Renewable and Sustainable Energy Reviews 42 (2015) 1164–1173

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Progress, prospect and challenges in glycerol purification

process: A review
M.S. Ardi, M.K. Aroua, N. Awanis Hashim n
Department of Chemical Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

art ic l e i nf o a b s t r a c t

Article history: Glycerol surplus in recent decades due to global increase in biodiesel production has created a new form
Received 8 July 2014 of challenge in terms of purification for crude glycerol. This review summarizes the progress of crude
Received in revised form glycerol purification technologies using various techniques. Critical insights are given regarding the
16 October 2014
application of suitable techniques for crude glycerol purification which includes chemical pre-treatment,
Accepted 25 October 2014
Available online 18 November 2014
methanol removal, vacuum distillation, ion exchange, activated carbon and membrane separation
technology. Extensive discussion is made in relation with stages and processes in the conventional,
Keywords: current and emerging glycerol purification technologies. Lastly, aspects concerning the challenges of
Crude glycerol glycerol utilization and purification are thoroughly discussed.
Biodiesel
& 2014 Elsevier Ltd. All rights reserved.
Purification
Membrane

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1164
2. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1165
2.1. Effect of impurities on glycerol utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1166
2.2. Grades specification of glycerol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1166
3. Glycerol purification technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1166
3.1. Neutralization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167
3.2. Methanol removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167
3.3. Purification and refinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167
3.3.1. Vacuum distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167
3.3.2. Ion exchange adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167
3.3.3. Adsorption using activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1168
4. Membrane separation technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1168
4.1. Application of membrane separation technology in glycerol refining. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1169
4.2. Prospect of glycerol refining using membrane technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1169
4.2.1. Hybrid membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1169
4.2.2. Membrane distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1170
5. Challenges of crude glycerol utilization and purification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1170
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1170
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1171
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1171

1. Introduction

As part of a recent renewable energy development interest,

biodiesel has attracted numerous researchers worldwide as a
n
Corresponding author. Tel.: þ 60 379676892. viable alternative to rapidly decline fossil fuel consumption.
E-mail address: awanis@um.edu.my (N.A. Hashim). Perhaps the wide interests are largely attributed to biodiesel

http://dx.doi.org/10.1016/j.rser.2014.10.091
1364-0321/& 2014 Elsevier Ltd. All rights reserved.
 M.S. Ardi et al. / Renewable and Sustainable Energy Reviews 42 (2015) 1164–1173
attracting factors such as a renewable energy source, biodegrad-
ability, and low in hazardous air pollutant emissions [1,2].
Globally, crude glycerol is produced as the main by-products of
the drastically increasing biodiesel production capacity. The rise
in biodiesel production capacity has led to present situations
whereby surplus of crude glycerol in the market contributes to
cheaper glycerol prices. The crude glycerol produced which
exceeds its demands further lowers its economic value [3]. More-
over, the crude glycerol produced contains a lot of contaminants
which decreases its quality [4]. So the question now is – how
exactly could we exploit crude glycerol or in other words, convert
low value crude glycerol to value added chemicals. Application of
the concept “from waste to worth” should be implemented for
biodiesel production to further enhance the economic feasibility of
the sustainable resources and exerting full capacity utilization of
the main by-product, crude glycerol [5].
Crude glycerol is a valuable by-product of biodiesel production
produced from animal, vegetable fats and oils such as palm oil as
the feedstock. Approximately, the amount of crude glycerol pro-
duced is around 1 kg for each 10 kg of biodiesel produced [6–9].
Refining crude glycerol into a chemically pure substance increases
its value for widespread uses and applications [4,10–12]. Glycerol
is well known as a building block for a lot of chemicals reactions
and applications [13,14]. There are already an extensive and huge
amount of industrial application and day to day uses of glycerol in
which they are very diverse in areas such as medical, pharmaceu-
tical, food (sweetener in candies and cakes), toiletries (soaps and
toothpastes), plasticizer, cosmetics, and lubricant in paper produc-
tion, textile industry, surface coatings and printing inks. Glycerol is
also widely used in production of several types of polymers as a
side product of glycerol production [15–18]. Fig. 1 shows the
distribution of glycerol consumption in different products and
industries. Essentially, the importance of glycerol is apparent
through its applications in key areas such as cosmetics, food and
pharmaceutical products. Utilization of glycerol in these products
requires one with high quality and purity.
