Review Article: Utilization of Biodiesel By-Products For Biogas Production

Hindawi Publishing Corporation
Journal of Biomedicine and Biotechnology

Volume 2011, Article ID 126798, 15 pages
doi:10.1155/2011/126798
Review Article
Utilization of Biodiesel By-Products for Biogas Production
Nina Kolesárová, Miroslav Hutňan, Igor Bodı́k, and Viera Špalková

Institute of Chemical and Environmental Engineering, Faculty of Chemical and Food Technology,
Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia
Correspondence should be addressed to Nina Kolesárová, nina.kolesarova@stuba.sk
Received 22 August 2010; Revised 22 November 2010; Accepted 7 January 2011
Academic Editor: Leon Spicer
Copyright © 2011 Nina Kolesárová et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.
This contribution reviews the possibility of using the by-products from biodiesel production as substrates for anaerobic digestion
and production of biogas. The process of biodiesel production is predominantly carried out by catalyzed transesterification. Besides
desired methylesters, this reaction provides also few other products, including crude glycerol, oil-pressed cakes, and washing water.
Crude glycerol or g-phase is heavier separate liquid phase, composed mainly by glycerol. A couple of studies have demonstrated
the possibility of biogas production, using g-phase as a single substrate, and it has also shown a great potential as a cosubstrate by
anaerobic treatment of different types of organic waste or energy crops. Oil cakes or oil meals are solid residues obtained after oil
extraction from the seeds. Another possible by-product is the washing water from raw biodiesel purification, which is an oily and
soapy liquid. All of these materials have been suggested as feasible substrates for anaerobic degradation, although some issues and
inhibitory factors have to be considered.
1. Introduction countries, such as India, Brazil, Argentina, Malaysia, and

Fiji.
Renewable energy sources and biofuels, including biodiesel, As a primary feedstock, vegetable oils, animal fats, or
have been gaining increasing attention recently as a replace- waste cooking oils can be used for the production of
ment for fossil fuels [1]. However, their implementation in biodiesel. In Europe, rapeseed oil is predominantly used,
the general market depends on making these fuels more while, in the world extent, highest quantities of biodiesel are
competitive. A convenient way to lower the costs of biofuels is produced from soya oil [3].
to use the by-products as a potential source of energy, rather The process of biodiesel production is usually carried
then treat them as waste. out by catalyzed transesterification with alcohol, most likely
Biodiesel is a prominent candidate as alternative diesel methanol (Figure 1). A catalyst is usually involved to improve
fuel. It is offering few advantages compared to conventional the reaction rate and yield [3]. Alkalies (sodium hydrox-
diesel, including the status of renewable energy source ide, potassium hydroxide, carbonates, and corresponding
and lower emissions. Advances against petroleum diesel sodium and potassium alkoxides), acids (sulfuric acid,
fuel are represented by the terms of sulfur content, flash sulfonic acid or hydrochloric acid), or enzymes can be used
point, content of aromatic substances, and biodegradability to catalyze the reaction. Base-catalyzed transesterification
[1]. is much faster than the acid-catalyzed one (base catalyzed
With approximately 245 processing plants and annual transesterif ication is basically finished within one hour) and
production of about 9 million tons, European Union is most often used commercially [4–6].
has had the leading position in both production and Besides the desired methylesters this reaction provides
consumption of biodiesel [2]. These plants are mainly also few other products. Isolation of oil from the oil seed
located in Germany, Italy, Austria, France, and Sweden. plants by pressing and extraction provides oil cakes or oil
Production of biodiesel has been expanding rapidly also on meal as a by-product. In the reaction of transesterification,
the other continents, mainly in the USA and developing triglycerides are converted into glycerol and methylesters
2 Journal of Biomedicine and Biotechnology
Table 1: Analysis results of macroelements, carbon and nitrogen in crude glycerol from different feedstocks (BDL indicates values that are
below the detection limit for the corresponding analytical method) [25].
Feed stocks Ida Gold Mustard Pac Gold Mustard Rapeseed Canola Soybean Crambe Waste vegetable oils
Calcium, ppm 11.7 ± 2.9 23.0 ± 1.0 24.0 ± 1.7 19.7 ± 1.5 11.0 ± 0 163.3 ± 11.6 BDL
Potassium, ppm BDL BDL BDL BDL BDL 216.7 ± 15.3 BDL
Magnesium, ppm 3.9 ± 1.0 6.6 ± 0.4 4 ± 0.3 5.4 ± 0.4 6.7 ± 0.2 126.7 ± 5.8 0.4 ± 0
Phosphorus, ppm 25.3 ± 1.2 48 ± 2.0 65 ± 2.0 58.7 ± 6.8 53.0 ± 4.6 136.7 ± 57.7 12.0 ± 1.5
Sulfur, ppm 21.0 ± 2.9 16.0 ± 1.4 21.0 ± 1.0 14.0 ± 1.5 BDL 128.0 ± 7.6 19.0 ± 1.8
Sodium, % wt 1.17 ± 0.15 1.23 ± 0.12 1.06 ± 0.07 1.07 ± 0.12 1.2 ± 0.1 1.10 ± 0.10 1.40 ± 0.16
Carbon, % wt 24.0 ± 0.00 24.3 ± 0.58 25.3 ± 0.58 26.3 ± 0.58 26.0 ± 1 24.0 ± 0.00 37.7 ± 0.58
Nitrogen, % wt 0.04 ± 0.02 0.04 ± 0.01 0.05 ± 0.01 0.05 ± 0.01 0.04 ± 0.03 0.06 ± 0.02 0.12 ± 0.01
R1 O Similarly to heterogeneous catalysis, it also provides a

