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Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-019-00385-6

REVIEW ARTICLE

Biogas generation from by-products of edible oil processing: a review


of opportunities, challenges and strategies
Charles Rashama 1 & Grace Ijoma 1 & Tonderayi Matambo 1

Received: 27 October 2018 / Revised: 21 January 2019 / Accepted: 24 January 2019


# Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
Edible oil processing by-products can be used to produce a renewable fuel called biogas through anaerobic digestion technology.
In this process, the physicochemical characteristics of the substrates dictate the process conditions, stability and microbial profile.
All these, in turn, affect the overall digester design and operational efficiency. Most edible oil processing by-products tend to
exhibit comparatively similar physicochemical properties, allowing for echo studies to be conducted on them. Naturally, residual
fats and oils in edible oil by-products should induce high methane production potential. However, this does not occur without
certain drawbacks. In this work, a review is conducted on biogas systems that use edible oil processing by-products as substrates
for anaerobic digestion. Anaerobic digestion opportunities and challenges associated with these substrates are identified by
analysis of factors that affect anaerobic digestion. The factors are scrutinised under different sub-headings, viz., substrate
physicochemical composition, process conditions and parameters. Knowledge gaps are identified. Additionally, strategies for
resolving some of the highlighted challenges while leveraging opportunities identified are discussed.

Keywords Biogas . Edible oil cake . Pomace . Microbial inhibition . Anaerobic digestion . Wastewater treatment

Abbreviations OMSW Olive mill solid waste


AD Anaerobic digestion FA Fatty acid
TS Total solids LCFA Long-chain fatty acids
RBDW Refined, bleached, deodorised and winterised SCFA Short-chain fatty acids
VS Volatile solids AnCod Anaerobic codigestion
COD Chemical oxygen demand ORP Oxidation/reduction potential
BOD Biological oxygen demand EGSB Expanded granular suspended bed
BMP Biomethane potential LPM Liquid poultry manure
n.d. No data FOG Fats, oils and grease
OFC Organic fraction composition UASB Upflow anaerobic sludge blanket
HRT Hydraulic retention time IASB Inverted anaerobic sludge blanket
OLR Organic loading rate UASFF Upflow anaerobic sludge fixed film
SRT Solids retention time CSTR Continuously stirred tank reactor
VFA Volatile fatty acids TAN Total ammonia nitrogen
POME Palm oil mill effluent TCOD Total chemical oxygen demand
OMWW Olive mill waste water CW Cheese whey
AMPTSII Automatic methane potential testing system ver-
sion II
* Charles Rashama
c.rashama@gmail.com

1
1 Introduction
Institute for the Development of Energy for African Sustainability
(IDEAS), University of South Africa’s College of Science,
Engineering and Technology, Cnr Pioneer and Christian De Wet Edible oil extraction from various oil bearing seeds and fruits
Roads, Private Bag X6, Florida 1710, South Africa is widely practiced around the globe [1]. From these oil
Biomass Conv. Bioref.

extraction activities arise a number of environmental con- AD offers an alternative waste management option for
cerns, such as the generation of solid wastes [1] and wastewa- both the solid and liquid fractions of edible oil processing
ter with high organic loading [1–4]. Dangerous leachates, ob- by-products. While managing the waste, AD technology
noxious gases and greenhouse gas emissions from landfills/ offers some additional benefits for dealing with the energy
wastewater lagoons that are used for the disposal of these oil [25], water and environment concerns. In the past, biolog-
processing by-products have been reported [4–6]. Most cur- ical treatments (anaerobic, aerobic and sometimes both
rent disposal methods for edible oil processing by-products used concurrently) have been reliably used to treat lipid-
are either insufficient or costly. In addition to the waste man- containing wastes. These were mainly wastes generated by
agement problem with edible oil plants, the high consumption restaurants and wastewater plants [26], as well as the waste
of water and energy in this industry also poses serious con- from edible oil refineries [3, 27–29]. Chipasa [27] makes
cerns [1]. The water and electricity are mainly used in steam the assertion that while physicochemical treatment may
generation activities required for process applications. succeed with pollutant removal of metallic salts and grit
Depending on the raw material used for oil extraction, the in the wastewater, only biotreatment processes have shown
solids fraction of this industry’s waste can be used in applica- the highest treatment efficiency, which is required to
tions like fueling boilers [4, 7, 8], animal feedstock supplemen- achieve effluent quality targets with respect to organics.
tation [4, 9–12] or soil conditioning [4]. A significantly large These sentiments were supported by the findings of other
fraction of this waste, for example 90% of fruit weight fed into researchers [30, 31], and it is generally agreed that, when
the process of avocado oil processing [13], currently ends up in compared to aerobic biotreatments, AD has the following
landfills. Furthermore, the liquid portion is mainly dumped in advantages: it produces a much more stable digestate, con-
open lagoons (facultative ponds) exploiting natural aeration sumes less energy and generates less sludge/wastewater
and subsequent evaporation for these pollutants [5]. This liquid [32, 33].
portion of edible oil processing by-products normally contains There have been reports of AD being applied to manage-
residual fats and oils (lipids) [2]. Proteins, carbohydrates, traces ment of oil processing or related residues [34]. Residues that
of vitamins and antioxidants have also been detected in some have been previously studied include milk whey [35, 36], dif-
edible oil factory effluents [14]. Because of this multi- ferent meats [37], olive and palm oil processing wastes [38,
compositional nature, the effluent is not adequately treated by 39], coconut [40], soya bean [41], cotton [42], rapeseed [43],
means of the natural facultative pond route and disposal deci- sunflowers as well as fats, oils and grease (FOG) from restau-
sions for this by-product are consequently complicated. rants [44]. However, this literature is fragmented. This review
The process of anaerobic digestion (AD)—also known as study attempts to provide an overview for conceptualising the
biogasification or anaerobic biotreatment—involves the con- design and operation of AD systems that utilise edible oil pro-
version of organic compounds in an oxygen-free environment cessing by-products. The review provides a quick aggregated
by a consortium of bacteria to produce a useful energy carrier reference on opportunities, challenges and approaches for
gas called biogas. This gas mixture consists mainly of 55– biogasification of these substrates, while triggering debate
70% v/v methane and 30–45% v/v carbon dioxide). The AD and interest regarding inadequately researched issues related
bioslurry can be used as biofertiliser [15]. AD proceeds to this subject.
through four stages, namely hydrolysis, acidogenesis,
acetogenesis and finally methanogenesis [16]. Hydrolysis
breaks down polymeric organics into simple monomers. 2 Potentially digestable edible oil processing
Under acidogenesis, acidogenic bacteria will consume prod- by-products
ucts of hydrolysis while producing a mixture of sugars, vola-
tile fatty acids and alcohols. These products are further de- Popular edible oils are extracted from groundnuts, soybean,
graded by acetogenic bacteria into acetates, hydrogen and car- olives and sunflowers. Due to increased awareness of health
bon dioxide during the acetogenesis stage. The products of foods and health complications, there is increased consump-
acetogenesis are finally converted to biogas by methanogens tion of premium grade or essential oils. Some of these oils are
which are microorganisms belonging to the domain of ar- avocado oil [45], olive oil [46], canola oil, coconut oil, palm
chaea. This series of biochemical activities leaves a stable oil [47] and macadamia oil [11]. Premium oils are rich in
digestate slurry that can be applied to several processes, in- unsaturated long-chain fatty acids that help fight cancer-
cluding soil conditioning [14, 17], duckweed fertiliser [15] related ailments and cardiovascular disorders [48–50]. They
and even feedstock supplementation in fish farming [18]. are also good at moisturising hair and skin, because of their
However, AD performance is dependent on a number of fac- anti-ageing oxidant constituents [13]. These benefits of pre-
tors, such as feedstock physicochemical composition [19], mium grade oils have prompted an upward trend in global
and process variables such as temperature, total solids (TS), consumption of these products, along with the concomitant
pH, reactor type [20–23] and reactor arrangement [24]. positive financial and economic implications [11, 13, 48].
Biomass Conv. Bioref.