Since the crude glycerol in its impure condition has a lesser
value and usage compared to refined glycerol, series of purifica-
tions are usually required preferably prior to further processes
[20]. Crude glycerol by-product of the transesterification process is
classified as waste under Schedule S181 of the Environmental
Regulations in Malaysia. It is stored in drums and disposed of in
landfills [21]. Since the disposal of crude glycerol is costly, it is
much advantageous to undergo purification process to generate
income [9]. Current purification and refining technologies are
already proven as an effective method to purify crude glycerol.
However, due to the cost constraints and high energy requirement
of the current method with exception to large scale plants, it is
GLYCEROL CONSUMPTION
Other uses
12% Cosmetics, soaps,
pharmaceuticals
26%
Resale
17%
Alkyd resins
Paper
6%
1%
Food and drink
Esters
8%
11%
Tobacco
Polyglycerol esters Cellulose films4%
12% 3%
Fig. 1. Distribution of glycerol consumption in different products and indus-
tries [19].
1165
deemed not feasible for small and medium plants as it has to
undergo costly purification process [22–24].
Besides the advancement in the biodiesel production techni-
ques, the recovery of high quality glycerol is identified to play a
key role in biodiesel production cost reduction [25,26]. On-going
development effort for cost reduction is visible through the
improvement of better catalyst selection for biodiesel production,
for example by employing heterogeneous catalyst which would
produce purer glycerol with less contaminant [27]. Solid catalysts
are not consumed or dissolved in the reaction and thus are easily
separated from the products. As a result, impurities in the product
that comes from the catalyst and the cost of final separation could
be reduced [28].
In recent years, membrane technology has emerged as a
promising technology to supplant the conventional glycerol
purification method. Membrane technology offers green, environ-
mental friendly and sustainable platforms with economic benefit.
Aspects concerning environmental impact are reduced through
process optimization, improvement in waste management and
realization of cleaner processes to produce environmental friendly
products.
Therefore, in this article we are interested to discuss more on
the improvements of current and emerging glycerol refining
techniques, particularly through the development of more efficient
and cost effective glycerol purification processes. Challenges in
purification and utilization of crude glycerol were also discussed as
part of an effort to modify and further enhance the technology
towards sustainable growth.
2. Background
Biodiesel is an alternative diesel fuel that contains a mixture of
mono-alkyl esters of long chain fatty acid which was derived from
vegetable oil or animal fat [29,30]. Direct usage of vegetable oils
and animal fats as combustible fuel would not be suitable as it is
high in kinematic viscosity and has low volatility. Therefore, in
order to reduce the viscosity of the oils, vegetable oils and animal
fats, they must be subjected to chemical reactions such as
transesterification [31–33], direct/blends [34], micro-emulsion
[35] and pyrolysis [36].
Transesterification is the most adopted technique for lowering
viscosity and biodiesel production [37,38]. The viscosities of
transesterified vegetable oil is closer to that of petrodiesel. Poor
quality fuel injection and formation of deposits are the operational
problem caused by high viscosity [39]. Fig. 2 presents the simpli-
fied transesterification process of triglyceride reaction to produce
biodiesel and glycerol [40]. Transesterification of vegetable oils
with alcohol can be carried out using either basic or acidic
catalysts [41]. The reaction is reversible and thus to improve the
reaction rate and yield, an excess amount of alcohol is used to shift
the equilibrium to the product side [25,42–44].
Transesterification of triglycerides with alcohol along with cat-
alysts such as sodium hydroxide produces methyl ester (biodiesel)
phase and glycerol phase. Advantages of using the base catalyzed
Fig. 2. Transesterification reaction of triglyceride [40].
1166 M.S. Ardi et al. / Renewable and Sustainable Energy Reviews 42 (2015) 1164–1173
transesterification process include high catalytic activity, low cost,
favorable kinetics and modest operation condition which are some
of the reasons why it is the most used technique for biodiesel
production [45,46]. Base catalyst is also preferable due to relatively
faster process and moderated reaction conditions [47]. It may be
noted that plant oils with high free fatty acid contents suffer soap
formation in the presence of homogeneous alkaline catalysts,
leading to product loss and problems associated with product
separation and purification [48]. On the other hand, while the use
of acid catalysts would avoid soap formation, it is deemed not
feasible due to issues such as corrosion, lower catalytic activity and
higher temperatures requirement of above 100 1C [49]. Table 1
shows the approximate amount of reactants and product amounts
for transesterification reaction.
The usage of methanol as the primary alcohol in the biodiesel
production is mainly attributed to its advantages as compared to
other alcohols. Methanol is less expensive [51], high in reactivity
using supercritical alcohol treatment [52,53], does not form
azeotrope which would make the methanol recovery easier [54]
and used for soap formation prevention during the biodiesel
production [55]. Excess amount of methanol is frequently used
as the reaction is a reversible process which can convert more fats
and oil into biodiesel [55]. The impurities such as soap, methanol,
water, salts, material organic non-glycerol (MONG) have more
tendencies to concentrate in the glycerol phase during phase
separation of biodiesel phase and glycerol phase [56,57].
