Separation & Purification of Crude Glycerol

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Recovery and Purification of Crude Glycerol from

Vegetable Oil Transesterification
ab
Wan Nor Roslam Wan Isahak , Zatil Amali Che Ramli , Manal Ismail , Jamaliah Mohd Jahim
& Mohd Ambar Yarmo

a
Department of Chemical Engineering and Process, Faculty of Engineering and Built

Environment, Universiti Kebangsaan Malaysia, Bangi, Malaysia
b
School of Chemical Sciences and Food Technology, Faculty of Science and Technology,
Universiti Kebangsaan Malaysia, Bangi, Malaysia
Accepted author version posted online: 11 Feb 2014.Published online: 10 Oct 2014.
To cite this article: Wan Nor Roslam Wan Isahak, Zatil Amali Che Ramli, Manal Ismail, Jamaliah Mohd Jahim & Mohd Ambar
Yarmo (2015) Recovery and Purification of Crude Glycerol from Vegetable Oil Transesterification, Separation & Purification
Reviews, 44:3, 250-267, DOI: 10.1080/15422119.2013.851696
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Separation & Purification Reviews, 44: 250267, 2015

Copyright Taylor & Francis Group, LLC
ISSN: 1542-2119 print / 1542-2127 online
DOI: 10.1080/15422119.2013.851696
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
Recovery and Purification of Crude Glycerol from

Vegetable Oil Transesterification
Wan Nor Roslam Wan Isahak,1,2 Zatil Amali Che Ramli,2 Manal Ismail,1
Jamaliah Mohd Jahim,1 and Mohd Ambar Yarmo2
1
Department of Chemical Engineering and Process, Faculty of Engineering and Built Environment,
Universiti Kebangsaan Malaysia, Bangi, Malaysia
2
School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti
Kebangsaan Malaysia, Bangi, Malaysia
This article reviews the purification techniques involved in producing high-purity glycerol in
the biodiesel industry. Utilization of glycerol by-products (contains less than 50 wt.% of glycerol and the remaining contents are water, salts, unreacted alcohol and catalyst) in biodiesel
production affords greener and less costly processes. Research has focused on several purification steps that are capable of producing high-purity glycerol. Various new techniques for
purifying glycerol promise better quality and lower cost and technologies are required to fulfil
increasing worldwide demand. Neutralization, ultrafiltration, the use of ion exchange resins,
vacuum distillation and other methods have been utilized in single or multiple stages. Recent
studies have demonstrated that the combination of more than one technique produces high-purity glycerol (>99.2%). Purifications cost can be as low as 0.149 USD$/kg. For many
applications, high-purity glycerol is more useful. In some cases, it is even necessary, particularly in the fields of hydrogen production, methanol production, pharmaceuticals and food
additives.
Keywords: Crude glycerol, purification, ion exchange resins, separation technique, ultrafiltration, vacuum distillation
BACKGROUND
Glycerol, or glycerine, or 1,2,3-propanetriol, can be produced from the transesterification or hydrolysis of natural
fats, vegetable oils or petrochemicals (1). In Malaysian
biodiesel processes, palm oil is the primary raw material
from which glycerol is produced as a transesterification byproduct. In these processes, palm oil is treated with methanol
and a basic homogeneous catalyst. Alternatively, acidic,
basic or enzymatic heterogeneous catalysts are used because
of their ease of separation from the products.
Received 19 August 2011, Accepted 30 September 2013.