The increase in edible oil production is, however, also as- Information about COD and BOD for sunflower oil cake,
sociated with an increase in the quantity of waste generat- soybean oil cake and palm kernel cake could not be found in
ed. Edible oil is generally extracted by squeezing it out the literature reviewed, but the VS and corresponding mea-
from the oil-bearing fruit or seed. In some cases, it is fur- sured BMPs for these potential substrates are all within the
ther refined through degumming, bleaching, deodorisation range of 75–95% for VS and 227–420 mL/gVS for the mea-
and winterising processes that are collectively referred to sured BMPs, which is comparable to the parameters for cow
using the acronym RBDW [51]. RBDW is applied to in- dung [12, 57, 72, 76, 77, 86]. This further emphasises the
crease the oil shelf life especially if the product is to be potential usefulness of these substrates in digesters, after fur-
used in applications like cosmetics. The solid and liquid ther confirmatory laboratory trials. The measured BMP for
wastes generated in edible oil processing is generally rich in cottonseed cake [12, 79] is much lower compared to that of
organic matter, with quantifiable estimation of these organics other oil cakes, i.e. about 90 mL/gVS. This is despite the high
done through measurement of volatile solids (VS) for solids, VS content of 87%, which the authors attribute to some pos-
and chemical oxygen demand (COD) or biological oxygen sible unidentified microbial activity inhibitor in this substrate.
demand (BOD) for liquids. By-products of edible oil process- The potential existence of such inhibitors was not tested in the
ing assaying as high as 162 g/L COD [52–55] and 95% VS work cited here, and the COD degradation levels were also not
[56–58] have been reported. For wastewater disposal, South reported, in order to ascertain completeness of degradation. In
African legislation prescribes a COD limit of 0.075 g/L in addition to the unavailability of COD and BOD information
general water bodies and 0.03 g/L in special water bodies. for groundnut oil cake, macadamia oil cake and avocado
Effluents from factories that engage in RBDW processes will seeds, it was also challenging to find BMP data. However,
not be considered in this review, as they contain too high a the VS data on each of these products was reported to be
pollutant load, much of which is in the form of insoluble 95% of TS [87] for groundnut oil cake; 92–96% of TS for
COD. This insoluble COD is generally non-biodegradable macadamia cake [88, 89] and 98% of TS for avocado seeds
and can be inhibitory to microorganisms [27, 59]. [90, 91]. Again, these numbers point to the suitability of these
Table 1 lists some of the edible oil processing by-products substrates for use in AD systems.
and their top producers globally as well as issues of seasonal Extra parameters that could be used to determine or support
availability. Specific climatic condition is a critical factor with the potential candidacy of avocado oil vegetative wastewater
the choice and type of crop that can be grown in a particular and avocado oil pomace for biogasification could not be found
region. This inadvertently dictates the by-products that be- in the reviewed literature. However, given the high volumes of
come popular in any one region. Another important aspect waste generated from this industry in South Africa which were
with agrobased AD substrates is seasonal availability. These approximately 1300 t in 2013 as reported by the Department
issues have an implication on the possible adoption, scalabil- of Agriculture, Fisheries and Forestry, it may be necessary to
ity, capacity utilisation, cosubstrate selection and general eco- investigate the possibility of biogas production from this
nomics of running an AD system based on these substrates. waste.
Options available to curb this problem include running the AD
plant on other substrates when the main substrate is offseason,
building a smaller plant then preserve surplus substrate for
future use or shutting down the plant for maintenance during 3 Factors affecting biodigestion of edible oil
the offseason period. processing by-products
Table 2 and Table 3 indicate edible oil processing waste by-
products that can be considered for AD. In Table 2, the VS for 3.1 Physicochemical composition
solids are comparable to other conventionally used AD sub-
strates, like pig and cow manure, whose organic contents are During AD, biogas is derived from the organic components in
at 85% VS [82] as well as sewage sludge which has a 50% VS the substrate of interest. The substrate parameters that are
[83]. The liquid by-products’ organic loadings are also in the closely linked to organic concentration are the dry matter or
range of conventional substrates like cheese whey wastewater TS, VS, organic elemental analysis, the COD/BOD and the
whose CODs range 50–100 g/L [84]. The biomethane poten- nutritional or organic fraction composition (OFC). These pa-
tials (BMPs) for most of these by-products, as shown in rameters dictate the biogas potential and production rates of
Table 2, are comparable to those of conventional substrates, the substrates, and the survival and activity of microbes in the
like cow dung and wastewater treatment plant mixed sludge digester—and hence the efficiency of the biogasification pro-
waste, which have measured BMPs of 190 mL/gVS and cess. The substrate’s morphology also matters in terms of
396 mL/gVS, respectively [85]. The by-products’ specifica- methane yields and process kinetics. This will be discussed
tions in Table 2 and Table 3 therefore assert suitability of these in detail in a later Sect. 3.1.3 under lignin and nutrient bio-
by-products’ application in biodigestion. availability subjects.
Biomass Conv. Bioref.

Table 1 World statistics of edible oil and estimated oil processing by-products produced in 2014

Edible oil World top Oil produceda Quantity of Seasonality of processing and by-products Reference
producers by-productsa

Soyabean Brazil, USA 45,705 223,145 Farming is seasonal but harvested bean can be stored so [60, 61]
continuous processing possible
Palm Indonesia 63,930 156,522 Harvested all year round. Substrate seasonality not an issue [60, 62, 63]
Olive Spain, Italy 3050 18,300 About 7-month harvesting period per year. Storage a [60, 64]
challenge as the by-products tends to change under
atmospheric conditions.
Avocado Mexico, Chile 2 16 About 7-month harvesting period per year depending also [45, 64, 65]
on variety. Storage a challenge as the by-products tend
to change under atmospheric conditions.
Coconut Indonesia 3106 1673 Available all year round [60, 61]
Rapeseed EU 25,944 52,674 Farming and harvesting is seasonal but processing can be [60, 61]
continuous since the seed can be stored over reasonable
periods.
Sunflower Ukraine 15,848 29,432 Farming and harvesting is seasonal but processing can be [60, 61]
continuous since the seed can be stored over reasonable
periods.
Cottonseed China 5036 40,747 Farming and harvesting is seasonal but processing can be [60, 61]
continuous since the seed can be stored over reasonable
periods.

By-products include both solid and liquid wastes but only potentially digestible ones (this excludes RBDW effluents). Quantities of by-products are
estimated based on average industrial oil production yields stated in referenced materials
a
Quantities are stated in thousand tonnes

3.1.1 Effect of TS content digestion. The study used fruit and vegetable waste as the
substrate for AD under mesophilic conditions, and it revealed
A study conducted by Bouallagui et al. [92] on the effect of TS that the organic (VS) degradation efficiency, the biogas pro-
on biodigestion performance showed that this variable in a duction rates and yields, the methane content and even the
constant volume tubular reactor affects different aspects of mineral composition of digestate were all affected differently

Table 2 Various edible oil by-products and their biogas potential related characteristics

By-product Waste description COD (g/L) BOD (g/L) VS (% of TS) BMP (mL/gVS) Referencesd

Soybean oil wastewater Liquid effluents generated from soybean oil 9.7 5.2 73–75 300 mL/g CODb [66, 67]
extraction processes.
Palm oil mill effluent Viscous brown liquid comprising steriliser 69 10–30 10–25 or 83 g/L 325b [28, 68]
(POME) condensate, hydrocyclone waste and
separator sludge.
Olive mill solid waste Decanter sludge (pomace) rich in residual 162 n.d. 88–98 185b [52–55]
(pomace) lipids, volatile fatty acids (VFAs),
proteins, phenols and carbohydrates from
the milled olive kernels.
Olive mill wastewater Greenish effluent mainly from press and 40–20 23–100 69–94 or 390b [4, 69–71]
(OMWW) decanter operations. May also contain 16–82 g/L
polyphenols, tannins and pectins.
Rapeseed oil cakea A hemicellulose and protein-rich cake. 1.4 g/g DM n.d. 92–95 225.8b [56–58]
a c
Coconut oil cake Mechanical press residue rich in 0.87 g/g VS n.d. 84 304.5 [40]
lignocelluloses, fats and proteins.

n.d. no data
a
The COD of sludge is better expressed in mass-to-solid mass terms, rather than per litre of substrate
b
Measured BMP results are deduced empirically in the laboratory
c
Theoretical BMP results are obtained from calculations based on reported COD
d
Multiple referencing against one by-product indicates that different parameters/variables for the same by-product were cited from separate sources. The
use of different units by different authors also necessitated this. No average values were used but where ranges where applicable (due to different
literature consulted), this was indicated in the table and also triggered multiple referencing
Biomass Conv. Bioref.

Table 3 Typical elemental analysis and BMPs for solid by-products of edible oil processing

By-product Composition (% w/w) Empirical formulab BMP (mL/g VS) Referencese

C N H S Oa c d

Palm kernel cake 52.53 2.86 5.65 0.03 38.93 C22H28O12N 320 486 [72, 73]
Olive pomace 54.7 1.14 5.24 < 0.1 31.97 C56H64O24N 185 568 [55, 74, 75]
Rapeseed oil cake 48.9 6.1 6.1 0.6 38.3 C9H14O6N 225.8 449 [56, 58]
Sunflower oilseed cake 49.8 4.7 7.2 0.3 32.2 C12H22O3N 227 735 [57, 76]
Soybean oil cake 44.48 8.21 6.28 0.54 40.49 C6H11O4N 421.4 395 [77, 78]
Cottonseed cake 52 1.3 5.9 ND 40.8 C47H64O28N 78 491 [79, 80]
Groundnut oil cake 46.37 6.89 7.015 0.287 39.438 C8H15O5N n.d. 446 [81]
a
By difference
b
Sulphur concentrations too low—not considered in deriving the empirical formulae
c
Measured BMP results
d
Theoretically computed BMPs using the Buswell equation from elemental analysis
e
Multiple referencing against one by-product indicates that different parameters/variables for the same by-product were cited from separate sources. The
use of different units by different authors also necessitated this. No average values were used but where ranges where applicable (due to different
literature consulted), this was indicated in the table and also triggered multiple referencing

as TS varied. The digestion performance recorded as TS was triggered by osmotic pressure disturbances around the microbe
varied is displayed in Table 4. vacuoles, as popularly understood in yeast fermentation sys-
In terms of the methane yield only, different researchers [92, tems [97]. This general increase in methane yield with an in-
95] have reported that an increase in substrate TS induces a crease in TS is not infinite; however, as too high TS may also
higher methane yield. The low methane yields associated with hinder substrate accessibility and transfer across the cell walls
lower TS (too much water) are partly attributed to potential of the microorganism. This will subsequently reduce the meth-
nutrient or microbial washout in non-mixed systems [96]. It ane yield. Digester acidification due to high loading rate and
is possible that this observed phenomenon can also be resulting acid accumulation is likely in high TS digestion.