2.1. Effect of impurities on glycerol utilization
Several studies have been conducted to investigate the char-
acterization and effect of impurities on the glycerol for further
process [58]. Impurities in crude glycerol has shown an inhibitory
effect on high cell density production of phytase [59]. It was found
that for initial concentration of 70 g/L crude glycerol, certain
impurities inhibited the cell growth. Soap and methanol have
been found to negatively influence the algae production of DHA
from crude glycerol [60] and the high salinity (Na or K) of crude
glycerol can largely inhibit the microbial activity in the anaerobic
digestion of crude glycerol [61]. Studies also show that saponified
fatty acids (SFA) have inhibitory effect on photofermentative
growth of Rhodopseudomonas palustris on crude glycerol to pro-
duce hydrogen [12]. The purification methods discussed in the
Table 1
Approximate reactant and product amounts for
transesterification reaction [50].
Chemicals/feedstock/product Amount (lbs)
Oil/fat 100
Methanol 22
Catalyst 0.3–0.5
Biodiesel 100
Glycerol 11
Excess methanol 11
Table 2
General specification of glycerol based on grades [3,15,62].
Types of glycerol Glycerol content (%)
Crude glycerol 70–90%
Technical grade 99.5% Technical grade (not certified, mostly 496.0%)
United States Pharmacopeia (USP) 99.5% USP (tallow-based)
99.5% USP (vegetable-based)
Food Chemical Codex (FCC) 99.7% USP/FCC-Kosher
study had found that pH adjustment and precipitation of SFA to be
effective methods to reduce the SFA concentration.
Glycerol conversion of oxidation reaction over alumina sup-
ported platinum catalyst was found to decrease dramatically with
the increase of matter organic non-glycerol – non-methanol
(MONG-NM) [62]. In the study, a similar trend was observed in
the presence of base and the absence of it. The main cause for
decrease in the glycerol conversion that hinders oxygen dissolu-
tion was the presence of soaps and intensive foaming in which the
catalyst surface was deactivated by strong adsorption of fatty acid
derivatives. In addition, for pharmaceutical and food applications,
heavy metals in crude glycerol might be harmful and present
safety concerns [60]. Methanol is a toxic chemical which could
cause damaging and harmful effects on health and environment
[55]. Due to various applications of glycerol especially in pharma-
ceuticals and food related sectors, glycerol produced must meet
certain requirements and standards.
2.2. Grades specification of glycerol
The goal of the purification process is to enhance usability of
glycerol by removing unwanted impurities according to different
sets of standard and purposes. Refined glycerol found in the
market comprises of three basic types which is based on their
purity and potential end use namely, technical grade, United States
Pharmocopeia (USP) and Food Chemical Codex (FCC) [3]. Technical
grade is mainly used as a chemical products building block and not
for food and medicine. United States Pharmacopeia (USP) glycerol
which is derived from animal fat or vegetable oil is suitable for
both pharmaceutical and food products while the Food Chemicals
Codex (FCC) glycerin which is mainly derived from vegetable oil
sources is appropriate for use in food. The grades of glycerol
according to purities are listed in Table 2.
3. Glycerol purification technology
Crude glycerol produced from various feedstock would have
different compositions, therefore the purification process is also
necessarily different. The consideration for initial purification or
final purification of glycerol utilization pathway is largely depen-
dent on the usage of glycerol and the effects of the impurities
on the process, which would be part of cost control and profit
measures. In cases where the glycerol utilization is mostly for
technical applications, the presence of some contaminants is
Fig. 3. General stages in the glycerol purification process [56].
Sources/applications
By-product of biodiesel production
Suitable for industrial application
Used in cosmetic, pharmaceutical and food
 M.S. Ardi et al. / Renewable and Sustainable Energy Reviews 42 (2015) 1164–1173
acceptable but for most cases, application of glycerol in food and
pharmaceutical sectors would require high purity glycerol. The
technology developed for purification of glycerol – derived from
biodiesel – is mainly adapted from existing soap making industry,
that utilizes vacuum distillation [63,64] and other treatments such
as ion exchange [65–67] and activated carbon [68,69]. As a rule
of thumb, a general purification of glycerol processes comprise of
three steps [70]. The first step involves the removal of non-glycerol
substances which can be achieved through precipitations
during neutralization, whereby free fatty acids and some salts
are removed. The next step is to concentrate the solution by
evaporation in which alcohol is removed from the glycerol stream.
