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Hydrothermal Treatment of Palm Oil Mill Effluent (POME) under

Oxidative and Non-oxidative Conditions
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International Conference on Engineering and Industrial Technology (ICEIT2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 965 (2020) 012002 doi:10.1088/1757-899X/965/1/012002

Hydrothermal Treatment of Palm Oil Mill Effluent (POME)

under Oxidative and Non-oxidative Conditions

Zhan Sheng Lee, Chin Kui Cheng, Sim Yee Chin*

Faculty of Chemical and Process Engineering Technology, Universiti Malaysia
Pahang, Lebuhraya Tun Razak, 26300 Gambang, Kuantan Pahang

[email protected]

Abstract. The performances of oxidative (OHT) and non-oxidative (NOHT) subcritical

hydrothermal treatments of palm oil mill effluent (POME) were investigated. The experiments
were performed in a pressurised 500 mL-autoclave at different temperature (493 K – 533 K) and
reaction time (2 h – 8 h). At 533 K and 8 h, the OHT reaction showed the highest removals of 5-
day biochemical oxygen demand (BOD ) and chemical oxygen demand (COD), recording
5

87.30% and 71.23% respectively, with the pH of liquid product attained 6.5 from an initial value
of 3.5. The reduction of COD and BOD in NOHT was lower than that in OHT, which were
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61.43% and 68.02%, respectively. The mechanism of OHT reaction was via the free radical’s
pathway. In contrast, the organic compounds originally present in POME degraded into water-
soluble products, accompanied by deoxygenation that consisted of decarboxylation and
dehydration during the NOHT.

1. Introduction
The thriving palm oil industry in Malaysia has led to a massive production of viscous organic waste
known as palm oil mill effluent (POME). The production of each tonne of fresh fruit bunches generates
an approximately 0.66 tonne of POME in the palm oil milling process [1]. POME contains numerous
suspended constituents, including the organelles, a number of nitrogenous compounds ranging from
amino acids to proteins, various carbohydrates such as simple sugars and hemicellulose, a group of
insignificant organic and mineral constituents, as well as free organic acids [2]. POME is acidic with an
average pH of 4, attributed to organic acids. The typical 5-day biochemical oxygen demand (BOD ) and 5

chemical oxygen demand (COD) values of POME are 30,000 mg/L and 54,000 mg/L, respectively,
which are higher than the other agricultural effluents [3].

Majority of the oil palm millers in Malaysia practise open ponding system for POME treatment.
However, this treatment method needs long hydraulic retention time (up to 60 days) and large land bank
for pond creation. Furthermore, the unpleasant odour as well as the complication in collecting biogas
and sustaining the liquor distribution are the other drawbacks [4]. Over the years, different POME
treatment systems have been evaluated, such as ultrafiltration membrane separation [5], steam reforming
[6, 7], and advanced oxidation processes [8-10]. Nevertheless, these studies remained at laboratory-scale
and were not investigated for their scalability for industrial application. This could be due to the
technical impracticability and infeasible cost.

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International Conference on Engineering and Industrial Technology (ICEIT2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 965 (2020) 012002 doi:10.1088/1757-899X/965/1/012002

Subcritical hydrothermal treatment involves initiation of reaction at pressurised condition, without

exceeding the critical pressure and temperature. This treatment method has been widely applied on wet
biomass as it circumvents the drying pre-treatment. Some of the other benefits are the ease of process
implementation, hazard-free reaction as well as the reasonable capital and operational costs due to mild
operating conditions [11, 12]. Generally, hydrothermal reaction can be performed under either oxidative
or inert (non-oxidative) atmosphere, where the former involves the addition of oxidant in the form of
compressed air. Urrea et al. compared the reaction atmosphere on biopolymers in hydrothermal
treatment of sludge [13]. They reported that OHT showed better results in terms of solubilisation,
settleability and mineralisation in sludge treatment. Yousefifar et al. reported the study of OHT and
NOHT on cellulose at different temperatures [14]. These authors concluded that non-oxidative process
showed a significant role in solid degradation and solubilisation at temperature higher than 240ºC. To
our best knowledge, no studies of OHT and NOHT of POME have been done. POME contains a small
portion of suspended solids that made up of lignocellulosic materials. Thus, POME could be treated
following the method of lignocellulosic wastewater.