O solution of avoiding difficult recovery of glycerol and
R1 OCH3 methylesters purification. Although this technology offers
O
O OH an attractive alternative, the industrial application has been
CH3OH slow due to feasibility aspects and some technical challenges,
R2 O + + HO OH
KOH R2 OCH3 resulting from the low solubility of methanol and glycerol in
Glycerol
O O O
biodiesel and high cost of lipases as catalyst.
O Transesterification with supercritical methanol provides
R3 R1 OCH3 several advantages, compared to traditional methods [21–
24]. The reaction is fast, in addition no catalyst is needed
Triglyceride Biodiesel
and therefore the separating process of the catalyst and
Figure 1: Reaction of biodiesel production by base-catalyzed saponified products becomes unnecessary. Generation of
transesterification with methanol. washing water can also be avoided. However the high
pressure and temperature (239–385◦ C) is required, which
leads to high energy consumption and production costs.
(biodiesel) are separated from the heavier glycerol phase Commonly the most important by-products from
(crude glycerine) by settling. To remove the impurities, biodiesel production are pressed cakes from oil extraction,
soaps, short chain fatty acids and excess methanol, crude crude glycerol and washing water [5, 7, 18]. The nature of
biodiesel is subsequently washed generating the washing these products is highly dependent on the character of raw
water as another potential by-product. material and processing technique, although generally they
Although the present production of biodiesel is mainly present suitable substrates for anaerobic digestion with the
carried out by homogeneous base-catalyzed transesterifi- production of biogas.
cation, implementation of alternative approaches has been
increasingly studied [7–24]. Homogeneous base catalysis has 2. Crude Glycerol
few disadvantages, such as the high requirement for the
purity of oil. The high consumption of energy and costly Crude glycerol (g-phase) is heavier separate liquid phase, co-
separation of the homogeneous catalyst from the reaction mposed mainly by glycerol. In general for every 100 kilo-
mixture have also called for development of new catalysts. grams of biodiesel about 10 kilograms of g-phase is pro-
Different alternative techniques have been applied for duced.
biodiesel production [7–11]. The most promising ones Crude glycerol generated by homogeneous base-cata-
include employing heterogeneous catalyst, lipase catalyst or lyzed transesterification contains approximately 50–60% of
supercritical alcohol [12]. glycerol, 12–16% of alkalies especially in the form of alkali
Catalysis using solid heterogeneous catalysts runs slower soaps and hydroxides, 15–18% of methyl esters, 8–12% of
than homogeneouscatalysis, however it can be integrated methanol, 2-3% of water and further components [25, 26].
with continuous processing technologies. A great variety Tables 1 and 2 summarize the characteristics of g-phases
of catalysts in catalytic transesterification of vegetable oils based on the source of oil used for the production of
have been used recently, including zeolites, hydrotalcites, biodiesel. Analytical results from the macroelement screen-
oxides, and so forth, [13–17]. Utilization of heterogeneous ing tests are listed in Table 1. Crude glycerol contains a vari-
catalysts provides few advantages over the homogeneous ety of elements, such as calcium, magnesium, phosphorus or
base catalysis, including mainly the easier purification of sulfur, originating from the primary oil. Larger quantities of
methylesters from glycerol and impurities. Also, the content sodium or potassium are also contained, coming from the
of free fatty acids and water in the raw material does not catalyst.
affect the reaction [12]. Table 2 shows the content of protein, fat, ash, carbohy-
Enzyme catalyzed transesterification using lipases for drates in percents and caloric value for kg. G-phase is mostly
biodiesel production is also increasingly studied [18–20]. composed of carbohydrates, represented by glycerol. The ash
Journal of Biomedicine and Biotechnology 3
Table 2: Food nutrient analysis for crude glycerol samples [25].
Feed stocks Ida Gold Mustard Pac Gold Mustard Rapeseed Canola Soybean Crambe Waste vegetable oils
Fats, % 2.03 1.11 9.74 13.1 7.98 8.08 60.1
Carbohydrates, % 82.8 83.8 75.5 75.2 76.2 78.6 26.9
Protein, % 0.14 0.18 0.07 0.06 0.05 0.44 0.23
Calories, kJ/kg 14.6 14.5 16.3 17.5 15.8 16.3 27.2
Ash, % 2.8 1.9 0.7 0.65 2.73 0.25 5.5
contained in crude glycerol is mainly sodium or potassium enzymes, microbial lipids (single-cell oils), medicinal drugs,
from the catalyst. antibiotics and fine chemicals. Bioconversion of g-phase
Considering that the processing technology of biodiesel into chemicals, such as dihydroxyacetone, 1,2-propanediol,
production affects the characteristics of by-products, the ethanol, hydrogen,citric acid, propionic acid, polyglycerols,
new technologies and modern catalysts can be expected to succinate, have been also increasingly studied recently
influence the composition and utilization of crude glycerol. [60–77].
For example, g-phase originating from biodiesel production Another option offers biological production of methane
using rapeseed oil with heterogeneous catalyst is limpid and from crude glycerol using anaerobic sludge [78–88]. Besides
colorless, containing at least 98% of glycerin and neither ash, the production of methane, the advantages include low
nor inorganic compounds were detected in it [27]. nutrient requirements, energy savings, generation of low
As the biodiesel production is increasing exponentially, quantities of sludge and excellent waste stabilization. Glyc-
the crude glycerol generated in this process has also been erol is a readily digestible substance, which can be easily
generated in a large quantity. Despite the wide applications stored over a long period. High energy content in g-phase
of pure glycerol in pharmaceutical, food and cosmetic makes it an interesting substrate for anaerobic digestion as
industries, the refining of crude glycerol to a high purity well, since it offers high production of biogas in smaller
is too expensive, especially for small and medium biodiesel reactor volumes. A great variety of microorganisms is able to
producers [28]. The investments for the construction and use this substrate as a carbon source for the growth under
startup operation of crude glycerol purification facility make anaerobic conditions, such as Citrobacter freundii, Kleb-
according to Singhabhandhu [29] roughly 65 million Euros siella pneumoniae, Clostridium pasteurianum, Clostridium
(facilities with production capacities of 1.4–2 ML/y). Weber butyricum, Enterobacter agglomerans, Enterobacter aerogenes
[30] mentions 27% of the capital investment costs going or Lactobacillus reuteri [28, 34, 58, 67]. The production of
to construction of the technical glycerin facility in a 12 ML biogas through anaerobic digestion offers significant advan-
biodiesel refinery (Aschach, Austria). tages over other forms of crude glycerol treatment. It requires
To improve the economic feasibility of biodiesel industry, lower investments and simpler operational conditions com-
new alternate ways of utilization of g-phase have been pared to more sophisticated preprocessing technologies,
studied recently. Possibilities such as combustion, coburning, which makes it ideal for local applications. Less biomass
composting, animal feeding, thermochemical conversions sludge is produced in comparison to aerobic treatment
and biological conversion have been applied for crude technologies. The digestate is an improved fertilizer in terms
glycerol processing [31–46]. of both its availability to plants and its rheology. A source of
One of the possible applications is utilization of g- carbon neutral energy is produced in the form of biogas.
phase as carbon and energy source for microbial growth in
industrial microbiology. Microbial conversion of glycerol to 3. Anaerobic Digestion of Crude Glycerol
various compounds has been investigated recently, with par-
ticular focus on the production of 1,3-propanediol [47–50], Considering anaerobic treatment of crude glycerol, potential
which has been considered as a main product of glycerol fer- of its main component glycerol has been well-known for a
mentation [28]. 1,3-propanediol presents several interesting longer period [89–91]. Digestion of pure glycerol has been
applications, it can be used as a monomer for polycondensa- investigated both as a primary substrate [89, 90], and as
tions to produce plastics with special properties, (polyesters, an intermediate product of anaerobic degradation of fats
polyethers and polyurethanes) [51–54] as a monomer for [91]. Biodegradation have been carried out using either pure
cyclic compounds, as a polyglycol-type lubricant [55] and cultures of microorganisms [90] or sludge composed of
it also may serve as a solvent [56]. The biotechnologi- mixed cultures from wastewater treatment plant [89].
cal production of 1,3-propanediol from glycerol has been Few studies focused on biogas production from g-
demonstrated for several bacteria, Klebsiella pneumoniae, phase [78–88] have also been realized recently. Anaerobic
Clostridium butyricum and Citrobakter freundii have been treatment of g-phase as a single substrate [78–81] was carried
most commonly used in the studies [47–50, 57–59]. out as well as coprocessing of crude glycerol with different
Besides the production of 1,3-propanediol, glycerol can substrates [82–88].
also be used as a carbon source to obtain other valuable Mesophilic anaerobic digestion of crude glycerol was
microbial products, such as recombinant proteins and studied in work Lopez et al. (2009). The substrate was
previously treated in two different ways: (1) acidification The laboratory-mixed reactor achieved stable operation at
with phosphoric acid and centrifugation (so-called acidified ORL of 4 kg/m3 ·d (COD). The specific production of biogas
glycerol) or (2) acidification followed by distillation (so- achieved ca0.980 m3 /L of glycerol added. The laboratory