The final step is the purification and refining step which can be
achieved to the desired degree with a combination of these
methods which are vacuum distillation, ion exchange, membrane
separation and adsorption. Fig. 3 shows the general stages in
glycerol purification.
3.1. Neutralization
Neutralization is the most common method as pre-treatment of
crude glycerol purification processes involving a chemical reaction
using a strong acid to remove catalyst and soaps. The reaction of
acid with soap would produce free fatty acids and its reaction with
base catalyst would give salt and water. The insoluble free fatty
acids and some salts will rise to the top and can be easily skimmed
off. The first step through the acidification process usually sepa-
rates the crude glycerol into three layers of free fatty acids at the
top, glycerol rich layer at the middle and inorganic salts at the
bottom.
Kongjao et al. reported that repeated acidification for crude
glycerol derived from waste used-oil methyl ester plant using
H2SO4 to the desired pH of 1–6 increases the yield of glycerol-rich
layer obtained [6]. High purity of glycerol was obtained at pH 1,
93.34% with relatively low contaminant levels after a series of
chemical, neutralization with 12.5 M NaOH and physical treat-
ment. Attempt by Ooi et al. to recover crude glycerol from glycerol
residue using 6% (v/v) H2SO4 reports that at a low pH, the
recovered glycerol was increased, ash content was reduced but
the matter organic non-glycerol (MONG) was slightly increased
[64]. Tianfeng et al. proposed acidification of crude glycerol
obtained from waste cooking oil biodiesel production using
5.85% H3PO4 and founded an increase in volume of glycerol-rich
layer content from 40% to 70% at pH 5 or 6 [71]. Acceptable yield of
semi-product glycerol of 81.2% was obtained after acidification at
optimum temperature of 70 1C and reaction time of 60 min.
Further treatment using vacuum distillation resulted in acceptable
glycerol purity of 98.10%. Hajek et al. proposed acidification of
glycerol phase from transesterification of vegetable oil through
addition of strong acid which converts impurities such as soaps to
higher fatty acids [72]. Meanwhile, Javani et al. proposed that
crude glycerol to go through saponification and produce potas-
sium phosphate as by-product using repeated acidification [73].
This is part of their proposed strategy to economize biodiesel
production while producing high quality free fatty acids and
glycerol due to the high price of the products.
3.2. Methanol removal
The second step in the general purification process is the
removal of methanol. In the transesterification process, excess
methanol is used in most biodiesel production to get high yield of
biodiesel. The excess methanol is distributed between the methyl
ester and crude glycerol phase [74]. The concern of major health
safety and environmental issue for residual methanol in both
biodiesel and glycerol is due to the toxicity of methanol in which
1167
the emission of excess methanol can have serious effects to the
environment and public health. Therefore, the excess amount of
methanol needs to be removed from the glycerol phase and
recycled back [55]. Methanol and water can be easily removed
by vacuum evaporation. For methanol removal, crude glycerol was
treated under vacuum conditions using a rotary evaporator at
50  90 1C for more than 2 h [75]. It is a common practice in the
industry to remove alcohol from both glycerol and biodiesel phase
to utilize either an evaporator or a flash unit [76]. However, due to
glycerol temperature susceptibility which can result in glycerol
decomposition, using falling film evaporators was found to be
more suitable and advantageous due to the fact that it keeps
shorter contact time. The purity of crude glycerol after methanol
removal will be approximately around 85%.
3.3. Purification and refinery
3.3.1. Vacuum distillation
Distillation is generally not applicable to feed streams which
are sensitive to thermal degradation or polymerize at elevated
temperatures. Operation of column under vacuum can help to
reduce or eliminate this problem [77]. Polymerization of glycerol
into polyglycerol would occur at temperature higher than 200 1C,
dehydration in slightly acidic conditions at temperature above
160 1C, and oxidation of glycerol into glycerose, glyceraldehydes
and di-hydroxylacetone [78]. In order to prevent degeneration of
glycerol, purification has to be done in vacuum where the pH,
temperature and pressure must be controlled. This is primarily
due to an adverse reaction that causes degradation of glycerol.
These are the reasons why vacuum distillation is the most
common method for glycerol purification [75,79,80].
Yong et al. reported that the purification of crude glycerol by
simple distillation at 120–126 1C would yield around 141 g gly-
cerol/kg of glycerol residue (  14% yield) at an acceptable purity of
96.6% glycerol [64]. The distilled glycerol product is of pH 3.5 con-
sisted of 0.03% ash, 1% water, 2.4% matter organic non-glycerol
(MONG). It was found that the optimum pH for the distillation was
less than 5 in which foaming was avoided. The distillation process
is a well-established technology [39], applicable for small to large-
scale continuous operation, low cost of chemicals as well as
process adaptability that suits varying qualities of crude and finish
products [81]. However, it should be noted that the distillation of
crude glycerol is an energy intensive process [39]. High-energy
input requirement for vaporization and creates thermal decom-
position due to high specific heat capacity of glycerol which makes
the process costly [52].