2. Materials and methods

2.1. POME sampling, storage and characteristics

30-L of raw effluent from the end-of-pipe of a local milling facility was acquired. The temperature and
pH value of the liquor were measured instantly, recorded readings of 360 K and 3.5, respectively. The
average concentration of COD and BOD of the fresh POME were 52,200 ± 800 mg/L and 18,020 ± 640
5

mg/L. The POME was preserved in a tight-sealed opaque container and stored in a chiller at 277 K. The
POME was homogenised prior to hydrothermal reaction.

2.2. Subcritical hydrothermal POME treatment

A pressure vessel (Model: Buchiglasuster Type 3E) of 1.0-L working capacity was used. 500 mL of the
wastewater was stirred consistently at 500 rpm using an electromagnetic-driven propeller to maintain
its homogeneity. The reactor temperature was varied between 493 K and 533 K with reaction time fixed
at 2 h. Meanwhile, the influence of reaction time on POME was examined by varying the reaction time
from 2 h to 8 h under a constant temperature of 533 K (highest temperature employed in the current
study). All the operating parameters were identical for both NOHT and OHT, except the gas medium
used to pressurise the reactor. For NOHT, 99.9995% purity nitrogen gas supplied by Alpha Gas Solution
Malaysia was introduced into the vessel for purging and pressurising purpose prior to each experiment.
The nitrogen gas was replaced by general industrial compressed air from Alpha Gas Solution Malaysia
for OHT study. An initial pressure of 50 bar was fixed in the reactor, followed by gradual autogenous
pressure build-up in concurrent with reaction temperature. The liquid product was sampled
intermittently from the reactor for further analysis. All the experiment sets were triplicated for
reproducibility assessment.

2.3. Liquid product analysis

The major components in fresh POME was identified using a gas chromatography coupled with mass
spectroscopy (GC-MS). 50 mL of POME was freeze-dried into solid powder using Labconco freeze
dryer. The freeze-drying process was carried out at 193 K under a 0.14 mbar vacuum. The POME
powder was transferred to an Agilent 7890A GC-MS via a single packed-bed column, namely Agilent
J&W DB 5-ms (30 m × 0.25 mm ID, 0.25 μm df, Fused Silica). The MS detector and injector port of
GC-MS were operated at 523 K while the operating temperature of GC oven was 573 K. The GC column
temperature was raised from 323 K to 473 K at 8 K/min, and then to 573 K at 10 K/min. The compounds
were identified using NIST mass spectral library. The liquid samples from various runs were subjected
to pH, COD and BOD analyses. A visual observation was done to compare the colour of all discharged
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products. A pH indicator strip from Merck was used to measure the pH value of POME and liquid

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International Conference on Engineering and Industrial Technology (ICEIT2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 965 (2020) 012002 doi:10.1088/1757-899X/965/1/012002

products. For the COD analysis, two mL of the diluted fresh POME and liquid samples was carefully
pipetted into the oxidation vials. A vial with distilled water was prepared as a baseline. A Hach DRB200
reactor was employed to digest the COD vials at 423 K for 2 h. The calculation of COD removal is
shown in equation (1).