called distilled glycerol) [78]. Either granular sludge from UASB reactor with granulated biomass achieved stable
anaerobic reactor treating brewery wastewater or nongranu- operation at ORL of 6.5 kg/m3 ·d and the specific biogas
lar sludge from anaerobic reactor treating urban wastewater production was ca0.840 m3 /L of glycerol added. Inoculation
was used for inoculation of batch laboratory-scale reactors, of the UASB reactor with suspended biomass showed that
having the working volume of one liter. The variations this type of sludge is not suitable for this purpose because
in the methane production were studied, considering the of sludge flotation during the reactor operation.
different ways of substrate pretreatment and different types Yang et al. (2008) examined biodegradation of glycerol-
of sludge. The use of the combination of granular sludge containing synthetic wastes using a fixed-bed laboratory
with acidified glycerol was found to be the best option for bioreactor packed with polyurethane under mesophilic and
anaerobic treatment of glycerol [78]. The organic loading thermophilic anaerobic conditions [81]. Better performance
rates for each substrate and sludge type were in the range was obtained from the reactor under the thermophilic con-
of 0.92–2.0 kg/m3 ·d (COD). Organic loading rate (ORL) ditions. When increasing the ORL from 0.25 to 1 kg/m3 ·d,
is presented as the weight of organic matter per day the COD removal efficiency was decreasing under mesophilic
applied over a specific volume of reactor. The parameter conditions, however under thermophilic conditions higher
COD (chemical oxygen demand) represents indirectly the COD removal was achieved corresponding to higher load-
amount of organic compounds in the sample. It is a ing rate. After 516 days of reactor operation, the bed
measure of the oxygen needed to degrade organic matter. materials under the thermophilic reactors were removed
A decrease in specific methane production was observed to measure the quantity of attached biomass and for
when the ORL was increased further. Considering the microscopic observation. The polyurethane immobilization
biomass production and cell maintenance null, 0.382 m3 of carrier retained more biomass than did the liquid phase of
methane are theoretically produced per kilogram of removed reactor. About 95% of the microbes were maintained on
COD. Experimentally, the effectiveness of the process in the fixed-bed. The immobilized microorganisms present in
each case was: 76% using granular sludge-acidified glycerol, the thermophilic reactor were primarily Methanobacterium
75% using nongranular sludge-acidified glycerol and 93% sp., Methanosarcina sp., Bacillus sp., Clostridium sp., Desulfo-
with granular sludge-distilled glycerol (0.292; 0.288 and tomaculum sp. and Ruminococcus.
0.356 m3 /kg COD removed, resp.). Besides the methane Feasibility of utilization of crude glycerol as a cosubstrate
production coefficient, the removed COD percentage is also has been proven for example in the work of Fountoulakis
important in order to determine biodegradability. This was (2009). The effects of g-phase on the performance of
found to be around 100% using granular sludge-acidified anaerobic reactor treating different types of organic waste
glycerol, 75% with nongranular sludge-acidified glycerol and (organic fraction of municipal solid waste, mixture of
85% using granular sludge-distilled glycerol. olive mill wastewater and slaughterhouse wastewater) were
Crude glycerol was processed in anaerobic laboratory- examined, in order to enhance methane production and
mixed reactor under mesophilic conditions for several moths increase the yield of hydrogen [82]. Digestion was carried
by Bodı́k et al. [79]. The anaerobic reactor achieved stable out in a single-stage reactor with a working volume of
operation at the volume loading of 4 kg/m3 ·d with biogas 3 liters, inoculated with anaerobic sludge from municipal
production ca0.980 m3 /L of dosed g-phase. The maximal sewage treatment plant and the share of crude glycerol
reached volumetric loading was 8–10 kg/m3 ·d, but the load- made 1% (v/v) of the dose. The supplementation of the
ing was considered to be very sensitive and unstable, because feed with crude glycerol had a significant positive effect
it caused decrease of the specific methane production and and the methane production rate in both cases increased
increase of concentrations of volatile fatty acids (VFA) and close to the theoretical values given total biodegradation
dissolved COD. Very effective transformation of g-phase into of glycerol. Addition of g-phase to a reactor treating the
biogas was measured (more than 95%) which gives very good organic fraction of municipal solid waste resulted in the
assumptions for posttreatment of sludge water. The concen- increase of methane production to 2.094 L/d, compared
tration of dissolved inorganic substances increased during to 1.400 L/d. An enhanced methane production was also
the monitored period very slowly but continuously from observed when a mixture of olive mill wastewater and
1.3 g/L up to 15 g/L. Higher concentrations of dissolved salts slaughterhouse wastewater was supplemented with crude
could cause inhibition of anaerobic degradation, however no glycerol. Specifically, by adding 1% of g-phase to the feed,
significant influence was observed during this experiment. the methane production rate increased from 0.479 L/d to
In the work Hutňan et al. (2009) results of crude glycerol 1.210 L/d. Stable concentration levels of COD indicated that
treatment in the laboratory-mixed reactor (with effective COD attributed to glycerol in the feed was totally digested
volume of 4 liters) and in the laboratory UASB (upflow in the reactor. The estimated yield of methane generated
anaerobic sludge blanket) reactors (volume of 3.7 liters) are from the digestion of glycerol was in both cases almost
described [80]. From this work resulted that the operation reaching the value of theoretical methane production. The
of mesophilic anaerobic degradation of crude glycerol as theoretical methane production from digestion of glycerol
the only organic substrate is feasible, however the process was estimated at 0.751 L/d (using the Buswell formula and
operation is very sensible to organic overloading of reactor. the ideal gas law).
Fountoulakis et al. studied also the feasibility of adding high methane production rates (14.4 L/kg·d (COD) and
crude glycerol to the anaerobic digesters treating sewage 12.8 L/kg·d (COD) resp.) compared to the control sample
sludge in wastewater treatment plants [83]. Both batch and using pig manure substrate (8.3 L/kg·d (COD)).
continuous experiments were carried out at 35◦ C. It was Anaerobic codigestion of crude glycerol in the reactors
observed that glycerol addition up to 1% (v/v) in the feed processing maize, maize silage and pig manure as main
increased methane production in the reactor above the substrates, is described in work of Amon et al. (2004).
expected theoretical value, as it was totally digested and Laboratory digesters under mesophilic conditions were pro-
furthermore enhanced the growth of active biomass in the cessing a basic mixture, which included 31% of maize silage,
system. On the other hand, any further increase of glycerol 15% of corn maize and 54% of pig manure, together with
caused a high imbalance in the anaerobic digestion process. addition of various levels of g-phase (3, 6, 8 and 15%).
The reactor treating the sewage sludge produced 1.106 ± The methane yield from the basic mixture without glycerine
0.036 L/d of methane before the addition of glycerol and addition reached 0.335 m3 /kg VS [86]. Addition of 3% of
2.353 ± 0.094 L/d after the addition of glycerol (1% in the glycerine increased the methane yield by 20% and achieved
feed). The extra glycerol-COD added to the feed did not 0.411 m3 /kg VS. The addition of 6% of glycerine resulted
have a negative effect on reactor performance, but seemed in the highest methane yield of 0.440 m3 /kg VS. Addition
to increase the active biomass (volatile solids) concentration of more than 6% glycerine to the basic mixture had only
in the system. Also, the kinetic experiments have shown that a low positive influence on the methane yield. Addition
glycerol biodegradation took place significantly faster than of 15% glycerine even decreased the methane yield to
propionate (which is an intermediate product) biodegrada- 0.400 m3 /kg VS and the duration of fermentation increased.
tion, and it was therefore suggested that the glycerol overload Methane formation at the start of the experiments was
in the reactors increased propionate concentration. delayed. Analysis of the VFA concentrations in the mixture
Ma et al. studied the improvement of anaerobic treat- during the experiments resulted in the hypothesis that the
ment of potato processing wastewater in a laboratory UASB inhibition of methane formation was caused by increased
reactor by codigestion with crude glycerol [84]. Influence concentration of propionic and butyric acids. The large
of three types of glycerol was tested: pure glycerol, crude amounts of these acids were built during decomposition of
glycerol and high conductivity glycerol. All 3 types of methanol. VFA accumulation reflects a kinetic uncoupling
glycerol are generated as a by-product by the production between acid producers and consumers and is typical for
of biodiesel. They are obtained by different processing stress situations [92]. The main cause of the toxic effects of
technologies and thus their characteristics differ. Supplement high VFA concentrations on the anaerobic digestion process
of pure glycerol of 2 mL/L of potato processing wastewater is generally considered to be the resulting drop in pH.
resulted in increase of the specific biogas production by Long-term operation of anaerobic digester for cofermen-
0.740 m3 /L of glycerol added. High COD removal efficiencies tation of maize silage and crude glycerol was studied in work
(around 85%) were obtained. Moreover, a better in-reactor Špalková et al. (2009). Two laboratory models of a volume