3.3.2. Ion exchange adsorption
Several types of impurities such as fatty acid, inorganic salt and
free ion impurities can be removed from crude glycerol by using
ion exclusion purification techniques [66,82]. The first early
commercial application of ion exchange unit for crude glycerol
(soap lye) purification at Lever Brothers Company plant in Los
Angeles, California is of a four-stage unit consisted of three pairs of
cation–anion exchangers and a mixed-bed. The plant which
started its operation in May 1951 has the purification capacity of
26,600 lbs of crude glycerol per day. The feed stream, crude
glycerol produced from soap lye normally contains 82% glycerol,
10% ash (6% of the ash is the NaCl), moisture and other impurities.
The final product produced is exceptionally high in quality which
compares favorably with high-grade distilled glycerol. The 95–99%
glycerol content confirms the pilot plant findings that indicate the
process holds a number of advantages over the conventional
distillation method. Among the advantages are low capital invest-
ment and exceptionally high product quality [82] which makes it
1168 M.S. Ardi et al. / Renewable and Sustainable Energy Reviews 42 (2015) 1164–1173
more suitable for smaller capacity plant [39]. It is also applicable to
a number of glycerol feed solutions such as separation of ionic
impurities directly from spent soap lye solution (contains 5–10%
glycerol, 12–15% salt) or solutions obtained from synthetic glycerol
processes (contains 7–8% glycerol, 12–15% salt) [66]. However,
later it was found that the technique results in poor separation due
to fewer exchange sites per unit volume (smaller exclusion factor).
Improvement based on this technique for crude glycerol from
biodiesel production is introduced where gel type acidic ion
exchange resin beads were used to eliminate several types of salts
such as fatty acid salts (5–50%), inorganic salts (1–5%) and free
ions impurities [83].
Ismail et al. utilized resin type AmberliteIRN-78 and Amber-
lite200 to purify crude glycerol and the effectiveness of resin was
investigated [84]. Column techniques were performed in the
experiments, where the ion-exchange resins were placed in a
vertical column forming a bed. High Performance Liquid Chromato-
graphy (HPLC) was used to analyze the glycerol samples obtained
after the purification. A single glycerol peak with a very smooth
baseline that matched to the pure glycerol profile was shown on the
chromatograms for the purified samples. These results indicated
that the application of the ion-exchange resin method is able to
remove the impurities such as inorganic salts and free ions.
However, for crude glycerol purification to be viable, issues con-
cerning the ion exchange method such as fouling by fatty acids, oils
and soaps, regeneration of the beds and large quantities of waste-
water produced needs further improvement [39].
3.3.3. Adsorption using activated carbon
Adsorption with activated carbon is mainly used as the finish-
ing step to further refine the purified glycerol; reduce the color, as
well as reducing some fatty acids and other components. Manosak
et al. used a commercial activated carbon in a sequential-refining
stages process where it was found that increasing the dose of
activated carbon had a significant effect on the color removal of
the refined crude glycerol [11]. They found that a clear color
(99.7%) reduction was achieved with higher dose of activated
carbon at 200 g/L glycerol. During this stage, some of the fatty
acids, such as lauric acid and myristic acid were eliminated.
Although other fatty acids, such as palmitic acid, oleic acid and
steric acid, as well as and some unknown compounds were still
present, the refined glycerol were all in the acceptable range of
values of the BS 2621:1979.
Table 3
List of membranes and filters used for glycerol purification.
Membranes/filters Material/types
CeramTec TF-E (Germany) Ceramic
Ultram SS316L/TiO2 (USA) Ceramic
HITK, Germany Ceramic
NF-PES-10 (Nadir NF Membranes, Celgard, Germany) Polyetersulfone, organic
NF30 PP100 (Nadir NF Membranes, Celgard, Germany) Polypropylene, organic
PVDF GE osmonic Polyvinylidene,
Organic
Flat sheet
HEEPM™ and HEEDs Model 400-B-75.2 glycerol desalting system Modular system
Syringe 0.45 μm filter Syringe filter
PES and PVDF Organic
Organic
DL (NF) GE osmonics Organic
SG (RO) GE osmonics
SR2 (NF) Koch
SR3 (NF) Koch
TRS83 (NF) TRISPE
Hunsom et al. in their work prepared a set of 15 activated
carbon derived from sewage sludge of waste water plant [4]. After
the two steps of the sludge derived activated carbon preparation,
pyrolysis and activation using different chemicals, KOH, K2CO3,
and H3PO4, adsorptive purification was carried out to pre-treated
crude glycerol. It was found that from all prepared sludge derived
activated carbon, one in particular namely KOH-800AC exhibited
the highest efficiency to adsorb impurities in pre-treated crude
glycerol. Based on the adsorptive result comparison between
commercial activated carbon and KOH-800AC, the latter showed
improved glycerol purity. Adsorptive purification using KOH-
800AC is 1.06-fold higher than that obtained with the commercial
activated carbon (84.1 wt%).