Table 4 Eff ect of feed TS and process hydraulic retention time (HRT) on AD system performance for a semicontinuously mixed tubular biodigester
using fruit and vegetable wastes as substrates. Adapted from Bouallagui et al. [92]

TS (%)a HRT OLR VS destruction Production Yield CH4 (%) Digestate mineral Comments and other references
(days)a (kgVS/m3 day) (%) rate (L/L day) (L/kgVSfed) content

N P K

4 20 1.77 74.4 1.16 695.45 65 4.7 9 19.9 Outside the HRT ranges stated
15 2.36 67.55 1.41 629.49 60 6.5 6 31.2 here by Bouallagui et al., digester
12 2.95 61.85 1.78 582.03 58 3.95 4.66 17.86 performance can be independent
of HRT if the HRT is high enough
[55].
6 20 2.65 75.91 1.63 707.18 64 5.38 8.6 28.4 Solid concentrations affect microbial
15 3.54 69.24 2.19 641.1 61 5.39 8.5 32 communities—hence pH, nutrient
12 4.42 65.63 2.62 594.96 55 2.92 8.08 16.22 release/solubilisation and the
general AD performance. A
solid content that is too high—
especially beyond 30%—is not
favourable [22, 93].
8 20 3.54 64.58 2.34 638.84 57 2.53 8.04 22.8 The general trends observed in AD
15 4.72 61.28 3.1 614.91 54 6.34 6.78 28 performance due to HRT and TS
12 5.90 58.58 3.2 514.01 50 4.85 6.03 26.8 can be modified in the presence
of other factors [6].

a
The type of reactor used in this experiment implies that solid retention time (SRT) is equal to HRT [94]. The same substrate was used throughout (with a
constant proportion of organics at 88.5% VS), so increasing the TS proportionally at a constant HRT or altering the HRT downwards for a constant TS
would have the same effect as increasing the organic loading rate (OLR) of the system. The calculated OLR per each experimental setup is recorded in
this table to reflect the interaction of these variables and impact on anaerobic digestion performance
Biomass Conv. Bioref.

Tekin and Dalgic [98] reported TS effects on olive pomace translate into more biogas. Organics are however further
digestions. In this study, pomace digestion at 5, 10 and 15% grouped into proteins, fats, carbohydrates and volatile fatty
TS under mesophilic conditions in a laboratory setup showed acids. Each organic component that contributes to the total or-
an increase in methane yield (in L/g of CODused), from 0.118 to ganic composition has a different biomethane potential. If a
0.122 as TS increased from 5 to 10% TS. However, a further substrate’s organic elemental analysis is known, then a mass
increase to 15% TS resulted in the methane yield reducing to balance approach can be used to predict the theoretical BMP.
0.105. It is, therefore, possible, that optimal TS must be appli- Consider a model substrate whose empirical formula is repre-
cable to each unique digestion system, which, in turn, implies sented by CaHbOcNdSe and whose biodegradation proceeds by
that experimental verification of each unique system might be reaction 1 as demonstrated by Buswell et al. [102] and later
necessary for optimal design, operation and troubleshooting. modified by Boyle (cited in Achinas et al. [103]). The model
TS has also been found to affect digester foaming tenden- substrate’s theoretical BMP can be calculated by Eq. 1 [104].
cies, with contrasting correlations having been established by
C a H b Oc N d S e ð1Þ
different investigators [95, 99] who experimented with waste-
water treatment activated sludge digestions. The findings of 1 1
þ ð4a−b−2c þ 3d þ 2eÞH 2 O→ ð4a−b þ 2c þ 3d þ 2eÞCO2
Jiang et al. [95] in which foaming height and propensity de- 4 8
1
creased with an increasing TS concentration are possibly more þ ð4a þ b−2c−3d−2eÞCH 4 þ dN H 3 þ eH 2 S
8
applicable to AD systems, because of the TS ranges (10–50 g/
L) which they used in their investigation and are applicable to (Reaction 1)
most AD plants. This contrast with the study done by Blackall 08   91
a b c 3d e
et al. [99], where a generalisation was made that foaming >
> þ − − − x 22400 > >
=C
B< 2 8 4 8 4
increases with TS and the TS ranges tested were not specified B
BMP ¼ @ C ð2Þ
> 12a þ b þ 16c þ 14d þ 32e > A
in spite of some activated sludges that can have as low as 1% >
: >
;
w/v TS. Cow dung and fruit/vegetable waste-based digesters
are the most commonly used AD systems, and these are op-
Theoretical BMP is stated in mL-CH4/gVSadded.
erated in the range of 6–10% w/v TS for optimal methane
When applying the above reasoning to individual nutrients
yield, consistent biogas composition and stable operation
constituting the organics found in an oil processing by-prod-
[100]. The foaming tendency associated with edible oil-
uct, it can be shown that lipids have a higher methane yield
based digestion systems might be further complicated by the
than proteins and carbohydrates [42], as indicated in Table 5.
presence of fats, which have a high tendency to float, despite
It then follows that if the nutritional compositions of certain
the TS composition of the slurry. Notwithstanding all these
substrates are known, their theoretical BMPs can be computed
general findings, it must be borne in mind that foaming is
and compared. These theoretical BMPs derived from Eq. 1 are
strictly dependent on a system, i.e. the type and size of solids,
normally much higher than BMPs measured in the laboratory
temperature, microbial profile, mixing regime, organic load-
or field experiments as shown in Table 3. This is because the
ing and potential for surface active agents in the particular
equation assumes 100% degradation of organics into methane
system [95, 101]. It follows that the relationship does not hold
which in practice is not realistically feasible. These theoretical
infinitely. There could be a concentration of solids that tends
BMPs are therefore used for preliminary evaluation only prior
to destabilise the foam.
to acquiring measured BMPs that consider real-life factors and
therefore glean more comparative information for different
3.1.2 Effect of OFC by-products.
Table 6 depicts the OFC profiles of the edible oil process-
For a given substrate, the OFC dictates the biomethane yield. ing by-products of interest in this study. As shown in this
OFC can be expressed in terms of VS, COD, BOD or nutritional table, palm oil effluents are highly lignocellulosic, which is a
composition. Generally, high total organic content should concern in terms of nutrient bioavailability, and hence

Table 5 Potential biogas production from different classes of nutrients [42]

Nutrient Methanogenic reaction Biogas (L/g) CH4 (%)

Lipids C50H90O6 + 24.5H2O → 34.75CH4 + 15.25CO2 1.425 69.5


Carbohydrates C6H10O5 + H2O → 3CH4 + 3CO2 0.830 50.0
Proteins C16 H24 O5 N4 þ 14:5H2 O→8:25CH4 þ 3:75CO2 þ 4NHþ −
4 þ 4HCO3 0.921 68.8
Biomass Conv. Bioref.

Table 6 Nutritional composition


of selected edible oil processing By-product Organic fractional (nutritional) composition (OFC) (% w/w) Referencesb
by-products
Proteins Lipids VFAs (mg/L) Carbohydrates Lignin

POME 9.07 13.21 2287 20.55 42 [14, 39, 105]


Palm kernel cake 14 8 49 [72]
OMWW 2.9 6–13.6 6000 31.4a [106]
Olive mill pomace 2.9 4.39 29.2a [52]
Coconut oil cake 19.95 3.22 10.59 [107]
Soya bean oil cake 39.0 14.9 27.8a 0.3-2.8 [12, 78, 88]
Cottonseed oil cake 24.0 5 56a 10.6 [12, 108]
Sunflower oil cake 23.72 2.75 23.47 7.72–11.1 [43, 57, 109]
Macadamia oil cake 39.5 15.3 49.6 [88, 89]
Rapeseed oil cake 34.5 13.05 22.08 6.53–9 [43, 56, 57, 109]
a
Calculated as the difference between total VS and volatiles stated
b
Multiple referencing in the context of this table are generated for the following reasons: (i) different parameters/
variables for the same by-product were cited from separate sources; (ii) the use of different units by different
authors with the implication that averages could not be calculated