biomass yield (surplus of active biomass in the reactor) was of 6 liters were fed by maize silage and a mixture of maize
observed for the UASB reactor supplemented with so-called silage with crude glycerol and operated under mesophilic
pure glycerol (0.012 g VS (volatile solids) per gram of COD conditions [87]. During the operation period, no negative
removed) compared to the reactor without added glycerol influence of supplementation of the feed with crude glycerol
(0.002 g VS per gram of COD removed), which suggests a was observed. Biogas production as well as the sludge water
positive effect of glycerol on the sludge blanket growth. quality (pH, concentrations of COD, VFA, ammonia and
Álvarez et al. carried out a laboratory study, aimed at phosphate) was similar in both reactors. Maximum portion
maximizing methane production by anaerobic codigestion of of g-phase added formed 41.5% of total daily COD dose
three agroindustrial wastes: crude glycerol, pig manure and (together with maize silage). Specific biogas production
tuna fish waste [85]. Experiments were performed by batch achieved was approximately 0.40 m3 /kg (COD) in the case
(discontinuous) assays and 500 mL reactors were operated of both sole maize silage and a mixture of maize silage with
under the temperature of 35◦ C. Different blends composed g-phase, meaning that both the maize silage and g-phase had
by various percentages of these substrates were fed into similar specific biogas productions per unit quantity of COD.
the reactors. Compositions of these blends were specified A positive effect of glycerol as a cofermentation medium
using linear programming optimization method to find most is supported by Amon et al. (2006). Biogas productions from
suitable ratios of cosubstrates which would achieve highest pig manure, crude glycerol and a mixture of 94% of manure
biodegradation potential or highest methane production with 6% of glycerol were compared in the study [88]. A 6%
rate. The highest biodegradation potential (methane pro- supplementation of glycerol to pig manure and maize silage
duction of 0.321 m3 /kg COD) was reached with a mixture resulted in a significant increase in methane production from
composed of 84% pig manure, 5% fish waste and 11% 0.569 to 0.679 m3 /kg (VS). The methane yield of the mixture
biodiesel waste, while the highest methane production rate supplemented with glycerine was higher than the combined
(16.4 L/kg·d (COD)) was obtained by a mixture containing methane yields of both substrates if digested separately.
88% pig manure, 4% fish waste and 8% biodiesel waste. Increase in the specific methane production could not be just
Mixture composed of 84% pig manure, 5% fish waste and corresponding to supplemented glycerol, but was also result
11% biodiesel waste and mixture of 79% pig manure, 5% of the improved anaerobic degradation caused by the effect
fish waste and 16% biodiesel waste have also achieved very of codigestion. Co-digestion of various substrates provides
in many cases suitable option for anaerobic processing the nature and the progressive adaptation of sludge to high
for various technical reasons. One of the main reasons is salinity and reactor configuration [93, 101].
the stability of pH and sufficient buffer capacity. Lack of These factors may be the cause of different results achi-
nutrients or high concentration of inhibitory agents can also eved in different studies. Some of the researchers reported
be improved by sensible choice of cosubstrates. A particularly the concentrations from 0.9 g/L to 8 g/L to be slightly
strong reason for codigestion of feedstock is the adjustment inhibitory (reduction in methane production by 10%), using
of the carbon-to-nitrogen (C/N) ratio. Digestion of hardly different types of substrates [102]. In other experiments, the
degradable substances was found to be faster by the addition concentrations in the range of 5.6–53 g/L, depending on the
of easily degradable substrates. Moreover some previously conditions, have been documented to cause the decrease of
problematic wastes were found digestible if digested in a methane production to a half [93, 101–103].
mixture of other waste. Adequate adaptation of the sludge appears to be of
The work by Hutňan et al. (2009) showed that crude extreme importance, hence the continuous exposure of
glycerol is also a suitable cosubstrate in the full scale methanogenic sludge seams to lead to the tolerance of a
biogas plant for anaerobic treatment of maize silage [80]. higher salinity compared to the sludge exposed to salt shocks.
Reactor was operated under mesophilic conditions and the The adaptation includes gradual increase of salt concen-
effective volume of a full scale anaerobic reactor was 2450 m3 . trations in the sludge, by low organic loading, providing
Evaluated specific production of biogas from crude glycerol adequate conditions for internal structural changes in the
was about 0.890 m3 /kg of crude glycerol added. Dose of predominant species of methanogens, to adapt to higher
crude glycerol, which represented only 5.2% of overall dose osmolarity [104]. Hence the startup period may take several
to biogas plant, produced almost 15% of overall biogas months [94]. According to Gebauer [97] is the adaptation to
production. A significant influence on positive economical high sodium concentrations more likely to happen as a result
balance of biogas plant using this cosubstrate has been of selection of tolerant species than by adaptation of every
demonstrated in this study. At the electrical power output single microorganism.
of cogeneration unit 300 kW is the daily share of electricity
Methanogenic microorganisms seem to be more affected
produced from crude glycerol 1067 kWh. At the current price
by sodium toxicity than other populations, such as pro-
of 0.15 C per 1 kWh, this represents a daily profit of 156.55 C
pionate utilizes [101]. The most sensitive appeared to be
and a saving of almost 15% silage (1865 kg at a price around
the nitrogen removing microorganisms [98]. Provided the
60 C for 1 ton).
biomass is acclimated, high salinity is reportedly not an
The possible inhibition effects, resulting from the sub-
obstacle to its growth and it has no negative influence on sed-
strate composition, have to be considered by anaerobic
imentation properties of the sludge or the granulated sludge
treatment of crude glycerol. Metabolism of the anaerobic
viscosity. The lack of macronutrients (nitrogen, phosphorus,
microorganisms may be negatively affected mainly by the
sulfur) in the medium was found to have a more pronounced
high salinity of g-phase [79, 80]. The relatively high content
negative effect on biomass under the saline conditions. On
of sodium or potassium salts (ca 20–100 g/L) originates
the other hand, the absence of micronutrients did not further
from the catalyst, used for the biodiesel production. Higher
reduce biomass activity under salinity [101, 105].
concentrations of sodium in the anaerobic reactor can
seriously inhibit the microbial activity [93]. Another important concern about the anaerobic diges-
Biological processing of organic materials in the presence tion of crude glycerol should be the concentration of
of salts have been studied mainly as an alternative possibility nitrogen-rich substances. Ammonium concentration up to
of treating wastewater from industrial processes [94–97] 200 mg/L in the anaerobic reactor is considered to be benefi-
(meat canning, pickled vegetables, dairy products, olive and cial [93], since nitrogen is an essential nutrient for microor-
fish processing industries, petroleum, textile and leather ganisms. Considering the low concentration of nitrogen in
industries). The anaerobic digestion of industrial saline the crude glycerol, it may be necessary to supply the nitrogen-
effluents, predominantly from seafood processing, at salt rich substances into the reactor. Urea or NH4 Cl are most
concentrations ranging from 10 to 71 g/L has been studied frequently used as external source of ammonium nitrogen.
recently,using different processes, such as an anaerobic filter,
UASB reactor and an anaerobic contact system [94, 95, 98]. 4. Oil Cakes
The COD removal efficiencies obtained, generally remained
between 70% and 90%, with OLR ranging from 1 to Oil cakes or oil meals are solid residues obtained after
15 kg/m3 ·d (COD). oil extraction from the seeds. Their composition widely
The concentration of sodium exceeding 10 g/L was for varies depending on the quality of seeds or nuts, growing
a long time generally considered to strongly inhibit methano- conditions and extraction methods. Oil cakes can be either
genesis [94]. However, the anaerobic digestion in the high edible or nonedible. Edible cakes have a high protein content
salinity level was proven to be possible for treatment of fish- ranging from 15 to 50%. The chemical compositions of oil
processing effluent [99, 100], if a suitable strategy for adapt- cakes originating from different types of plants are listed in
ing the methanogenic biomass was applied. Furthermore, it Table 3 [106].
was shown, that the toxicity of sodium in sludge depends on In our geographic area (EU), rapeseed and sunflower are
several factors, such as the type of methanogenic substrate the most frequently used substrates, hence we are focusing
used, the antagonistic or synergistic effects of other ions, on the by-products from their processing.
Table 3: Composition of oil cakes.
Oil cake Dry matter % Crude protein % Crude fibre % Ash % Calcium % Phosphorus %
Canola oil cake 90 33.9 9.7 6.2 0.79 1.06
Coconut oil cake 88.8 25.2 10.8 6.0 0.08 0.67
Cottonseed cake 94.3 40.3 15.7 6.8 0.31 0.11
Groundnut oil cake 92.6 49.5 5.3 4.5 0.11 0.74
Mustard oil cake 89.8 38.5 3.5 9.9 0.05 1.11
Olive oil cake 85.2 6.3 40.0 4.2 — —
Palm kernel cake 90.8 18.6 37 4.5 0.31 0.85
Sesame oil cake 83.2 35.6 7.6 11.8 2.45 1.11
Soy bean cake 84.8 47.5 5.1 6.4 0.13 0.69
Sunflower oil cake 91 34.1 13.2 6.6 0.30 1.30
Table 4: Composition of rapeseed, rapeseed cake after extraction of 60, 70, and 75% of oil and rapeseed meal, in percents of total solids
[111].
Feed stock Rapeseed Rapeseed cake Rapeseed meal

