 This study absorption technique with four different solvents. The
40 KOH 5.0 94 This study highest hydrogen purity (99% v/v) was found when using
40 NaOH 5.0 73 This study an MEA solution at a concentration of 5 M and a 280
Chusut et al. Sustainable Environment Research (2023) 33:35 Page 9 of 10
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