substrate degradability. Macadamia and soybean oil cakes whose measured BMP is the highest among all the by-
have a higher lipid content than other substrates, which is a products reviewed here. This anomaly may be explained in
positive finding, as more biogas is expected; however, the risk terms of the recalcitrance of lignin which reduces the bioavail-
of rapid acidification is also high in this case. The OFC of ability of other nutrients in a substrate for conversion to meth-
coconut oil cake could not be found in the literature reviewed, ane. Soyabean cake has the lowest lignin content among the
but its measured BMP was reported to be 320 mL/g VS [40]. by-products discussed in Table 6. This implies that despite
soyabean cake’s unfavourable C/N ratio, most of its nutrients
3.1.3 The effect of C/N ratios are available to the microorganisms. The same reasoning may
explain why cottonseed cake in Table 3 shows a good C/N
Carbon is required by microorganisms for energy, while nitro- ratio but very low measured BMP. This may be attributed to a
gen normally provided by proteins is a necessity in the internal high fraction of lignin in this typically high carbohydrate con-
metabolic processes of the microorganisms. An imbalance of tent by-product. It is therefore imperative to take a holistic
the carbon-to-nitrogen (C/N) ratio in a substrate either im- approach when evaluating AD factors and parameters.
pedes growth or introduces ammonia inhibition challenges. Consideration of factors individually and making decision
Previous studies recommend a C/N ratio of between 20:1 based on one parameter alone may cause wrong deductions
and 35:1 as optimal for a healthy AD process [110, 111]. to be made, and therefore affect the whole AD process. It is
OMWW has too high a C/N ratio (100:1.77) and improve- pertinent to include the sulphur (S) and phosphorous (P) con-
ments on its digestion (both the biogas production rate and tents of the substrates when considering the C/N ratio as these
COD removal) were noted when this substrate was supple- affect AD processes. Just like nitrogen, phosphorous is re-
mented with high ammoniacal nitrogen wastes such as derived quired in minute quantities for growth by the microorganisms.
from laying hen litter and cheese whey [19]. Cattle manure, Conversely, sulphur in small quantities may be toxic especial-
piggery waste and even urea are also potential cosubstrates ly in the sulphate or hydrogen sulphide form [113, 114].
and supplements to correct nitrogen deficiency in substrates. Sulphur is generally related to protein content and is low in
The proportion of carbohydrates to proteins in a substrate also plant-based proteins when compared to animal (meat)-based
dictates the kinetics of digestion, since carbohydrates hydro- proteins. Table 3 shows the sulphur levels in edible oil pro-
lyse faster than proteins [112]. This observation implies that cessing by-products. Sulphur may therefore pose little threat
digestion of oil cakes, which are rich in proteins like rapeseed, in the digestion of these by-products. There is limited infor-
soyabean cake and groundnut cake may therefore be poten- mation from literature reviewed regarding phosphorous con-
tially rate limited by the hydrolysis step. There is also threat of tent of edible oil processing by-products; however, a recom-
ammonia inhibition associated with these by-products and a mended optimum ratio for C/N/P is 100:2.5:0.5 when
high carbon source cosubstrate may be necessary to improve digesting vegetable-related wastes [115]. If this ratio is not
the biodigestion of these by-products. Surprisingly, in this met, then codigestion may be an option to rectify inconsis-
group of low C/N ratio, by-products falls soyabean cake tencies in the elemental composition of these nutrients.
Biomass Conv. Bioref.

3.1.4 Effect of lignin content and phenolic organics methanogenesis may result in digester acidification [123].
Palmitic acid is the most common saturated LCFA among
Lignin is a carbohydrate polymer that is common in almost all edible oil processing by-products constituting between 11
plant-based substrates including edible oil processing sub- and 42% of total fatty acids in a substrate. The unsaturated
strates. Although the presence of lignin in a substrate gives acids in most by-products are oleic (15–71%) and linoleic (5–
an apparent high COD and VS, this compound is almost indi- 52%) [120]. Other saturated fatty acids that are found in these
gestible by most microorganisms [116]. The complex structure by-products though in low quantities are myristic, stearic and
of lignin and its non-biodegradability, furthermore, its structure arachidic acids. Unsaturated acids found in low quantities in-
traps other digestible nutrients, thus preventing access for clude palmitoleic and linoleic acids. Other concerns with the
microorganisms—this explanation can be summarised in the type and quantity of LCFA are the inhibition challenges,
concept described as bioavailability [117]. This apparent low sludge floatation and washout exhibited by these nutrients
bioavailability of nutrients for lignocellulosic substrates lowers [124, 125]. The LCFA recalcitrance to AD and their tendency
the actual BMP of a substrate when compared to its theoreti- to dictate the AD rate determining step are further discussed in
cally computed value. As such, this could plausibly explain the Sect. 3.1.6.
observation with cottonseed cake in Table 3. Theoretical It should be noted for Fig. 1 that ATP is involved at acti-
biomethane potential computations that are based on vation, and several enzymes are involved in β-oxidation cycle
Buswell’s formula assume 100% bioavailability, which is not but are not included here; they can be found in literature [126,
possible with lignin-containing substrates. Biodegradability is 127].
a measure of the actual performance of a substrate–
microorganism mixture compared to its theoretical perfor- 3.1.6 Addressing AD bottlenecks induced by substrate
mance, and it is therefore required for practical assessment of physicochemical characteristics
a material’s candidature in biodigestion applications. Despite
this shortcoming in theoretical BMP calculations, the method Substrate biodegradability through AD can be improved by
can be used as a precursor for initial screening of substrates, altering or enhancing the physicochemical composition through
before expensive resources are committed to do further tests on pretreatment, codigestion and digester additives. Most feed-
a substrate. Furthermore, the choice of lignin-containing sub- stock pretreatments are done to facilitate the breakdown of
strate must include considerations of a pretreatment [118]. complex organic compounds into smaller and easily digestible
Similarly, the presence of phenols, tannins, anthocyanin and molecules. In a review done by Okudo et al. [128], various
tocopherols in edible oil by-products will increase the apparent pretreatment methods for cassava were discussed, and these
organic fraction of such substrates, without a corresponding may be extended to other substrates like edible oil processing
increase in the measured BMP realised. Instead, these com- by-products given the structural similarities of many organic
pounds have been reported to induce adverse effects [69, substrates. Examples of pretreatment include ensilage,
119] on microbial activity, as described later in the toxicity thermomechanical or thermochemical treatment and ultrasonic
section of this study. or ultraviolet radiation [128–130]. Other pretreatments may tar-
get pH correction, such as the addition of sodium hydroxide or
3.1.5 Effects of type and quantity of fatty acids ammonia to OMWW [4, 70, 131]. Adding salts and external
microorganisms (bioaugmentation and bioprospecting) to the
Fatty acids (FA), which are a common feature in edible oil by- digester may also help with coagulation or neutralisation of
products, arise from the breakdown of lipids (tryglycerides). toxic substances prior to or during AD [130]. Suttinun et al.
Premium grade oils are rich in long-chain fatty acid types [132] achieved a 61% removal of phenolics in POME by aer-
(LCFAs) with a 12-carbon composition and more. The obically treating the POME using the Bacillus thermoleovorans
short-chain fatty acids (SCFAs) contain less than 12 carbon strain A2 at 60 °C. This detoxification improved anaerobic
atoms. LCFAs are either saturated or unsaturated, and these methane production by 1.7–10 times compared to untreated
differences ascribe different biogasification pathways for them POME digestion [132]. Aeration of OMWW for 7 days prior
as a consequence. Generally, SCFAs degrade faster than satu- to AD [71] and without any bacterial addition has also been
rated LCFAs and saturated LCFAs degrade faster than their successfully used to reduce phenolics by approximately 90%.
unsaturated counterparts. This kinetic behaviour is attributed This resulted in doubling of the methane yield.
to the fact that unsaturated LCFAs must undergo saturation Anaerobic codigestion (AnCod) has been found to assist
first, then oxidation to SCFAs; before methanogens can finally with improving biodegradability and microbial activity in di-
derive methane from them [120], it is possibly a factor in the gesters [133] by altering the C/N ratio towards the optimum
lengthy incubations often associated with AD. The degrada- range. This would be very helpful when dealing with edible
tion pathway for LCFAs is depicted in Fig. 1. However, rapid oil processing by-products; most of whose C/N ratios as seen
accumulation of SCFAs without a corresponding high rate of in Table 3 are below the recommended optimum of between
Biomass Conv. Bioref.

Fig. 1 Degradation pathway of


LCFAs to SCFAs, as described by
Novak and Carlson [121] and
Nunn [122]. Adapted from Hwu
[120]

25:1 and 30:1. AnCod also promotes favourable AD results by accompanying increase in methane production [19]. In the
shifting the overall thermodynamics of the system [14] and OMWW studies, more than 90% increase in methane produc-
diluting the effects of toxicity agents [134]. Beccari et al. [135] tion when codigested with chicken litter and a 22% increase
(also cited by Ahmad et al. [14]) observed that oleic acid at an for cheese whey were recorded when compared to raw olive
organic loading of 3 g COD/L is not degraded without glucose waste digestion.
supplementation of a minimum 6 g COD/L. When degrada- Digester additives like essential elements, detoxifying
tion proceeds under AnCod, it is assumed that the lipid oxi- agents and even microbes (biostimulation/bioaugmentation)
dation that is associated with a highly positive (+ 345.6 kJ/mol have been successfully used to improve the performance of
for palmitic acid) standard free Gibbs energy change [122] is digesters. Ni2+ and Mn2+ cations were identified as being es-
driven by the highly negative (− 457.5 to − 610.5 kJ/mol) sential for most methanogenic archaea with unconditional di-
standard free Gibbs energy change of glucose fermentation. valent ion requirement having been specifically reported for
Thermodynamic parameter shifting may also be induced by Methanococcus jannaschii [136, 137]. Besides Ni2+ and
bioaugmentation which in turn also improves AD perfor- Mn2+, other microelements that were studied and discovered
mance. Hydrogen-scavenging bacteria have been used to shift to be necessary, at different critical concentrations, by differ-
Gibbs free energy changes in a digester in a way that fast ent microorganisms, for improved biodigestion [138–140]
tracked and promoted lipid rich substrate degradation [120]. were Fe2+, Co2+, Mg2+, Ca2+, Cd2+ and Cu2+. However, be-
The hydrogen scavenging methanogens cause a reduction in yond certain concentrations in the digester, some metal cations
system pressure and a subsequent shift of Gibbs free energy caused an inhibition of methane-producing bacteria
from a positive value towards a negative value. The system [140–142]. Trace element/metal speciation, effects and bio-
pressure effect and the contributions of bacteria to that effect availability in anaerobic digesters were reviewed in detail by
on Gibbs free energy are indicated in Table 7. Thanh et al. [141]. A further review of the role of other addi-
The application of AnCod in edible oil processing by- tives in biodigesters is given by Romero-Guiza et al. [143].
products has been explored previously. Satyanarayan et al. These researchers included other important additives like bio-
[133] reported enhanced biogas production and better manure char, substances capable of suppressing ammonia inhibition,
effluent in terms of nitrogen and phosphate content and higher substances with a high biomass immobilisation capacity, bio-
methane content in biogas when cow dung was codigested augmentation and inoculation of enzymes that facilitate deg-
with soya sludge. AnCod experiments involving olive mill radation of certain compounds [144, 145]. Lessons learnt from
waste with chicken litter and cheese whey were also reported the soyabean sludge, POME and OMWW pretreatment exper-
to have improved the olive mill waste degradability, with an iments can be extended to other edible oil processing by-
Biomass Conv. Bioref.