COD removal (%) = (COD – COD )/COD × 100

f i i (1)
where COD represents COD value of POME, ppm
i

COD represents COD value of liquid discharge, ppm

f

The BOD method was employed to measure the oxygen consumption by the microorganisms in the
5

samples. One mL for each of the calcium chloride, magnesium sulphate, ferric chloride and phosphate
buffer solutions were stirred thoroughly. The mixture was subsequently diluted to 1-L of dilution water.
The dilution factors of the discharged products and raw POME were 100 and 1500 respectively. The
diluted samples were shifted to a 300-mL incubation bottle. 1 N NaOH was added gradually to ensure
that the pH was in the region of 6.5 to 7.5. The initial value of dissolved oxygen (DO) was recorded
before depositing the incubation bottles in a BOD incubator. The incubation was done at 293 K for five
consecutive days. The BOD readings were obtained using equation (2). Equation (3) shows the
5

calculation for BOD removal percentage.

5

BOD = (DO – DO ) / V
5 i f (2)
where DO represents the initial DO value in ppm
i

DO represents the DO value after five days in ppm

f

V represents the decimal volumetric fraction of sample used

BOD removal (%) = (BOD – BOD )/BOD × 100

5 5(f) 5(i) 5(i) (3)
where BOD represents the BOD value of POME, ppm
5(i)

BOD represents the BOD value of liquid discharge, ppm

5(f)

3. Results & discussion

3.1. Fresh POME Characterisation

The fresh POME from the end-of-pipe of milling process was blackish brown and has unpleasant odour.
Table 1 summarises the properties of raw POME in this study and in the past studies. The POME
characteristics in this study were similar to literatures [6, 15, 16].

Table 1. The characteristics of fresh POME of the present study and literature works.
Properties Typical range [6, 15] Present study [16]
Temperature (K) 353-363 360
COD (ppm) 44,300-70,900 52,200
BOD (ppm)
5 11,000-27,000 18,020
pH 3.6-4.3 3.5

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International Conference on Engineering and Industrial Technology (ICEIT2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 965 (2020) 012002 doi:10.1088/1757-899X/965/1/012002

Figure 1. GC-MS spectra of the freeze-dried POME.

The GC-MS spectra of raw POME after being freeze-dried is as in figure 1. Eleven compounds were
positively-identified from the NIST mass spectral library and summarised in Table 2. Significant amount
of N-hexadecanoic acid (palmitic acid) was found in the fresh POME. This compound is a natural
component of palm oil. The other minor organic compounds were in a good agreement with the
literatures [17, 18].

Table 2. Identification of organic compounds in POME using GC-MS analysis.

Retention Organics Molecular Molecular xi

time formula weight (%)

4.297 Allyl ethyl ether CH O
9 10 134.18 7.26
5.949 1-Buten-3-yne, 2-methyl- CH
5 6 66.10 2.65
11.091 4-Hydroxy-2-methylacetophenone CH O
9 10 2 150.17 2.42
11.735 1-Ethyl-2,2,6-trimethylcyclohexane CH
11 22 154.292 0.17
11.835 Ethyl (Z)-non-3-enyl carbonate CHO
12 22 3 214.30 0.44
15.056 Benzene, 1,4-dimethoxy-2-methyl- CH O
9 12 2 152.1904 1.62
19.942 1-Propanol, 2-methyl- CH O
4 10 74.122 0.28

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International Conference on Engineering and Industrial Technology (ICEIT2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 965 (2020) 012002 doi:10.1088/1757-899X/965/1/012002

22.162 n-Hexadecanoic acid CHO

16 32 2 256.40 81.84
23.607 5-Octadecene, (E)- CH18 36 252.49 1.54
33.572 Propylene oxide CHO
3 6 58.079 0.42
37.319 1,4-Hexadiene, 3,3,5-trimethyl- CH9 16 124.223 1.35

3.2. Visual Appearance

Figure 2 visualises the comparison among the raw POME and liquid products. The colour of liquid
discharge of NOHT was darker than OHT. The presence of solid hydrochar (also found deposited on
the reactor wall) may describe the dark colour of NOHT liquid product. The liquid discharge of NOHT
exhibited a burnt charcoal smell while the OHT product was odourless. Therefore, the discolouration
occurred in OHT could be due to the oxidation of tannins in POME.