Portion of extracted oil 60% 70% 75%
Crude oil 45 24.7 19.7 17 4.5
Crude protein 23 31.5 33.6 34.7 40
Crude fibre 7 9.6 10.2 10.6 12.3
Ash 5 6.8 7.3 7.5 7.7
Depending on the method of oil extraction from the agroindustrial residues, alternative utilization for oil cakes
seeds, two basic types of solid by-products are generated. has been required.
Oil cakes are produced when simple oil pressing system is Utilization of oil cakes as an energy source is under
used. In case that pressing is followed by advanced extraction examination for now. Some of the oil cakes have been studied
techniques, residues are usually referred to as oil meals. as possible feedstocks for biogas production, combustion
As can be seen in Table 4, main difference between the oil or pyrolysis [117]. Considering the high content of fats, oil
cakes and oil meals is based on the content of fats. The cakes have a high energetic value. They could be suitable
more effective is the extraction process, the fewer lipids substrates for combustion, however because of the large
remain in the cakes. About 12% of fats (or even 20% in quantity of ash and high emissions of nitrogen oxides,
case of small processing facilities) may remain in the oil advanced purification technology is required.
cake when simple pressing method is employed. Second Oil cakes and meals contain a high portion of digestible
pressing, sometimes accompanied by water vapor extraction, substances, which makes them suitable substrates for the
can lower the content of fats to approximately 8%. If the production of biogas. Nutritional content should not be
extraction using hexane is engaged, oil meal with fats content significantly affected by the anaerobic degradation (nutrients
about 1–3% can be generated. such as nitrogen and phosphorus stay in the digestate after
Oil cakes have been currently in use predominantly degradation) and the digestate should be a convenient agri-
for feed applications to poultry, ruminant, fish and swine cultural fertilizer. In addition, the plant nutrients contained
industry [107–110]. Some of them are considered to be suit- in cakes are more easily available after the biodigestion.
able organic nitrogenous fertilizers. Several cakes have been
utilized for production of proteins, enzymes, antibiotics, 5. Anaerobic Digestion of Rapeseed Oil Cake
mushrooms, ethanol [107–112]. Biotechnological applica-
tions of oil cakes also include production of vitamins and Rapeseed cake and rapeseed meal are degradable organic
antioxidants [111, 113]. substances. They are suitable for anaerobic digestion, how-
Current prices of oil cakes are relatively high (rapeseed ever supplementation of other organic substrates might be
cake and meal are in Europe worth approximately 166 and required to achieve better process performance and particu-
161 Euros per ton, resp.), compared to other agroindustrial lar problems of digestion should be more closely studied.
by-products and wastes, which could be also used as sub- Rapeseed cake is a protein-rich substrate, hence the
strates for biogas production. However experts are warning decomposition and conversion to biogas takes longer time
against their expected drop due to possible overproduction than decomposition of substrates rich in carbohydrates. In
[114–116]. Moreover, with increasing emphasis on cost case of protein degradation, hydrolysis is the limiting step,
reduction of industrial processes and value addition to specifically the cracking of proteins into amino acids and
Table 5: Methane production potential from rapeseed, rapeseed cake and meal in m3 /kg VS [111].
Feed stock Rapeseed Rapeseed cake Rapeseed meal