Table 7 Gibbs free energy changes at 25 °C for the (possible) reactions involved in syntropic conversion of oleate and palmitate during methanogenic
decomposition (adapted from Ahmad et al. [14])

Reaction Process Reaction ΔGo (kJ/rxn)a ΔGo (kJ/rxn)b Shift b to c % shift ΔGo
no.
− −
1 Oleate degradation C 18 H 33 O22 þ 16H 2 O→9C 2 H 3 O2 þ 15H 2 þ 18H þ + 391 − 131 260 134
− −
2 Palmitate degradation C 16 H 31 O22 þ 14H 2 O→8C 2 H 3 O2 þ 14H 2 þ 7H þ + 419 + 81 338 81
3 Hydrogentrophic 4H 2 þ H þ þ HCO−3 →3H 2 O þ CH 4 + 136 + 20 116 85
methanogens
4 Acetoclastic C 2 H 3 O−2 þ H 2 O→HCO−3 þ CH 4 + 31 + 19 12 39
methanogens
a
Gibbs free energies (at 25 °C) calculated under standard conditions (solute concentrations of 1 M and gas partial pressure of 105 Pa)
b
Gibbs free energies (at 25 °C) for oleate/palmitate concentration of 1 mM, acetate concentration of 10 mM and H2 partial pressure of 1 Pa

products to improve these by-products’ biodigestion since digesting oleate in an expanded granular suspended bed
most of these by-products have similar physicochemical char- (EGSB) reactor at 55 °C, compared to runs for the same sub-
acteristics. A summary of the different additives, their effect strate at mesophilic ranges of 30–40 °C, where the highest
on anaerobic digestion and possible application in edible oil COD removal was recorded at 86.9%. This is only true if
processing AD is provided in Table 8. one is operating below toxicity levels of oleate; otherwise,
mesophilic operation becomes more stable than thermophilic
3.2 Process parameters and conditions operation at high oleate concentrations [160].
Prasad et al. [161] observed that temperature sensitivity on
3.2.1 Effect of temperature the biogas production rate is substrate dependent. They noted
that the gas production from cow and pig waste did not fluc-
Temperature has a profound effect on the biogas yield, com- tuate much as the temperature was varied from psychrophilic
position and production rate [155] and consequently on mate- to thermophilic; however, with chicken waste, significant sen-
rial degradation efficiency. Methanogens that perform opti- sitivity was noted when this temperature variation was
mally at temperatures ranging between 15 and 25 °C are effected. Another study, done by Ng et al. [39], confirmed
termed psychrophiles. Dhaked et al. [156] reviewed the same trend, i.e. thermophilic temperatures exhibited a
biodigestion at these temperatures. More research continues higher COD removal in digestion of POME, but this did not
to be done with psychrophiles including isolating microorgan- coincide with higher gas production. Instead, there was higher
isms acclimatised to cold climates and genetic modification of gas production in the two-phase but mesophilic setup than the
such microorganisms [157, 158]. Microorganisms that operate thermophilic run. This observation necessitates reliance on
at around 37 °C are called mesophiles, while those operating empirical data for each specific substrate when designing
at 50 °C and above are referred to as thermophiles. and operating a digestion system instead of using general
Ibrahim et al. [68] studied biodigestion of POME at two findings.
thermophilic temperatures of 45 °C and 50 °C and established
that higher COD removal, higher biogas production rates and 3.2.2 Effect of pH and buffering capacity
higher organic loading were possible by increasing the tem-
perature from the mesophilic range towards the thermophilic The digester pH affects the digestive performance of each type
range. This improved biodigestion efficiency was however of microorganism to a different extent [129]. Acidogenic mi-
accompanied by scum formation and clogging of pipes. In croorganisms are active across a wider pH range of 4 to 8, but
digesting castor oil cake at two temperatures of 30 °C and as the pH changes, the different acidogens that are responsible
37 °C, Gollakota and Meher [155] noted that more biogas for producing different VFAs have demonstrated variable per-
and higher production rates were recorded at 37 °C than at formance [162–165]. Propionic acid production is favoured at
30 °C. In addition, a tubular digester and codigestion system the pH lower end, while acetic acid and butyric acid produc-
of OMWW and OMSW thermophilic regime gave 427 kJ/day tions are favoured at a slightly higher pH. The ideal pH range
more energy than the mesophilic counterparts operated at sim- conducive for performance of methanogens has been reported
ilar hydraulic retention times (HRTs) and conditions [29, 69]. to be 6.5 to 7.5 and is narrower compared to that of acidogens
Edible oil processing wastes are characterised by high con- [166, 167]. Lay et al. [22] recommended an optimal pH range
tent of residual lipids (or LCFAs) and their response to tem- of 6.6 to 7.8 for mixed culture (acidogens and methanogens)
perature variation is therefore important. Hwu et al. [159] digestion and warned against process failure with a pH below
reported a significantly higher COD removal of 89.1% when 6.1 and above 8.3. Alternatively, a two-stage digestion
Biomass Conv. Bioref.

Table 8 Summary of additives on AD systems performance (expanded with permission from Romero-Guiza et al. [143]

Additive Impact Pros Cons Possible application in edible oil References


processing by-products
MY PS

Inorganic Micronutrients Fe, Mo, Se √√√ √√ Biomass stimulation Concept of bioavailability not Biostimulations may be necessary in these [141]
Sulphide fixation properly understood lipid-rich, phenolic-containing and poor
Higher waste solubilisation C/N ratio substrates. With lignin content
around 10% for most of these wastes,
Lower ORP
solubilisation may need to be assisted also.
Ni and Co √ √√√ Biomass stimulation Biomass inhibition by overdosing. [146]
Macronutrients Carbon sources, √√ √√ Alleviates ammonia inhibition Cost may not justify the small Risk of ammonia inhibition high due to poor [147, 148]
urea, K, Ca, Mg benefits. C/N ratios; hence, macronutrients can be
employed to rectify.
Materials Ammonia sequencing √√ √√ Lower ammonia concentration Precipitation and clogging risk. Same as above [145, 149]
agents Reagents cost.
Adsorbents for inhibitors √√√ √ Inhibitors deactivated or Lots of potential inhibitors (LCFAs,
concentration lowered ammonia, phenolics) require management
in these by-products.
Biomass support √√ √√ Higher kinetics and yields Scalability, especially in CSTR. Presence of proteins likely to reduce [28, 150, 151]
Process robustness hydrolysis kinetics. Biomass support could
be helpful.
Biological Bioaugmentation √√ √√ Better response to stressful or Scalability LCFAs are likely to be the major stressors [152–154]
transitory states. common and abundant to all substrates.
Increased methanogenic activity Cost Appropriate microorganisms to curb adverse
Increased hydrolytic activity Difficult monitoring. effects of these would be very useful here.
Enzymes would be necessary as lipids through
Enzymes √√√ √ Higher waste solubilisation Cost
coagulation and lignin by its macrostructure
tend reduce organics solubilisation

MY methane yields, PS process stability


Biomass Conv. Bioref.