Address correspondence to Mohd Ambar Yarmo, School of Chemical
Sciences and Food Technology, Faculty of Science and Technology,
Universiti Kebangsaan Malaysia, Bangi 43600, Malaysia. E-mail:
ambar@ukm.my
Crude glycerol production from biodiesel conversion is

increasing yearly. From 2008 to 20011, total worldwide
crude glycerol output increased from 2.06 to 2.88 million tonnes (2,3). The global demand for glycerol was
1,995.5 kilo tons in 2011 and is expected to reach
3,060.4 kilo tons by 2018, growing at a Compounded Annual
Growth Rate (CAGR) of 6.3% from 2012 to 2018 (4).
The Malaysian palm-based oleochemical industry is growing rapidly and produces products such as fatty acid methyl
esters (FAMEs), fatty alcohols and crude glycerol (5,6).
The abundant crude glycerol generated by this industry
affords a great opportunity for scientists to explore new glycerol applications. High-purity glycerol finds wide use as
an ingredient or processing aid in healthcare products, fuel
additives, lubricants, personal care products, cosmetics and
food (7,8).
However, the glycerol produced as a by-product of transesterification from biodiesel processes is not pure enough for
GLYCEROL RECOVERY FROM VEGETABLE OIL
direct use in high-tech applications. To overcome this problem, numerous treatments are required to remove impurities.
Moreover, the manufacturing and pharmaceutical industries have increasingly demanded high-quality, food-grade
glycerol because of its superior physical properties, low
contamination and odorlessness (9).
Therefore, an effective, efficient glycerol purification
process is needed to minimise production costs, minimise
industrial waste and maximise the utility of biodiesel industrial processes. Because of the enormous demand for the
production of glycerol from biodiesel waste, we have
thoroughly reviewed vegetable oil transesterification and
hydrolysis as a glycerol synthetic route. Various purification methods for producing high-purity glycerol are herein
discussed, and some glycerol conversion processes are
summarized.
CHEMICAL COMPOSITION OF CRUDE

GLYCEROL
The factors that influence the quality of crude glycerol
derived from biodiesel production processes include catalyst type and quantity, recovery methods, unreacted methanol
and other impurities. For example, a crude glycerol extracted
from sunflower oil biodiesel had a composition (w/w) of
30% glycerol, 50% methanol, 13% soap, 2% moisture,
2-3% salts (primarily sodium and potassium) and 23%
other impurities (7). In contrast, Hansen et al. (10) reported
glycerol contents of 38 to 96% in a set of 11 crude glycerol samples collected from 7 different Australian biodiesel
producers. Some of those samples contained more than
14% methanol and 29% ash. Because most biodiesel production uses low-grade methanol and homogeneous alkaline catalysts (sodium methoxide or potassium hydroxide),
the quality of the afforded glycerol is poor (11). Saman
et al. identified several contaminants in crude glycerol
methanol, soaps, catalysts, salts, non-glycerol organic matter
and excessive water (12).
Even when identical feedstocks were employed, the
crude glycerol produced from alkali- and lipase-catalyzed
transesterifications was reported to differ in purity (13).
For biodiesel production that utilized homogeneous alkaline catalysts, the crude glycerol produced contained 5 to
7% salts (14), making conventional purification techniques
more costly. Heterogeneous processes using enzymes and
solid metal-oxide catalysts have been promoted as alternatives that afford higher-quality crude glycerol. However,
with heterogeneous catalysts, impurities present in natural
raw feedstocks tend to accumulate in the glycerol phase.
Therefore, purification remains a requirement for meeting
current standards. Moreover, each contaminant requires a
different method of removal.
251
PRODUCTION OF GLYCEROL FROM