Portion of extracted oil 60% 70% 75%
Saccharides 0.11 0.16 0.17 0.17 0.20
Lipids 0.43 0.24 0.19 0.16 0.04
Proteins 0.12 0.16 0.17 0.18 0.20
Together 0.66 0.55 0.53 0.51 0.45
Together (kg) 0.47 0.39 0.37 0.36 0.32
Calorific value (MJ) 23.4 19.5 18.6 18.1 15.8
polypeptides by extracellular enzymes. The hydrolysis of process, the possible biogas production from rapeseed cake is
carbohydrates takes place within a few hours, while the decreasing.
hydrolysis of proteins within few days. Rate and readiness Antonopoulou et al. carried out batch mesophilic
of degradation of different types of carbohydrates can quite biochemical methane potential tests using rapeseed and
vary. Fats are often decomposed completely. Hemicellulose sunflower residues as a substrate [119]. The experiments
and lignin, forming the shells of rapeseed, could be quite indicated that the biological methane potential of rapeseed
difficult to decompose in the process of biogas production. and sunflower meal were 0.450 m3 /kg and 0.481 m3 /kg,
Accumulation of free fatty acids can cause a problem respectively. Compared to commonly used substrate maize
by digestion of materials with higher content of oil, con- silage, the potential of these oil meals are about 40% higher,
sidering that the fats decomposition step is faster than so it suggests interesting substrates for the production of
the methanogenesis. Generally, hydrolytic and acidogenic biogas. Various pretreatment methods, such as thermal,
microorganisms are growing about ten times faster than chemical (through alkali or acid addition) or combination of
methanogens. Co-digestion of rapeseed cake or meal with the above methods were also tested in the effort to enhance
other feedstocks, such as manure, provides an alternative the methane productivity and yield. Thermal pretreatment
solution. Improvement of the biogas production is expected, method was conducted at 121◦ C for 60 minutes in a pressure
based on the high oil content. cooker. Acid or alkali pretreatment of the feedstocks was
Rapeseed cake and rapeseed meal are nitrogen-rich conducted by the addition of 2% w/v H2 SO4 or NaOH,
media, they content about 35–40% of nitrogen substances respectively, for 60 minutes at a temperature of 25◦ C or
[106]. These substances are predominantly proteins, con- at 121◦ C for 60 min in a pressure cooker (thermal acid
taining amino acids. Expressed in the terms of carbon-to- or thermal alkali pretreatment). The experiments showed
nitrogen ratio, this makes about 5–8 in case of rapeseed cake. that the pretreatment methods tested did not enhance the
Compared to other materials, the C/N ratio of lignocellulosic methane potential of the rapeseed and sunflower residues.
materials is in the range of 60–400, grass and silages have This could be attributed to the inhibitory compounds which
C/N about 20–40, swine manure about 12–15 and sunflower were possibly released during the pretreatment.
cake about 12-13 [118]. The C/N ratio of substrate is
an important parameter to be considered by anaerobic
degradation, since high content of nitrogen may cause too 6. Anaerobic Digestion of Sunflower Oil Cake
high content of ammonium nitrate in the biogas reactor.
Ammonium nitrogen levels of about 4 g/L of wet sludge bring Sunflower oil cakes and meals are also feasible feedstocks for
the risk of process inhibition. If the ammonium content is anaerobic digestion. Raposo et al. examined their anaerobic
too high, it is necessary to dilute the substrate with water or degradability, biochemical methanogenic potential and the
nitrogen-poor material. influence of substrate to inoculum ratio in batch laboratory-
Phytotoxic effects of rapeseed cake, caused by the con- scale digesters [120, 121]. High stability of the anaerobic
tent of glucosinolates, must also be considered. They play an digestion process of sunflower oil cake under mesophilic
important role in the process of digestion, since in hig- conditions was demonstrated.
her concentrations they may have harmful effect on metha- The experimental study, with the duration of 7 days, was
nogenic. The risk of inhibition is getting less serious with carried out in a multibatch reactor system [120, 121], which
decreasing of the glucosinolates level in the rapeseed meal consisted of continuously stirred flasks with an effective
and cake. volume of 250 mL. The six different inoculum to substrate
There is not much information about experimental anae- ratios were tested: 3.0, 2.0, 1.5, 1.0, 0.8 and 0.5. The ultimate
robic processing of rapeseed cake or meal in the available methane yield decreased considerably with the inoculum to
literature. substrate ratio. The yield of methane was in the range from
Bernesson et al. estimated the potential biogas pro- 0.227 m3 /kg for the ratio of 3.0 to 0.107 m3 /kg (VS) for the
duction from rapeseed, rapeseed meal and rapeseed cake ratio of 0.5. Biodegradability copied this trend, from 86%
after 60–75% extraction of oil [111]. Table 5 indicates, to 41% was achieved. Higher contribution of substrate may
that with the increased amount of oil extracted in the cause lower methane yield due to higher energy consumption
in the hydrolytic-acidogenic stage. However, the net VS 12 and 15 days) were tested to check the effect of each
removed only varied from 42% to 36%, when the ratio operational variable. Hydrolysis yields obtained for all HRTs
decreased from 3.0 to 0.5, which demonstrated the adequate and OLRs assayed were in the range of 20.5–30.1%.
operation of the hydrolytic-acidogenic stage. Variations inHRT did not affect the COD solubiliza-
The increase in CODs concentrations presented 780– tion of this substrate withinthe HRT range (15–8 days)
6100 mg/L for the inoculum to substrate ratios of 3.0–0.5, researched. Variations in OLR affect the organic matter lique-
respectively. In case of inoculum-substrate ratio of 3.0 or faction slightly, the highest value (30.1%) being achieved for
2.0, the final values of total VFA were proportional to the HRT of 10 days andOLR of 6 kg/m3 ·d(VS). The acidification
amount of substrate added, and no accumulation occurred. yield increased with OLR up to 6 kg/m3 ·d(VS), the highest
However, when the ratio was lower than 2.0, an imbalance of value (83.8%) being achieved for HRT of 10 days and an
the process was observed, when the VFAs increased to 2050 OLR of 6 kg/m3 ·d(VS). However, higher loading provokes a
or 5500 mg/L (for ratios 0.8 and 0.5, resp.). The dissolved decrease in the acidification yield, probably due to the fact
CODs also increased, reaching the levels of 3380–12100 mg/L that the acidogenic bacteria could have been affected and
after seven days for the inoculum-substrate ratios of 3.0–0.5, inhibited at the highest OLR studied.
respectively. The trend in the increase of COD with digestion
time observed was due mainly to the accumulation of VFA,
which reflects a kinetic uncoupling between acid formers 7. Washing Water
and consumers and is typical for a stress situation. This Another possible by-product from biodiesel production
means that the hydrolytic-acidogenic stage was carried out offers the water, generated by washing of raw biodiesel.
satisfactorily and the imbalance of the process was due to the Under the conventional process (alkali-catalyzed transester-
stress of methanogenic microorganisms. ification) for every 100 L biodiesel produced about 20 L of
The net production of total ammonia nitrogen increased washing water is discharged(or more in case of prior acid
with the load added, as a consequence of degradation of pretreatment) [123].
proteinsfrom the sunflower oil cake, achieving a maximum
Washing water (usually referred to as biodiesel wastewa-
value of 1085 mg/L at the ratio of 0.5 (198 mg/L at the ratio
ter) is a viscous liquid with an opaque white color similar to
3.0). However, the specific total ammonia nitrogen reached
aqueous soap. It contains significant amounts of methanol,
in all ratios similar production of about 40 mg/g VS added.
glycerol and soaps. Methyl esters bound with soap, NaOH or
Identification of the individual VFA may also provide
KOH from the catalyst, sodium or potassium salts and trace
valuable information on the metabolic pathways involved in
mono, di- and triglycerides bound up with the soap are also
the process. The high influence of inoculum-substrate ratio
contained in the water.
on the composition and concentration of the different VFA
was shown. By the inoculum to substrate ratio of 3 and 2, A great variety of systems for biodiesel purification is
the predominant VFA were valeric and butyric acids, but available commercially and new alternative technologies are
the residual compound was the latter. The absence of acetic also being investigated. The possible options include dry
and propionic acids indicated, that the methanogenic stage washing. In this case, the impurities from biodiesel (free
was not disturbed and the formation of methane from these glycerol, soap, free fatty acids, catalyst,glycerides, etc.) are