process, in which the acidogenesis reactor is separate from the recommended [150, 174] that in order to guard against acidi-
methanogenesis reactor, can be employed, which will allow fication risks and run a stable AD process, the VFA/alkalinity
the system to operate the two different pH ranges necessary ratio in the slurry must be in the range 0.3–0.4.
for optimal microbial activity by each bacterial species.
Rapid hydrolysis of lipids to VFAs is one risk that edible oil 3.2.3 Effect of hydraulic and solid retention times (HRT
processing by-products are prone to and affects process pH and SRT)
badly [168]. Rapid accumulation of VFAs in a digester causes
acidification and affects the internal metabolic processes of Generally, digester performance as assessed in terms of COD/
microorganisms and the microbes’ overall effectiveness in VS degradation and methane content improves with an in-
AD. On the other end, high pH promotes degeneration of crease in HRT, as indicated by Bouallagui et al. [92] in
nitrogenous compounds (proteins) in the substrates to form Table 4. This trend of a higher HRT (in the range 12–20 days)
ammonia, which further increases the pH. This problem is accompanying better digestion performance was observed on
often observed when chicken manure is used as a substrate digestion of fruit and vegetable wastes in a tubular reactor
[148, 169]. As the pH continues to rise, methanogens that under mesophilic conditions. However, once optimal HRT is
operate optimally in a pH range of 6.8–7.2 will slowly lose attained, no further improvement in performance will be not-
efficiency and ultimately die, leading to digester fouling ed. High HRTs require bigger digesters and therefore more
[385]. The protein content in palm and olive products is lower capital expenditure [129]. Rincon et al. [55] experimented
than in other products (see Table 6), and this translate into high with olive mill pomace while varying HRT between 15 and
carbon/nitrogen ratios for these by-products. Ammonia inhi- 108 days and established that the performance of the anaero-
bition is therefore not a common threat with these substrates bic reactor becomes virtually independent of HRT, provided
because of this characteristic. Contrary to this, soyabean and that the HRT of the reactor is maintained above 28 days. For
rapeseed oil cakes exhibit slightly higher protein content than an HRT lower than 17 days, the performance of the reactor
other by-products. This lowers the C/N ratios and may neces- deteriorated sharply.
sitate strategies to supplement the carbon source during AD of In terms of biogas productivity, an increase in HRT reduces
these substrates for optimal microbial activity. Total ammonia the biogas production rates and the converse is also true. Tekin
nitrogen levels below 200 mg/L are reported to be necessary et al. [98] cited Martin et al. [175, 176], who worked with
for microbial growth, while concentrations exceeding 660 mg/ olive wastewater and established that there exists an optimal
L may inhibit AD process [170]. Masse et al. [171] reviewed HRT of around 12 days for the highest methane yield with this
ammonia inhibition and digester recovery options after inhi- substrate under their experimental conditions. Below or be-
bition in varying pH, temperature, reactor types and inoculum yond this number, the methane yield dropped, but, as previ-
sources. ously reported by Rincon et al. [55], beyond 28 days, there
Alkalinity measures the pH buffering capacity of the di- was no significant difference in the yield for both studies of
gester. Different chemical compounds like ammonia, VFAs, Martin op cit.
etc., affect digester alkalinity. It has been reported that the The negative correlation between methane yields and HRT
carbonic system dominates in determining pH stability [113, is explained in terms of the obvious inverse proportionality
172]. Recycling the digestate has been proposed as a solution relationship of organic loading rate (OLR) and HRT [29]. In
to digester alkalinity stabilisation, and this phenomenon has the codigestion of OMWW and OMSW under mesophilic
been studied during digestion of soyabean oil cakes from bean conditions and using a tubular reactor, Boubaker and Ridha
curd processing [67]. The study revealed that every system [29] noted that a total COD greater than 80 g/L and an HRT
has an optimal recycle ratio that improves COD removal with less than 12 days significantly reduced the biodigestion level.
minimum impact on the methane production rate and VFA Besides the impact of HRT on fermentation results, other re-
production or distribution in the effluent. Adding bicarbonate searchers established that HRT had a significant impact on
salts like sodium, potassium and lime into the digester have methanogenic bacteria, homoacetogens as well as sulphate-
also been suggested for alkalinity manipulation in POME di- reducing bacteria washout, while it had little influence on
gestion, which has a very low alkalinity [23]. Caustic soda is microbial populations for hydrogen-producing acetogens and
not recommended for pH correction, because of sodium tox- hydrolytic bacterial species [98, 177, 178]. Reducing HRT
icity, which can only be corrected with carbonate salts [173]. washed out the acetate-utilising and methanol-utilising
Khoufi et al. [134] demonstrated improved digestion of methanogens but increased the populations of hydrogen
OMWW by codigesting this substrate with liquid poultry ma- utilising and homoacetogens [177]. The effects of shifting
nure (LPM) in a ratio of 70:30 (OMWW/LPM) and using a microbial profiles were also reported to arise from fluctuating
jet-loop reactor. In doing this, the pH of OMWW was im- SRTs [179]. Appels et al. [113] reported that it is difficult to
proved, with an increase in alkalinity and a further improve- achieve stable digestion with SRTs below 10 days. Higher
ment of the C/N ratio within this system was observed. It is SRTs are also associated with better bacterial adaptation to
Biomass Conv. Bioref.

the substrate [179]. Adekunle and Okolie [180] recommended high concentrations of both cosubstrates were added into dif-
an HRT of at least 10–15 days to ensure that the slow-growing ferent digesters, biogas production reduced in both. The study
methanogens, with a doubling time of around 5–16 days, can later demonstrated that when the reactors were subjected to the
be retained and allowed to acclimatise. second shock loadings, there was quicker recovery to stability
Some of the approaches recommended for achieving with glycerol than with FOG. The authors concluded that by
higher SRTs include the use of a bigger reactor volume, re- managing microbial communities through OLR fluctuations,
ducing the influent flow and sludge (biomass) recycling [181]. VFA and biogas production profiles can also be controlled
Hwu et al. [182] observed an increase in OLR and methane [187]. This finding offers some operational flexibility to bio-
yields by recycling digestate in the thermophilic digestion of gas operators in optimising processes and managing
LCFA (oleate) wastewater. The digester without recirculation biodigestion of effluents loaded with high organics, like those
failed, due to inhibition at an influent concentration of 2 g emanating from edible oil processing plants. Optimisation of
oleate-COD/L producing 135 mg CH4-COD/(gVSS day), OLR in either codigestion or monodigestion setups is there-
while with recirculation, a maximum influent concentration fore pivotal to the success of the AD process.
of 4 g oleate-COD/L could be digested without significant
inhibition. The methane yield at this higher LCFA concentra- 3.2.5 Effects of agitation
tion coupled with recirculation was 300 mg CH4-COD/
(gVSS day). Mixing improves temperature distribution, solid suspension
and the interaction between microbes and the substrate while
3.2.4 Effects of OLR also reducing dead zones and short circuiting effects [113,
188]. Mixing also improves gas release from sludge [189].
Biogas is derived from the organic degradation process; This ultimately improves the substrate degradation [129].
hence, it could be expected that increasing the OLR should Gollakota and Meher [155] studied castor oil cake digestion
increase the specific gas production. Wirth et al. [183] report- under mesophilic conditions and noted that the optimal load-
ed this phenomenon in the AD of liquors from hydrothermal ing rate without stirring was 4 g of TS per litre per day; with
carbonisation of sewage sludge. The authors reported a steady stirring, it went up to 8 g of TS per litre per day. However, it
rise in specific gas production from 0.204 to 1.164 L/L/day has been established elsewhere that continuous or excessive
during thermophilic AD conditions, as ORL steadily rose mixing can also impede digester performance, especially at
from 1 to 5 g COD/L/day. In related studies, Xie et al. [184] higher loading rates [190, 191]. The excessive mixing intro-
and Gollakota et al. [155] reported that increasing OLR result- duces digester instability by reducing the oxidation rate of
ed in improved specific gas production until it reached a pla- fatty acids [190].
teau, but beyond this level, the system performance started to Another drawback of excessive mixing is potentially
deteriorate [155, 184]. High OLR has therefore been reported wasteful energy consumption by the AD system [192].
to increase VFA concentrations and ultimately reduce pH in Gomez et al. [188] demonstrated that in a low mixing regime,
the digester [185]. This condition inhibits methanogenic the digester could absorb shock loading and disturbances bet-
growth and activity in the digester [186]. ter than in a continuously mixed or high intensity mixing
Reduction in biogas production was noted as the initial regime. Stroot et al. [190] established that reduced mixing
volatile solid concentration in a batch experiment was in- can actually help to restore a destabilised continuously stirred
creased from 4.5 to 5 VS/L in coconut oil cake digestion digester. Optimal mixing should therefore be established, as
[40]. The organic overload emanated from residual fats and either extreme case has its disadvantages: too much mixing
oils in the cake, which normally assays 5–6% w/w of the TS. has been reported to stress the microorganisms, while foaming
In experiments involving olive mill waste, an increase in ef- can be an issue in a digester without mixing [180].
fluent VFA and COD was also noted when the OLR went up Detrimentally high organic loadings—and therefore possible
[55]. These authors noted a sharp decrease in pH to 5.3 when digester instability and foaming—are characteristic of most oil
OLR was set at 11 g COD/L/day and VFA correspondingly processing effluents, making agitation a very important pa-
reached 6.1 g/L. rameter to monitor and optimise when dealing with these ed-
Another concern that arises with high OLR is washout of ible oil processing by-products. Mild agitation requirements
the bacteria, which also triggers process failure [115]. can be met by frequent substrate feeding, as opposed to long
Manipulation of OLR can therefore be used as a tool to man- breaks before feeding [129]. However, if more agitation is
age digester microbial communities, as each cause of shock required, mechanical stirrers should then be installed or noz-
load brings about a different change in the microbial profile zles for slurry flushing. Federico et al. [193] studied the impact
and induces digester resilience to future shocking to a different of differently shaped agitators/impellors on AD system per-
extent. Ferguson et al. [187] experimented with two formance when handling an olive pomace-wastewater mix-
cosubstrates—FOG and glycerol—and established that when ture, and their findings indicate that viscosity plays a
Biomass Conv. Bioref.