Figure 2. (from left) Fresh POME, liquid product of NOHT at 533 K & 8 h and liquid product of OHT
at 533 K & 8 h.

3.3. Effect of Hydrothermal Treatment Conditions

The pH, COD and BOD values for all the liquid products from both OHT and NOHT are tabulated in
5

Table 3. The pH value of treatment effluent was higher than the fresh POME and showed a consistent
increase with the elevation of reaction temperature and time. The However, the pH value indicated that
the liquid discharge still exhibited a mild acidic nature. It could be caused by the remaining refractory
organic acids in the discharged products [19]. The increase of pH supports the idea that the organic acids
in POME showed further reactions as reaction temperature and time increased under hydrothermal
treatment [20].

In NOHT, both BOD and COD reduction increased gradually with the hydrothermal temperature.
5

This was reported before by [21]. At 493 K, the final COD reading was 36400 ± 550 ppm while the final
BOD was 9178 ± 150 ppm. At 533 K, the COD reading was the lowest, at 21500 ± 300 ppm while the
5

BOD showed a mean value of 6763 ± 75 ppm. Based on the removal percentage shown in Table 3,
5

prolonging the reaction time from 2 h to 8 h only marginally increased both the COD and BOD 5

reduction. The increments were only 8.88% and 4.46%. The highest COD and BOD removal were 5

achieved through NOHT at 533 K for 8 h at 61.43% and 68.02% respectively. The detailed reaction
pathways were described in our previous work [14]. In NOHT, the reaction mechanism can be
summarised as in a course of reactions, comprising of hydrolysis, decarboxylation and dehydration, that
occur con-currently. Hydrolysis occurs in the beginning of the reaction to initiate the decomposition of
POME into water-soluble intermediates [22]. The reaction is followed by decarboxylation and
dehydration of the hydrolysed components that take place simultaneously.

For the OHT process, the COD and BOD removal percentage were higher than NOHT under similar
5

operating condition. The highest COD reduction was 71.23%, which was achieved at 533 K after an 8-

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International Conference on Engineering and Industrial Technology (ICEIT2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 965 (2020) 012002 doi:10.1088/1757-899X/965/1/012002

hour OHT duration. The superior COD and BOD reduction were ascribed to the enhanced oxidation of
5

organic compounds in the presence of air. The increase of temperature resulted a higher oxidation
effectiveness, which is consistent with the literature finding [14]. The reactions that occurred during
OHT is more complicated as it involves an additional series of oxidation reactions that are expected to
take place in the organic content of POME. The chemical step involves the reaction between the supplied
oxygen molecules or the oxidation intermediates and the organic compounds in POME. The organic
compounds could be oxidised by a free-radical intermediate generated during the oxidation of another
compound [23]. The formation of free radicals should be further investigated and supported with
evidence, such as by using electron spin resonance or free radical inhabitation technique [24].

Despite the high COD and BOD reduction, the final BOD of the hydrothermally treated POME still
5 5

did not comply the discharge regulatory (below 100 ppm). The increase in hydrothermal temperature
did not improve dramatically the treatment performance. This may be owed to the refractory phenolic
compounds present in POME. It was reported that POME has high lignin-to-cellulose ratio [25]. A
catalytic reaction study is necessary in the future work to determine a suitable catalyst in achieving
higher organic pollutants degradation. The heterogeneous catalytic reaction is potential to offer a higher
versatility and greater efficiency in the treatment of pollutants with a promising economic benefit [26]
Nonetheless, the degradability of the organic substances in POME by hydrothermal reaction is still
remarkable compared to the existing open ponding treatment method [27].