4. Membrane separation technology
The membrane separation process is a very simple process. The
driving force of the most isothermal membrane separation process
involves the difference in concentration or electrical potential and
hydrostatic pressure. Employment of different types of mem-
branes, microfiltration (MF), ultrafiltration (UF), nanofiltration
(NF), reverse osmosis (RO) and electrodialysis (ED) has been
reported for various applications [85–91]. Different types of
membrane are employed for different types of separation process,
for example microfiltration involves in separation of particles,
whereas separation of macromolecules utilizes ultrafiltration and
reverse osmosis is capable of separating ionic components [89].
A membrane is a barrier, which separates two phases and restricts
transport of various chemical species in a selective manner [92].
Either one of the permeate and retentate be the end-use products
in a membrane-based separation process [93]. Liquid separation of
various chemicals-based product using membrane based process
are usually employed for concentration and purification opera-
tions, water and waste water treatments. The wide applications of
membranes include employment of the mentioned process in
Fig. 4. EET corporation glycerol purification using membrane separation technol-
ogy [56].
Process References
Lazarova [95]
Nanofiltration
Nanofiltration
Ultrafiltration Mah et al., [96]
High efficiency electrodialysis/nanofiltration EET Corporation [97]
Microfiltration Ismail et al., [82]
Ultrafiltration Indok et al., [98]
Nanofiltration Traving [99]
Nanofiltration Muralidhara [100]
Reverse osmosis
 M.S. Ardi et al. / Renewable and Sustainable Energy Reviews 42 (2015) 1164–1173
chemical, dairy, food, beverage industries and in fermentation and
biotechnology [94]. Membrane technology has been used recently
in biodiesel purification due to its advantage as an environmental
friendly solution in which usage of water in water washing step is
avoided [95,96]. Table 3 lists membranes and filters used for
glycerol purification.
4.1. Application of membrane separation technology in glycerol
refining
The application of membrane separation technology in purifi-
cation of glycerol developed by EET Corporation is depicted in
Fig. 4. The patented technology of High Efficiency Electro-Pressure
Membrane (HEEPM™) employing an integrated approach in which
the membrane units operated in integrated configurations with
nanofiltration and/or reverse osmosis units, in a single synergistic
unit operation [56].
Mah et al. investigated the fouling pattern of oleic acid and
palm oil from glycerol solutions through the ultrafiltration mem-
brane process [97]. A commercial GE PVDF 30 kDa membrane was
used in the study to the effect of different palm oil, oleic acid, oleic
acid and palm oil concentrations, pH on membrane flux and
rejection ability. It was found from the investigation that the
membrane is capable to remove palm oil and oleic acid from
glycerol solution with sustainable flux. Jeromin et al. proposed an
application of pressure driven membrane technology such as
ultrafiltration based on a patent to remove unreacted oil or fat in
glycerol-rich solution [98]. The glycerol-rich solution or sweet
water from hydrolysis reaction contains a mixture of glycerol,
water and impurities such as free fatty acid, unreacted mono-, di-,
and triglycerides, inorganic salts and variety of matter organic
non-glycerol (MONG). However, frequent cleaning is required due
to the fouling of fatty acid. Indok et al. studied the ability of two
ultrafiltration polymeric membranes to clarify synthetic glycerin-
rich solutions containing triglycerides [99]. The membranes tested
in the experiment were made of poly (ether sulfone) (PES) and
poly (vinylidene fluoride) (PVDF). The reported molecular-weight
cut off (MWCO) values were 25,000 and 30,000 Da, respectively.
They studied the effects of membrane surface chemistry and
solution pH on the permeation flux and triglycerides retention
rate. It was found that in glycerol–water mixtures containing
triglycerides, the contribution of the solute to fouling was more
severe than that of fatty acid with lower permeation rates being
shown. Based on the findings, PVDF membranes were found to
provide higher fluxes and lower triglycerides rejection rates (81%)
than PES membranes (91%). Lazarova tested different types of
membrane to purify pre-treated crude glycerol derived from
biodiesel production [100]. The biodiesel production uses rape-
seed oil as the feed of transesterification process with methanol
and KOH as catalyst. The crude glycerol was pre-treated prior to
the membrane separation process. Sulfuric acid was added which
resulted in three-phase mixture consisted of a solid salt phase,
liquid glycerol phase (middle layer) and liquid fatty acid phase.