significant role in impeller selection. Each impellor shape is membrane surface coating of bacterial species, which then
also well suited to a specific reactor arrangement; for example, hinders mass transfer of solubles across the bacterial cell
in the experiments executed by Federico and colleagues, the walls. In the case of LCFA inhibition, Palatsi et al. [202]
marine impellor performed much better in two-stage digestion reported that the best recovery strategies are increasing the
than the anchor impellor; however, the latter show superior inoculum: LCFA ratio and adding adsorbents like bentonite
performance compared to other impellors when single-stage and calcium carbonate. The authors were able to reduce re-
digestion is adopted. covery times from 10 to 2 days using these strategies in di-
Agitation helps in breaking the floating scums, though gesters that were fed semicontinuously. Other strategies to
there is debate in literature as discussed before on optimal reduce LCFA inhibitions (though not currently fully under-
mixing intensities and frequencies. The intensity and frequen- stood or studied) include enzyme pretreatment of substrates,
cy seem to be substrate dependent. For the digestion of edible codigestion with easily degradable materials, like glucose and
oil processing by-products, which are rich in lipids, CSTRs cysteine, then saponification of lipid-rich substrate before di-
have been reported [194] to achieve superior results due to the gestion [124]. Goncalves et al. [106] successfully combined
more aggressive agitation that prevents coagulation and sub- intermittent feeding practice with biomass retention (through a
sequent floating of materials. It is also reported that the upflow modified reactor design), including nitrogen supplementation
anaerobic sludge blanket reactor (UASB) suffers a lot from to combat LCFA inhibition, and prevent sludge flotation and
floating and washout because of the absence of mixing while microbial washout while digesting OMWW. These strategies
the inverted anaerobic sludge blanket reactor (IASB) actually also helped in abating phenolic inhibition. Nitrogen supple-
benefits from these floating aspects. The expanded granular mentation on the two reactors used in their work is reported to
sludge bed (EGSB) is also cited to be superior in lipid-rich have increased methane yields from 18% and 21% to 93% and
effluent digestion than the UASB [195]. The authors recom- 76%, respectively. The strategies used by these researchers
mend CSTR use with a recirculation stream that takes any would be advantageous in terms of production costs, as they
floating material from the top of the digester to the bottom eliminate the need for pretreatment when digesting these lipid-
to alleviate the material floating problems of these substrates rich substrates.
previously cited. Intermittent LCFA additions and codigestions with a max-
imum 65% VS from LCFAs have been reported to increase
3.2.6 Toxicity the methane yield. Beyond this LCFA contribution, inhibition
began to affect process efficiency and microbial profiles
Toxicity to microorganisms in AD arises from different [204]. This observation is supported by studies done on the
sources [196], including VFAs [123], LCFAs and heavy effects of lipids on municipal waste digestion [203].
metals [142], detergents [197], ammonia [170, 198] and anti- Phenolics and pectins/tannins that are found mainly in
biotics [199]. Chen et al. [196] reviewed and described in OMWW, OMSW and POME are also refractory to AD and
detail the effect of various inhibitors on AD. For edible oil partly toxic to microorganisms. This group of compounds
processing by-products that are rich in lipids, the greatest tox- include the tocopherols and anthocyanins. OMWW has been
icity risk could possibly arise from VFAs, where the mecha- reported to assay as high as 1% tannins and as high as 2.4%
nism of inhibition is related to pH disturbance. The pH distur- polyphenol content [4]. Although adequate literature on tan-
bances will interfere with microbial activities and functional- nins and polyphenols mode of toxicity could not be found,
ity, as previously discussed. Wang et al. [123] established the Chantho et al. [132] reported a very encouraging biological
critical concentrations for the main VFAs of ethanol, acetic (aerobic) pretreatment that removed more than 60% of the
acid and butyric acid (i.e. 2400, 2400 and 1800 mg/L, respec- phenolics found in POME [132]. Subsequent digestion of
tively), to observe significant inhibition in digesters. Propionic the pretreated substrate showed a 10% increase in specific
acid proved to be more inhibiting than the other VFAs, how- methane yields. In this work, Bacillus thermoleovorans strain
ever, and a 900 mg/L dose of propionic acid triggered inhibi- A2 bacteria was used. In a different research Aspergillus niger
tion. An optimisation study on these four VFAs led the authors bacteria was used to achieve the same goal on OMWW [205].
to establish the optimal VFA concentration in a digester for With these pretreatments, the recalcitrance of anthocyanins
ethanol, acetic acid, propionic acid and butyric acid as being and tocopherols could not be resolved but partial detoxifica-
1600, 1600, 300 and 1800 mg/L, respectively. These concen- tion of the total effluent was achieved which ultimately im-
trations corresponded with a maximum accumulative methane proved the effluent’s biodegradability. These findings can be
yield of 1620 mL, with a maximum methanogenic bacteria extended to investigate application on other edible oil process-
concentration of 7.3 × 108/mL. ing by-products.
Inhibition of AD from LCFAs has been extensively studied Intoxication of microorganisms from heavy metals is a
and reviewed by various authors [124, 126, 200–204], and complex phenomenon that, in most cases, is poorly under-
there is consensus that LCFA inhibition occurs through stood due to synergistic and antagonistic effects; the different
Biomass Conv. Bioref.

levels of toxicity, which are dependent on temperature; sub- 3.2.7 Foaming


strate redox potentials; the carbon source; Pearson index; sol-
ubility product; covalent index, etc. [142]. Due to these issues, Digester foaming is an undesirable condition that results in
it may be adequate within the scope of this study to just ac- inefficient gas recovery; causes an inverse solids profile, with
knowledge that beyond certain concentrations in the digesting higher solid concentrations at the top of the digester; creates
media, heavy metals can induce inhibition; therefore, in case dead zones; and reduces the active volume of the digester
of digester challenges, this aspect can also be investigated. [207]. These disturbances result in sludge that has not received
Toxicity in other lipid-rich substrates like rapeseed oil the same degree of stabilisation. Additional problems that
cake has also been registered with thiocyanates. Gell et al. arise in foaming digesters include: blockage of gas mixing
[206] demonstrated the feasibility of biogas production devices, foam binding of sludge recirculation pumps, fouling
from rapeseed oil cake, with codigestation being necessary of gas collection pipes due to entrapped foam solids, foam
to counter gradual inhibition from glucosynolates. These penetration between floating covers and digester walls and
glucosynolates normally break down into thiocyanates and tipping of floating covers during foam expansion and collapse
nitriles [206]. [207–210]. Krishma et al. [211] noted that in the digestion of

Table 9 Advantages and disadvantages of various anaerobic treatment methods for POME reproduced with permission from Chong et al. [220]

Method Advantages Drawbacks

Conventional AD (pond Low capital cost Large volume for digestion


and digester) Low operating and maintenance cost Long retention times
Able to tolerate big range of OLR (pond), thus can easily No facilities to capture biogas
cope with POME discharge during high crop season
Recovered sludge cake from pond can be used as fertiliser Lower methane emission
Anaerobic filtration (packed Small reactor volume Clogging at high OLRs
fixed bed reactor) Producing high-quality effluent High media and support cost
Short hydraulic retention times Unsuitable for high suspended solids wastewater
Able to tolerate shock loadings
Retains high biomass concentration in the packing
Fluidised bed Most compact of all high rate processes High power requirements for bed fluidisation
Very well-mixed conditions in the reactor High cost of carrier media
Large surface area for biomass attachment Unsuitable for high suspended solids wastewater
No channelling, plugging or gas holdup Normally does not capture generated biogas
Faster start-up
Upflow anaerobic sludge Useful for treatment of high suspended solid wastewater. Performance dependent on sludge settleability
blanket (UASB) Producing high-quality effluent Foaming and sludge flotation at high OLRs
No media required (less cost) Long start-up period if granulated seed sludge is used
High concentration of biomass retained in the reactor Granulation inhibition at high VFA concentration
High methane production
Upflow anaerobic sludge Higher OLR achievable compared to operating UASB Lower OLR when treating suspended solid wastewaters
fixed film (UASFF) or anaerobic filtration alone
Problems of clogging eliminated
Higher biomass retention
More stable operation
Ability to tolerate shock loadings
Suitable for diluted wastewater
Continuously stirred tank Provides more contact of wastewater with biomass Less efficient gas production at high treatment volumes
reactor (CSTR) through mixing
Increased gas production compared to conventional Less biomass retention
method
Anaerobic contact process Reaches steady state quickly Less stable due to oxygen transfer in digesting tank
Short hydraulic retention time
Produces relatively high effluent quality Settleability of biomass is critical to successful
performance
Table 10 Comparison of single- versus multi-phase digestion on edible oil processing by-products

Substrate Single or VS/COD BMP or productivity Comments on stability Test conditions References
multi-stage degradation