intermediates was quick. absorbed to form a solid waste product instead of a liquid.
When the ratios of 1.5, 1.0 and 0.8 were applied, the Dry washing replaces water with an ion exchange resin or
predominant VFA during the first few days were acetic a magnesium silicate powder. Both these methods are being
and propionic acids, followed by valeric and butyric acids. used in industrial plants [124]. No regeneration is normally
Although in the end valeric acid dominated. This perfor- applied and the spent material has to be disposed of to
mance demonstrated that the lower inoculum-substrate ratio landfill or other applications (compost, potential animal feed
causes the greater accumulation of the longer chain VFA. additive and potential fuel).
By the ratio of 0.5 the predominant VFA were acetic Relatively expensive ultrafiltration or reverse osmosis
and propionic acids during the first few days, followed by a could also be applied for purification of biodiesel. Yet, the
decrease in acetic acid with time, with a significant residual washing with water remains the most convenient alternative
concentration of propionic, valeric and butyric acids. The [125–127].
VFA profile obtained is a consequence of the imbalance in Besides crude glycerol, oil cakes and biodiesel wastewater,
the methanogenic stage. other potential by-products can be generated in the biodiesel
De La Rubia et al. investigated also influence of the industry. These products are specific, depending on the
hydraulic retention time (HRT, it is a measure of the length processing technologies in biodiesel plants. For example,
of time that sludge remains in reactor.) and OLR on the some facilities utilize citric acid solutions in order to wash
performance of the hydrolytic-acidogenic step of a two-stage reactors and other equipment, which produces possible
anaerobic digestion process of sunflower oil cake [122]. The additional waste.
experiments were performed in laboratory-scale completely Like the raw glycerol, washing water has also high
stirred tank reactors, with a working volume of 2 L, at levels of COD, values in the range of 18–800 g/L have been
mesophilic (35◦ C) temperature. Digesters were operated reported [123, 128–130]. High content of degradable organic
over a total period of approximately 350 days. Six OLRs substances makes it a suitable source of carbon for microbio-
(ranging from 4 to 9 kg/m3 ·d(VS)) for four HRTs (8, 10, logical processes, however some issues have to be considered.
The wastewater is basic (alkaline), due to the significant levels the inhibition of the microbial growth, the raw biodiesel
of residual KOH, and contains a high level of oil and grease wastewater was diluted with the same volume of water. The
and has a high solid content. Nutrients for microbial growth optimal initial concentration of yeast extract was 1 g/L and
(such as nitrogen and phosphorus) are not abundant in the optimal C/N ratio was between 17 and 68 when using
washing water, except for the carbon source. Together these urea as a nitrogen source. Authors suggest this biological
components inhibit the growth of most microorganisms treatment system to be useful for small-scale biodiesel
making this wastewater difficult to degrade naturally [123]. production plants, because it is simple and no controllers,
Focusing on anaerobic degradation, long-chain fatty acids, except for a temperature, are necessary.
which are present on a high level in the washing water, have Kato et al. (2005) proposed a continuous-type consor-
been reported to be inhibitors of the digestion process [93]. tium bioreactor for treatment of washing water [131]. The
To reduce this effect, electrocoagulation has been proposed main component of this reactor was bacteria-fixed ceramic
as a successful pretreatment for oily wastewater with a material with high-oil degrading capability. A series of oil
subsequent anaerobic treatment [129, 130]. decomposition tests was carried out using the consortium
With the likely expansion of biodiesel production by system, in which the most important bacteria types were
plants using the conventional method, comes the inherent Acinetobacter, Bacillus and Pseudomonas. The optimal con-
need to treat the wastewater. The main component of ditions for operation were confirmed by batch tests: air
the wastewater is the residual remaining oil, thus, such agitation, pH of around 6 and water temperature of 30◦ C.
wastewater should not be discharged into public drainage This reactor operated almost maintenance-free for one year.
because the oil causes plugging of the drainage and decreases The field test results for washing water showed that oil and
biological activity in sewage treatment. Some of the typical grease concentrations decreased from an initial 120 g/L to a
commercially available treatments of oily wastewater employ treated range of 10–30 mg/L.
a dissolved air floatation technique or oil and grease trap unit Papanikolaou et al. investigated valorization of soaps
[130]. Currently, several processes have been developed to from washing water for the production of microbial lipids
treat the biodiesel wastewater, such as the use of chemical of specific structure [132–134]. Several oleaginous yeasts and
recovery approach and electrochemical treatment [128, 130], molds are able to accumulate in abundance storage lipid, and
but also the employment of microbiological processes [123, at the same time modify the composition of the fat utilized
131–134] and anaerobic digestion [129]. as the carbon source. In the case of various crude fats or
In the work of Jaruwat et al. (2010), the management of fatty wastewaters of low value, this may be an industrially
raw biodiesel wastewater was carried out at a laboratory scale and financially interesting approach. Potential production
at ambient temperature by a combined protonation based of cocoa-butter substitute by Yarrowia lipolytica was studied
chemical recovery of biodiesel followed by electrochemical and the cell growth and lipid accumulation of Y. lipolytica
treatment of the residual wastewater [128]. The combined was investigated [132].
treatment completely removed COD and oil and grease, and
reduced BOD (biologic oxygen demand) levels by more than The anaerobic codigestion of glycerol and wastewater
95%. derived from biodiesel manufacturing was studied in batch
In the study, carried out by Chavalparit and Ong- laboratory-scale reactors of 1 L volume, inoculated by gran-
wandee (2009), electrocoagulation was adopted to treat the ular biomass, at mesophilic (35◦ C) temperature [129]. The
biodiesel wastewater [130]. This study demonstrates that the main purpose of this study was to evaluate the performance,
electrocoagulation process using an aluminum anode and stability, biodegradability, methane yield coefficient, kinetics
graphite cathode is effective in reducing oil and grease and of methane production, inoculum-substrate ratio and OLR
suspended solids by more than 95% in the washing water. of the anaerobic codigestion of these by-products derived
However, the COD removal is achieved by 55% due to less from biodiesel manufacturing.
significant removal of glycerol and methanol. Therefore, the Prior to the biological treatment, glycerol was acid-
electrocoagulation process is possibly suitable for a primary ified with H3 PO4 in order to recover the alkaline cat-
treatment for biodiesel wastewater and it still requires a alyst employed in the transesterification reaction (KOH)
further biological treatment process. Authors believe that as agricultural fertilizer. Wastewater was subjected to an
pretreatment with electrocoagulation followed by a biolog- electrocoagulation process in order to reduce its oil content.
ical treatment process is feasible and competitive compared The pretreated washing water was mixed with glycerol at a
with evaporation or pure physicochemical treatments. It proportion of 85–15 (COD), until obtaining a final soluble
requires less energy consumption, short process time, no COD of 300 g/L. After mixing, the anaerobic revalorization
chemical addition and less sludge production. of the wastewater was studied employing inoculum-substrate
The biological treatment of washing water was inves- ratios ranging from 5.02 to 1.48 kilogram of VSS (volatile
tigated by Suehara et al. (2005). For the microbiological suspended solids) per kilogram of COD and OLR of
degradation using a 10-L fermentor, oil degradable yeast, 0.27–0.36 kg/kg·d (COD/VSS). Biodegradability was found
Rhodotorula mucilaginosa, was used and the optimum to be around 100%, while the methane yield coefficient
conditions were determined [123]. The pH was adjusted was 0.310 m3 /kg COD removed. The results showed that
to 6.8 and several nutrients such as a nitrogen source anaerobic codigestion reduces the clean water and nutrient
(ammonium sulfate, ammonium chloride or urea), KH2 PO4 requirement, with the consequent economical and environ-
and MgSO4 ·7H2 O were added to the wastewater. To avoid mental benefit.
8. Conclusions methanogenic microorganisms. The concentration of