Table 3. The analyses of pH, COD and BOD of the end-of-pipe POME and all the liquid discharges.
5

Process Reaction Reaction pHᵃ BOD ᵃ 5 CODᵃ

temperature (K) Time (h) removal (%) removal (%)
NOHT 493 2 5.5 49.07 30.27
NOHT 503 2 5.5 57.09 46.74
NOHT 513 2 5.8 59.92 48.85
NOHT 523 2 6.0 61.16 50.38
NOHT 533 2 6.3 62.47 58.81
NOHT 533 4 6.3 63.50 59.23
NOHT 533 6 6.5 66.21 61.00
NOHT 533 8 6.5 68.02 61.43
OHT 493 2 6.0 69.90 58.21
OHT 503 2 6.3 73.16 60.98
OHT 513 2 6.5 77.39 63.45
OHT 523 2 6.5 79.31 65.39
OHT 533 2 6.5 80.25 66.93
OHT 533 4 6.5 83.31 69.21
OHT 533 6 6.5 85.12 70.71
OHT 533 8 6.5 87.30 71.23
ᵃ Mean values from the triplicate measurement

4. Conclusion
Subcritical hydrothermal process is deemed a new pathway for a more effective POME treatment. The
treatment performance was evaluated in the aspects of COD and BOD removal, where OHT showed
5

promising results compared to the NOHT. The best operating condition was determined at the
temperature of 533 K and process time of 8 h under oxidative environment, with the highest COD
(71.23%) and BOD (87.30%) removal, respectively. In addition, the pH was 6.5 due to the elimination
5

of carboxylic compounds. The liquid product from the treatment was comparable with the effluent via
open ponding method. Post treatment of the hydrothermally treated liquid product is suggested to meet
the local discharge standard. For NOHT, deoxygenation that comprises of both dehydration and

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International Conference on Engineering and Industrial Technology (ICEIT2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 965 (2020) 012002 doi:10.1088/1757-899X/965/1/012002

decarboxylation is most likely the dominant post-hydrolysis process. In contrast, free radical pathway
could be the major degradation process of the organics in OHT.

Acknowledgments
The authors appreciate Universiti Malaysia Pahang for supporting this project through UMP Flagship
Strategic Leap 3 Grant (RDU172202) and UMP Short-Term Grant (RDU170325).

References
[1] Stichnothe, H. and F. Schuchardt, Life cycle assessment of two palm oil production systems.
Biomass and Bioenergy, 2011. 35(9): p. 3976-3984.
[2] Wu, T.Y., et al., Pollution control technologies for the treatment of palm oil mill effluent (POME)
through end-of-pipe processes. Journal of Environmental Management, 2010. 91(7): p. 1467-
1490.
[3] Tabassum, S., Y. Zhang, and Z. Zhang, An integrated method for palm oil mill effluent (POME)
treatment for achieving zero liquid discharge – A pilot study. Journal of Cleaner Production,
2015. 95: p. 148-155.
[4] Lee, Z.S., et al., Treatment technologies of palm oil mill effluent (POME) and olive mill
wastewater (OMW): A brief review. Environmental Technology & Innovation, 2019: p.
100377.
[5] Ali, A.N.A., et al., Tackling colour issue of anaerobically-treated palm oil mill effluent using
membrane technology. Journal of Water Process Engineering, 2015. 8: p. 221-226.
[6] Cheng, Y.W., et al., Syngas from catalytic steam reforming of palm oil mill effluent: An
optimization study. International Journal of Hydrogen Energy, 2019. 44(18): p. 9220-9236.
[7] Cheng, Y.W., et al., Harnessing renewable hydrogen-rich syngas from valorization of palm oil
mill effluent (POME) using steam reforming technique. Renewable Energy, 2019. 138: p.
1114-1126.
[8] Ng, K.H., et al., Photocatalytic degradation of recalcitrant POME waste by using silver doped
titania: Photokinetics and scavenging studies. Chemical Engineering Journal, 2016. 286: p.
282-290.
[9] Ng, K.H. and C.K. Cheng, A novel photomineralization of POME over UV-responsive TiO2
photocatalyst: kinetics of POME degradation and gaseous product formations. RSC Advances,
2015. 5(65): p. 53100-53110.
[10] Saeed, M.O., et al., Treatment of POME using Fenton oxidation process: removal efficiency,
optimization, and acidity condition. Desalination and Water Treatment, 2016. 57(50): p.
23750-23759.
[11] Abu Tayeh, H., et al., Subcritical hydrothermal pretreatment of olive mill solid waste for biofuel
production. Bioresource Technology, 2016. 199: p. 164-172.
[12] Osada, M., et al., Low-Temperature Catalytic Gasification of Lignin and Cellulose with a
Ruthenium Catalyst in Supercritical Water. Energy & Fuels, 2004. 18(2): p. 327-333.
[13] Urrea, J. L., García, M., Collado, S., Oulego, P., & Díaz, M. (2018). Sludge hydrothermal
treatments. Oxidising atmosphere effects on biopolymers and physical properties. Journal of
Environmental Management, 206, 284-290.
[14] Yousefifar, A., et al., Hydrothermal processing of cellulose: A comparison between oxidative and
non-oxidative processes. Bioresource Technology, 2017. 226: p. 229-237.
[15] Ng, K.H., et al., A study into syngas production from catalytic steam reforming of palm oil mill
effluent (POME): A new treatment approach. International Journal of Hydrogen Energy, 2018.
[16] Lee, Z.S., S.Y. Chin, and C.K. Cheng, An evaluation of subcritical hydrothermal treatment of
end-of-pipe palm oil mill effluent. Heliyon, 2019. 5(6): p. e01792.
[17] Cheng, J., et al., Palm oil mill effluent treatment using a two-stage microbial fuel cells system
integrated with immobilized biological aerated filters. Bioresource Technology, 2010. 101(8):
p. 2729-2734.