Soybean Single stage ND 421.4 mL/gVS Stable with kinetics resembling those of Standard measured BMP test using [77]
wastewater microcrystalline cellulose. AMPTSII kit
Single stage ND Approx. 110 High TAN concentration of 4730 mg 2-L batch reactors operated at 37 °C [66]
L-CH4/kg VSfeed TAN/kg recorded, which is assumed to for 42-day incubation period.
be the cause of poor methane productivity
when compared to codigested scenarios
where the TAN was 3720 mg TAN/kg
with productivity of 258
L-CH4/kgVSfeed.
4-stage ABR 97% total COD 113.9 L methane per day Improved tolerance to shock loadings Influent concentration of 10 g/L [223]
removal revealed due to different microbial COD, T 35 °C, OLR up to
profiles in each compartment. Ammonia 6 kg-COD/m3 day and HRT
and high solids inhibition avoided. 39.5 days per stage. Macro and
micronutrient supplementation
implemented.
Olive oil Single stage 51% TCOD 53.2 mg-CH4/gTS Biogas production trend was positive in first Batch measured BMP assay at T of [134]
wastewater removal 10 days and thereafter began to fluctuate 37 °C using 120 mL (working
on daily basis, perhaps because of volume 60 mL) bottle reactors. pH
phenolics and LCFA induced was adjusted to 7.2. Incubation for
inhibition-recovery cycles. 65 days.
Two stage 64% TCOD removal 243 L-CH4/kg CODadded Generally stable TS removals and stable pH Feedstock was OMWW codigested with
41% TS removal in the reactors. Minor fluctuations in gas liquid cow manure (LCM) and cheese
59% VS degradation production rates and in methane content. whey (CW) in the ratio of 55:40:5
No detrimental process failure recorded. (OMWW/LCM/CW) % wt basis.
Two CSTRs used at 35 °C. Overall
HRT was 19 days. OLR was 5.5 g
COD/L day.
Single stage (batch) 7.8% COD removal 11.4 mL CH4/gCODremoved High VFAs to alkalinity ratios and high Batch test in 100 mL serum vials at [132]
phenolic levels are possible reasons for 35 °C, pH 4.7. No pretreatment for
low measured BMP. balancing pH or nutrients.
Single-stage 75% total COD 234 mL CH4/gCODapplied Scum formation and solids floating at higher 2-L semi-continuous reactor operating at [38]
(semi-continuous) removals OLR. Fats and grease solidifying and 5.6 days HRT and max OLR 12 g
blocking discharge lines. COD/L day. Temp. 35 °C and pH
adjustment using NaOH 7–7.5.
Two stage 64% TCOD removal 264 mL CH4/gCODutilised n.d. First stage ran at HRT of 1 day. Second [39]
at HRT of 10 days at HRT of 10 days. 559 stage HRT varied (10, 20, 30 days).
74% TCOD mL CH4/gCODutilised Recirculation of stage 2 digestate to 1.
removal at HRT at HRT of 30 days. pH correction at start-up only
of 30 days (Na2CO3). T − 32 °C. OLR 1.2–3.4 g
COD/L day.
Canola or Single stage n.d. 530 mL CH4/gVS Inhibition noted with continuous operation A CSTR operating at OLR 2.42 kg/m3 [56]
rapeseed cake if it proceeds for too long on days of VS. Temperature was 37 °C
monodigestion of the rapeseed cake.
Glycerol for codigestion was proposed.
Two stage The above study on single-stage digestion noted that there was no justification for two-stage digestion with this substrate [56].
Biomass Conv. Bioref.
Biomass Conv. Bioref.

wastewater sludge when using air agitated and mechanically Digestion in one reactor (single-phase system) or separat-
agitated digesters, there was more foam in the air agitated ing the hydrolysis-acidogenic phase from the acetogenic-
digester (2.4 m) than that in mechanically agitated one methanogenic phases (two-phase system) can also introduce
(1.3 m). They further observed that the higher foaming digest- some performance differences [218, 221, 222]. Table 10 sum-
er produced less gas (0.74 m3/kg VS destroyed) than the low marises the benefits and disadvantages of single- and multi-
foaming one (0.93 m3/kg VS destroyed). phase digester arrangements. For improved waste stabilisation
An extensive review of foaming causes in digesters was and higher digestion efficiencies compared to single-stage
conducted by Ganidi et al. [207], who concluded that for systems, Matsuo and Jeyaseelan [224] recommended the use
foaming to take place, initiation substances must be present of a two-stage system for lipid-rich substrates such as milk by-
in the digesting slurry. A number of studies have implicated products [224]. However, contrary to the observations made
Microthrix parvicella [212–214] as being mainly responsible by many researchers—that two-stage biodigestion induces
for initiating foaming in digesters. Fats, proteins, oils and higher VS/COD degradation [225], accommodates higher
grease (FOG) have been reported to promote metabolism of HRTs, improves methane yields, gives a more stable digestate
these microorganisms; hence, the presence of these nutrients and many other advantages [24, 226, 227]—none of these
in edible oil processing by-products must pose a foaming claims were significantly fulfilled in the case of experiments
threat [213]. The presence of LCFAs also promotes growth with rapeseed oil cake [43]. Single-stage codigestion of rape-
of M. parvicella [215, 216]. The bacterium M. parvicella seed cake and glycerol was therefore recommended in this
thrives in low temperatures of around 25 °C, and therefore, study for purposes of capital cost savings and the suppression
foaming has been found to be more severe in wintertime than of inhibitors. This anomaly between most substrates and rape-
in summertime. A solution that has been posited to manage seed cake may possibly be explained in terms of variations in
foaming induced by this bacterium is to use polyaluminium phytonutrients that may induce complicated phytotoxicity to
salt-based coagulants [212, 214], to operate the digesters at microorganisms.
mesophilic or even thermophilic temperatures, and, if possi- Fixed film reactors (sometimes called biofilters) are a spe-
ble, to avoid operating within the psychrophilic range. cial design of digester that offers a high surface area for bac-
terial attachment [129]. This feature helps to increase micro-
bial population density and improve the microorganism’s re-
3.3 Effects of reactor configuration tention time which subsequently reduces HRTs. Kumar et al.
[129] reported HRT reduction from 30 to 40 days to a few
Biogasification can be carried out in different digester config- hours and emphasised that the fixed film reactor is well suited
urations (CSTR, plug, fixed film, garage type dry fermenters, for effluents with low solid concentration. This implies that
covered lagoon and UASB) whose performances also tend to possibly only low TS edible oil processing effluents can be
be different [217–219]. Ghosh and Bhattacherjee [217] report- considered for digestion in this reactor while other high TS
ed the performance of plug flow versus CSTR and, in most streams will use other reactor types. In their review, Chimain
respects (HRT, specific volume, specific production), the plug et al. [23] described in detail the different reactors and their
flow showed superior performance. Another reactor configu- performance, particularly with palm oil mill effluent as the
ration aspect is bacterial entrapment, which is associated with substrate.
sludge blanket reactors (UASB, IASB and EGSB), and it has Another AD differentiation is made between dry and wet
been suggested that fixed film reactors are helpful in reducing systems. Dry digestion takes place when slurries with solid
washout while operating at lower SRTs and HRTs. SRT and content are between 20 and 40% w/w, while wet digestion
HRT have implications on throughput and digester sizing operates with solid concentration below 10% w/w [228].
[180], so if these can be manipulated through the selection Normally, the choice of dry or wet mode of operation is guid-
of digester type one has to make a wise decision on this aspect ed by process water constraints. Digesters can also be operated
at plant design stage. Chong et al. [220] reviewed the various in continuous, semi-continuous and batch modes.
digester setups when applied to POME digestion and focused
on mode of operation and the relative advantages and disad-
vantages of each. Table 9 summarises their findings on a va- 4 Concluding remarks
riety of digesters. However, it should be noted that each reac-
tor type has its advantages and shortcomings so not all di- This paper attempted to conduct a detailed survey of the liter-
gesters reviewed here will be applicable on every edible oil ature on edible oil processing wastes used as substrates for AD
processing by-product. As such, it is suggested that every by- systems. A number of insights can be drawn and explored for
product with its unique specifications must be matched with future use in the design of new processes dealing with these or
the reactor capability and limitations to evaluate suitability for related substrates. The opportunities and challenges unearthed
use. in this study could also be used in the day-to-day process
Biomass Conv. Bioref.

troubleshooting and operation of AD processes handling edi- regarding AD of high lipid-based wastes, like by-products of
ble oil processing-related substrates. edible oil processing. AD studies of the liquid portion of ef-
The following are some of the major findings from this fluents arising from edible oil refining, bleaching, deodorising
review. and winterising (RBDW) units also requires attention.

1. To some extent, edible oil processing wastes from differ- Acknowledgments This research was supported by the University of
South Africa (UNISA) through the Institute for the Development of
ent oil seeds or fruits share similar physicochemical char-
Energy for African Sustainability (IDEAS). The authors are grateful to
acteristics, e.g. the presence of residual fats and proteins, UNISA for the resources provided to enable this work to be conducted.
as part of their organic fractional composition. However,
there are notable differences among some of these wastes, Compliance with ethical standards
which confer different biodigestion characteristics to each
substrate. One example of such differences is the presence Conflict of interest The authors declare that they have no conflict of
of polyphenols in avocado and olive oil processing by- interest.
products, while groundnut and soybean-based wastes do
Publisher’s note Springer Nature remains neutral with regard to jurisdic-
not contain these. Each substrate must therefore be
tional claims in published maps and institutional affiliations.
experimented separately to establish suitable operating
or design conditions. However, echo-studies can be
consulted as a starting point for such substrate-specific
studies. References
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