VEGETABLE OIL
The two primary processes for biodiesel production are
hydrolysis and transesterification. Hydrolysis refers to a
chemical reaction in which water molecules are split into
oxygen and hydroxide anions, whereas a biodiesel transesterification refers to a reaction that occurs between a triglyceride or fat and an alcohol to form alkyl esters (biodiesel
fuel) and glycerol (Figure 1). The theoretical stoichiometric ratio of alcohol to lipids for these transesterifications is
3:1. In reality, a 6:1 ratio is necessary to achieve practical
yields. The alcohol molecules displace the triglyceride (triacylglycerol) molecules in forming an ester. This process is
also known as alcoholysis because cleavage of an alcohol
is involved. Most biodiesel producers utilize homogeneous
alkaline catalysts such as sodium hydroxide or potassium
hydroxide (15). These catalysts also saponify the starting
materials into foams. Consequently, yields decrease, and
major problems in catalyst recovery, product separation and
product purification are encountered (1618).
Transesterification requires an alcohol. Methanol and
ethanol are the most frequently used alcohols for biodiesel
transesterification reactions; propanol and butanol are also
widely employed. For environmentally friendly processes,
ethanol is chosen because it can be derived from agricultural products or other renewable resources. Alternatively,
methanol is chosen for its lower cost, high polarity and short
alkyl chain (19).
Hydrolysis Processes
Vegetable oil hydrolysis is achieved using an acid or base
catalyst and produces glycerol and free fatty acids or soaps.
Base-catalyzed ester hydrolysis is commonly called saponification. Both processes are shown in Figure 2. The performances of various vegetable oil hydrolyses are summarized
in Table 1. In previous studies, Hammond and Inmok (20)
reported that lipase split triglycerides into free fatty acids
and glycerol. Their hydrolyses were performed with 17 to
44% moisture, and water was applied by various suitable
techniques, e.g., soaking and spraying.
Hydrolysis without a catalyst at 270350 C, 20 MPa and
a water/oil feed ratio of 50/50 (v/v) afforded approximately
FIGURE 1 Transesterification process that produces alkyl esters and

glycerol.
252
W. N. R. WAN ISAHAK ET AL.
Homogeneous Catalytic Systems
FIGURE 2 Hydrolytic processes: a) acid-catalyzed hydrolysis and b)

base-catalyzed hydrolysis (saponification).
90% biodiesel and 10% glycerol (25,26). The water concentration was sufficient for both hydrolysis and triglyceride
cracking (24,27,28). Commonly, vegetable oil hydrolysis
involves the use of rotating hydrothermal reactors operated
at high temperatures and pressures. Several companies in
Malaysia namely, Cognis Oleochemical Industries, FPG
Oleochemicals Sdn Bhd and Pacific Oleochemicals Sdn
Bhd are using this catalyst-free hydrolytic technology in
their biodiesel production processes. The basic scheme for
biodiesel and glycerol production via transesterification is
shown in Figure 3.
Transesterification Reactions
In transesterification, basic, acidic or enzymatic catalysts are
employed (29,30). Major differences exist between homogeneous and heterogeneous catalysts in terms of activity,
product separation and production cost (31). In Malaysia,
transesterification reactions are widely applied in biodiesel
production by Malaysian Palm Oil Board, Golden Hope
Plantation Sdn Bhd and Emery Oleochemicals. The other
international companies such as P & G Chemicals (USA) and
BASF Chemical (Germany) also produced glycerol in huge
volume. Unfortunately, the glycerol produced by their processes is low in quality and thus limited in utility. The poor
glycerol quality provided by these companies is attributed to
difficult separations and the high costs associated with the
development of purification techniques.
The most active catalysts, alkaline metal alkoxides such