The liquid glycerol phase was then further treated using pressure
driven membrane separation at various transmembrane pressures
and feed flow rate. A membrane test unit (Amafilter) for flat
membranes was used to compare permeate fluxes and retention
capacities of the membranes and purification effect was evaluated
based on the data from a UV/VIS analysis. Ismail et al. used a
syringe filter 0.45 μm as part of pre-treatment process to filter
inorganic salts as a result of the neutralization with 85% v/v
phosphoric acid [84]. The crude glycerol was then further treated
with the ion exchange resin method. An application of nanofiltra-
tion polymer membrane as proposed by Traving et al. was able to
obtain salt free permeate stream after purification of crude
glycerol [101]. The nanofiltration used has pore size between
1169
0.01 mm and 0.05 mm. Another application of membrane to purify
crude glycerol obtained from the transesterification process pro-
poses a series of two or more nanofiltration or reverse osmosis
membrane [102]. The process requires at least one of the mem-
branes to have contact angle between 441 and 561. A result of
glycerol purity of 99.0% is achievable, filtering and purifying crude
glycerol of impurities and salts.
4.2. Prospect of glycerol refining using membrane technology
At present, an emerging technology in biodiesel derived crude
glycerol purification and refining, that is membrane technology is
identified as a feasible solution for the future sustainability of
biodiesel production. Membrane technology is considered as an
emerging technology that provides much cheaper and decent
performance as alternatives for the glycerol purification process
[56,103]. Although conventional methods, such as combinations of
chemical and physical treatments (vacuum distillation, evapora-
tion), produce good quality of purified glycerol, maintaining the
facilities, equipment and operational costs are the major hurdles
for optimization and cost control. The cost limitations are easily
minimized and reduced with the implementation of membrane
technology as it requires less energy.
Membrane technology is considered a good alternative with
regards to current methods for glycerol purification process. The
broad range of membranes applications and advantages has
attracted researchers to develop crude glycerol purification meth-
ods using membranes. Numerous studies have been engaged in
developing the glycerol purification technology based on mem-
brane and other alternatives [97,99,100]. However, the incorpora-
tion of membrane technology for industrial practice is still found
to be lacking despite the obvious advantages of low energy and
cost. Perhaps it is largely attributed to membrane disadvantages
which have prevented even wider applications of membrane-
based processes and have not been studied extensively, such as
the fouling of the membranes, the durability of membranes and
the availability of suitable membranes for specific operations
[104]. More research is required to make membrane technology
a feasible solution for the sustainability of biodiesel production.
4.2.1. Hybrid membrane
Another exciting prospect of membrane separation technology
is the utilization of hybrid membrane. Improvement of membrane
performance while combining organic and inorganic materials has
been explored in the last few years. The combinations of inor-
ganic/organic material of desired properties have led to a better
performance in terms of mechanical and thermal properties from
the inorganic part whilst maintaining the flexibility of the organic
part of the membranes. According to Zulfikar et al. [105] it was
found that water permeability increases with silica content for
Poly(methyl methacrylate) (PMMA)-SiO2 composite membranes
characterization in which additional amount of tetraethoxysilane
were added to PMMA solutions during the membrane formulation.
The deposition tetraethoxysilane were made possible due to
formation of hydrogen bond between organic phase and inorganic
phase during the sol–gel process [106]. Crude glycerol purification
process using membrane would be benefited from the improve-
ment of these properties, for example water permeability increase
would improve the permeation of water soluble material through
the membranes. Improvement in other properties such as thermal
and mechanical would produce a membrane with much higher
quality, both in terms of performance and sustainability.
1170 M.S. Ardi et al. / Renewable and Sustainable Energy Reviews 42 (2015) 1164–1173
Table 4
Summary of glycerol purification technologies.
Techniques Advantages
Vacuum distillation  Established method
 Produce high quality glycerol
Ion exchange  Inherent low cost
 Ease of unit scale-up
Membrane  Low energetic requirement
 Simplicity of operation
 Ease of unit scale-up and control
 Environment compatibility
 Large operation flexibility
Activated carbon  Color reduction
Chemical treatment  Used as a pretreatment (neutralization)
 Produces high quality by-product (fatty acids)
 Removal of soaps
4.2.2. Membrane distillation
Application of membrane contactor is a potentially viable
technique to purify crude glycerol. An emerging prospect in terms
of membrane separation technology is by utilizing membrane
distillation. Unlike conventional membranes which are pressure
driven, membrane distillation is a thermally driven membrane
process. Most of the current applications of membrane distillation
involve removal of water in which water vapour transport occurs
through a non-wetted porous hydrophobic membrane. The tem-
perature difference across the membrane would produce a vapour
pressure gradient that would be the main driving force for
membrane distillation process [107].