ammonium should also be monitored. Since nitrogen
The process of biodiesel production is predominantly car- is an essential nutrient for microorganisms, the low
ried out by catalyzed transesterification. Besides desired concentration in the crude glycerol and washing
methylesters, this reaction provides also a few other products, water has to be compensated by ammonium sup-
including crude glycerol, oil-pressed cakes and washing plement. On the other hand, rapeseed cake contains
water. Although their composition widely varies depending a high portion of nitrogen-rich substances, which
on the parameters and substrates used for biodiesel pro- may cause inhibition of digestion due to ammonium
duction, all these by-products provide valuable feedstocks accumulation in the reactor.
for biogas generation. The possibility and performance of
anaerobic digestion of these materials have been studied Utilization of the by-products as a potential source of
to various extents. The results can be summarized in few energy, rather then treat them as a waste, seems to be a
points: convenient way of lowering the costs of biodiesel and making
it more competitive.
(i) Crude glycerol from biodiesel production was proven
to be a suitable substrate for anaerobic degradation. Acknowledgment
A couple of studies have demonstrated the possibility
of biogas production, using g-phase as a single This work was supported by the Slovak Grant Agency for
substrate. Science VEGA (Grant 1/0145/08).
(ii) G-phase has also shown a great potential as a
cosubstrate by anaerobic treatment of different types
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Review Article: Utilization of Biodiesel By-Products For Biogas Production

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Journal of Biomedicine and Biotechnology

Nina Kolesárová, Miroslav Hutňan, Igor Bodı́k, and Viera Špalková

Correspondence should be addressed to Nina Kolesárová, nina.kolesarova@stuba.sk

Received 22 August 2010; Revised 22 November 2010; Accepted 7 January 2011

Academic Editor: Leon Spicer

1. Introduction countries, such as India, Brazil, Argentina, Malaysia, and

R1 O Similarly to heterogeneous catalysis, it also provides a

Table 2: Food nutrient analysis for crude glycerol samples [25].

Table 3: Composition of oil cakes.

Feed stock Rapeseed Rapeseed cake Rapeseed meal

Feed stock Rapeseed Rapeseed cake Rapeseed meal

8. Conclusions methanogenic microorganisms. The concentration of

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