as sodium methoxide (CH3 ONa), are commonly used in
methanolyses because of their high conversions (>98%),
short reaction times (approximately 30 minutes) and low
molar concentrations (0.5 mole %). However, anhydrous
requirements have rendered those catalysts inappropriate for
typical industrial processes (18). Moreover, the separation
of the homogeneous catalyst from the glycerol mixture has
been cost-prohibitive (32). Transesterification reactions are
also performed using acid catalysts. In many cases, the reactions with acid catalysts have been reported to be slower
than the reactions with base catalysts. However, acid catalysts exhibit high activity at high temperatures and high
oil-to-alcohol ratios. Among the catalysts reported in the literature, trifluoroacetic acid was been observed to perform the
best, affording 98.4% conversion in 5 hours with an alcoholto-oil molar ratio of 20:1 and at a reaction temperature of
120 C (33).
Catalytic sodium hydroxide was observed to produce side
reactions and form sodium soaps easily. This sodium soap
formation was also observed when catalytic sodium methylate was employed in the presence of trace water amounts.
These sodium soaps were soluble in the glycerol phase. The
soaps required neutralization to fatty acids and decantation
(34). Furthermore, even when a water-free alcohol/oil mixture was used, some water was introduced into the reactor
system by the deprotonation of the alcohol by hydroxide. The
presence of water enabled hydrolysis and resulted in soap
formation. This undesirable saponification reaction reduced
fatty acid methyl ester yields and considerably hindered
glycerol recovery due to emulsion formation (18). The performances of various homogeneous catalysts are shown in
Table 2.
Heterogeneous Catalytic Systems
The heterogeneous catalysts of vegetable oil transesterification can be categorized as either acidic or basic. Alkali
catalysts are commonly used in transesterification and
exhibit higher activities than acidic catalysts. Furthermore,
basic catalysts have afforded particularly high conversions
TABLE 1
Performance of various vegetable oil hydrolytic processes
Type of catalyst/reaction
Lipase-catalyzed hydrolysis
Lipase-catalyzed hydrolysis
Base-catalyzed hydrolysis
Acid-catalyzed hydrolysis
Non-catalyzed hydrolysis
Molar ratio
(Oil: water)
Temperature
( C)
Time (h)
Conversion
(%)
References
1:20
40
27
100
190
270350
2
5
3
8
15 min
95
88
98
99.4
100
(20)
(21)
(22)
(23)
(24)
253
TABLE 2
Homogeneous catalysts in glycerol production
Homogeneous basic
NaOH
KOH
NaOCH3
Homogeneous acidic
AlCl3 and ZnCl2
H2 SO4
H2 SO4
H2 SO4
Trifluoroacetic acid
Temperature ( C)
Time (h)
Conversion (%)
References
6:1
6:1
6:1
45
60
60
0.25
1
2
98
100
97.1
(35)
(36)
(37)
24 : 1
50 : 1
20 : 1
245 : 1
20 : 1
110
80
95
70
120
18
4
20
4
5
98
97
>90
99
98.4
(38)
(39)
(40)
(41)
(33)
Molar ratio
when supported on alumina, metal or zeolites. A comparatively high reaction temperature is required to achieve only a
slow reaction rate in acid-catalyzed transesterifications.
Previous studies have reported that vegetable oil transesterification using heterogeneous acid catalysts is not a practical process because it requires high temperatures, lengthy
reaction times and large catalyst charges. In addition, synthesizing the catalysts was reported to be complicated and
uneconomical. Catalyst leaching also presented a risk of
product contamination. These drawbacks led to higher separation costs and created additional problems we will not discuss. However, the solid acid catalysts could be regenerated
and reused.
Supported basic heterogeneous catalysts, such as potassium hydroxide on alumina (KOH/Al2 O3 ), have exhibited high activities and basicity (11). One optimized
KOH/Al2 O3 reaction afforded 90.54% diesel and 9.46%
glycerol. Arzamendi et al. (42) reported conversions up to
99% when sodium hydroxide on alumina (KOH/Al2 O3 ) was
employed. The high conversions resulted from the catalysts
high number of active sites and the catalysts basicity.
FIGURE 3
Sparingly soluble catalysts such as calcium oxide, sodium

methoxide and barium hydroxide have exhibited high activities for rapeseed oil transesterification (43). During vegetable oil transesterification using calcium oxide, calcium
glyceroxide was produced through the reaction of calcium
oxide with glycerol. This by-product created more active
sites and thus enhanced the reaction rate (44). The activities of heterogeneously catalyzed reactions are listed in
Table 3.
The Supercritical Methanol System
Transesterification reactions using basic or acidic catalysts are relatively time-consuming and require complex
separations, resulting in high production costs and energy
consumption. To overcome these problems, supercritical
methanol (SCM) has been proposed for catalyst-free vegetable oil transesterifications (5759). Whereas vegetable
oil transesterifications with regular methanol are biphasic
reactions, the lower dielectric constant of supercritical
methanol results in a one-phase reaction solution. The single
Basic scheme for biodiesel and glycerol production.
254