7
International Conference on Engineering and Industrial Technology (ICEIT2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 965 (2020) 012002 doi:10.1088/1757-899X/965/1/012002

[18] Cheng, Y.W., et al., Hydrogen-rich syngas production via steam reforming of palm oil mill
effluent (POME) – A thermodynamics analysis. International Journal of Hydrogen Energy,
2018.
[19] Berge, N.D., et al., Hydrothermal Carbonization of Municipal Waste Streams. Environmental
Science & Technology, 2011. 45(13): p. 5696-5703.
[20] Arauzo, P., Olszewski, M., & Kruse, A. (2018). Hydrothermal Carbonization Brewer's Spent
Grains with the Focus on Improving the Degradation of the Feedstock. Energies, 11, 3226.
[21] Karagöz, S., et al., Low-Temperature Hydrothermal Treatment of Biomass: Effect of Reaction
Parameters on Products and Boiling Point Distributions. Energy & Fuels, 2004. 18(1): p. 234-
241.
[22] Williams, P.T. and J. Onwudili, Subcritical and Supercritical Water Gasification of Cellulose,
Starch, Glucose, and Biomass Waste. Energy & Fuels, 2006. 20(3): p. 1259-1265.
[23] Bhargava, S.K., et al., Wet Oxidation and Catalytic Wet Oxidation. Industrial & Engineering
Chemistry Research, 2006. 45(4): p. 1221-1258.
[24] Robert, R., et al., Intermediates in wet oxidation of cellulose: identification of hydroxyl radical
and characterization of hydrogen peroxide. Water Research, 2002. 36(19): p. 4821-4829.
[25] Kang, S., et al., Hydrothermal conversion of lignin: A review. Renewable and Sustainable Energy
Reviews, 2013. 27: p. 546-558.
[26] Arena, F., et al., Recent advances on wet air oxidation catalysts for treatment of industrial
wastewaters. Inorganica Chimica Acta, 2015. 431: p. 101-109.
[27] Othman, M.R., et al., Treatment of effluents from palm oil mill process to achieve river water
quality for reuse as recycled water in a zero emission system. Journal of Cleaner Production,
2014. 67: p. 58-61.