Membrane distillation processes have advantages compared to
conventional separation technologies; it uses relatively lower
energy compared to distillation, reverse osmosis and pervapora-
tion. Membrane distillation also has considerable rejection of
dissolved, non-volatile species. Furthermore, compared to conven-
tional membrane separation technologies such as microfiltration,
ultrafiltration and reverse osmosis, membrane distillation would
have lower membrane fouling. It would also operate at much
lower operating pressure compared to pressure-driven membrane
and lower operating temperature in comparison with conven-
tional evaporation [108–114]. However despite having a lot of
advantages as compared to conventional membranes, membrane
distillation possesses a technical drawback in terms of having low
transmembrane flux compared with reverse osmosis. It was
proposed to combined membrane distillation with other mem-
brane system such as microfiltration, ultrafiltration, nanofiltration
as to improve transmembrane flux, recovery factor and product
recovery [109,115–123].
5. Challenges of crude glycerol utilization and purification
The challenges in terms of utilization and purification of crude
glycerol, a by-product of biodiesel production requires develop-
ment of new approaches and alternatives as to ensure the
sustainability of biodiesel production industries [86]. The current
scenario in terms of bio-glycerol utilization and purification
challenges are best described through vast efforts to find strategic
methods that involve turning the waste into valuable products
Disadvantages References
 High energy requirement [39, 73, 77–79, 52]
 Unfeasible for small and medium enterprise
 High maintenance
 Sensitive to feed stream variations
 Washing water – requires treatment [39, 65, 80-82]
 Chemical regeneration cost for resins is high for salt content (5–7)%
 Unfeasible for high salt content glycerol
 Not fully optimized for industrial scale [82,95–100]
 Inefficient for removal of other impurities [4,11]
 Repeated acidification would result in low glycerol yield [6,63,70,71]
 Requires further purification to produce high quality glycerol
with cost reduced. A good example of this effort is shown by
incorporation of the glycerol purification process in biodiesel
plants [15]. While the ‘waste’ actually has a wide variety of
applications yet one of the main challenges lies with the purifica-
tion of crude glycerol, converting crude glycerol to more usable
state for current and emerging uses [124–127]. This is primarily
due to the fact that most industrial product uses refined glycerol as
raw material [128]. Table 4 summarizes the purification technol-
ogies for crude glycerol.
Another form of challenge is derived from the biodiesel
production processes itself. As mentioned before, new approach
in biodiesel production process is needed as current technology
although capable of producing a good quality biodiesel but still has
a number of disadvantages. The drawback includes the utilization
of base catalyst that induces soap formation which needs to be
removed, the excess amount of alcohol used to shift the equili-
brium to more biodiesel produced (more alcohol needs to be
separated and recycled), homogenous catalyst that requires neu-
tralization which in turn producing a huge amount of salt in the
waste stream, high operating cost and expensive separation
procedures. Furthermore, vegetable oil and alcohol must be con-
siderably anhydrous and have a low free fatty acid content,
because the presence of water or free fatty acid or both promotes
soap formation [30].
6. Conclusion
Glycerol purification technology offers promising opportunities
towards establishing glycerol as a platform for various purposes as
well as in the conversion of bio-glycerol to value added chemicals.
The excessive supply of crude glycerol would encourage the
applications of chemicals using glycerol which will then elevate
glycerol stature as key building block chemicals in the industry.
The technologies mentioned here present ways for the devel-
opment and sustainability of biodiesel production process in the
long run. At present, vacuum distillation albeit costly and energy
intensive would still remain as the leading purification method for
pure glycerol. However, in order to support sustainable growth of
biodiesel production in the long run it is very essential to explore
more economical crude glycerol purification techniques. The
 M.S. Ardi et al. / Renewable and Sustainable Energy Reviews 42 (2015) 1164–1173
application of alternative methods such as membrane separation
technology is seen as an emerging technology that have positive
and promising future. Though, many of these technologies still
require additional research and development to make them
economically and operationally feasible. Improvement of the
glycerol purification method with less energy intensive that is
capable to yield pure glycerol purity will be most likely incorpo-
rated in biodiesel plant as part of a sustainable structure.
Acknowledgments
The authors greatly appreciated financial supports by program
HIR-MOHE (UM.C/HIR/MOHE/ENG 59) of University of Malaya,
Malaysia.
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