TABLE 3
Various heterogeneous catalytic systems employed in glycerol production
Molar ratio
Temperature ( C)
Time (h)
Conversion (%)
References
65:1
12:1
15:1
65:1
12:1
30:1
20:1
9:1
18:1
60
65
<70
60
65
60
120
60
170
3
5
23
5
3
1
1
30 min
12
94
94
91.07
97
95
94
98.6
97.3
92.5
(45)
(46)
(47)
(48)
(49)
(50)
(51)
(52)
(53)
10:1
20:1
12:1
80
60
150200
2
1
3
97.1
100
9
(54)
(56)
(55)
Heterogeneous basic
Ca (NO3 ) 2 /Al2 O3
CaO/Al2 O3
KOH/Al2 O3
Mg-Al hydrotalcite
CaO
CaO/ZnO
Sulfated zirconia
Sr-Mg
Alum (KAl (SO4 )2 12H2 O)
Heterogeneous acidic
p-Toluenesulfonic acid (PTSA)
Metal acetates and stearic acid
Silicotungstic acid
Immobilized Enzyme Catalytic System
phase allows for a short reaction time (60). Compared with

catalytic processes carried out at atmospheric pressure, the
non-catalytic SCM process involves a considerably simpler
purification step, a lower reaction time and lower energy.
In addition, the SCM method is more environmentally
friendly.
In investigating product separation problems, Hawash
et al. (61) reported that a non-catalytic transesterification
reaction using supercritical methanol afforded a 100% ester
yield within four minutes. However, a reaction temperature
of 593 K and a reaction pressure of 8.4 MPa were necessary.
Moreover, a high molar ratio of methanol to oil was utilized
(61,62). Although high, the cost of the SCM process could
be offset because this reaction produces high-purity methyl
esters (99.6%) and glycerol (96.5%) (63). Glycerol production using the SCM technique is summarized in Table 4.
The transesterification reaction is also performed using

enzyme catalysts. Lipase is the most efficient and active
enzyme for the reaction. To immobilize the enzyme, the
carbodiimide activation method is the most effective. The
penicillium expansum lipase (PEL) systems discussed by
Yang et al. (66) and Xu and Ma (67) are summarized in
Table 5.
Nanoparticle Catalytic Systems
Over the past three years, nanoparticle heterogeneous catalysts have been used in vegetable oil transesterifications
to easily separate the catalyst from the glycerol phase.
The activity and performance was reported to increase
TABLE 4
Transesterification using supercritical methanol (SCM)
SCM
SCM
SCM
NaOH in SCM
KOH in SCM
Molar ratio
(MeOH:Oil)
Temperature ( C)
Time (min)
Conversion (%)
References
43:1
45:1
36:1
41:1
250300
320
350
250
287
715
4
5
8
30
98
100
96
98
>98
(58)
(61)
(64)
(65)
(63)
TABLE 5
Performance of transesterification reactions using immobilized enzymes as catalysts
Immobilized lipase NOVO435
Immobilized lipase on magnetic
nanoparticles
Molar ratio
Temperature ( C)
Time (h)
Conversion (%)
References
2.2:1
1:1
43
45
36
25
100
94
(91)
(67)
255
TABLE 6
Performance of transesterification reactions using nanoparticle catalysts
Molar ratio
Temperature ( C)
Time (h)
Conversion (%)
References
KF-loaded nano--Al2 O3
CaO nanopowder
Nano-MgO
Nanocrystalline CaO
15:1
15:1
36:1
27:1
65
65
240
Room temperature
8
2.5
16 min
97.7
94
99.28
99
(68)
(69)
(70)
(71)
PRODUCTS SEPARATION AND CATALYST

RECOVERY STAGE
for nano-sized catalytic particles because of their higher

surface area and availability of active sites. Boz et al.
(68) demonstrated KF-loaded nano--Al2 O3 as a versatile catalyst for transesterification. The catalytic performance of various nanoparticle catalysts is summarized in
Table 6.
Homogeneous catalysts are the most active catalysts for

the vegetable oil transesterification reaction. However, the
higher residual catalyst amounts associated with these catalysts compared with those encountered in heterogeneous processes lead to higher separation costs. Furthermore, unlike
heterogeneous catalysts, homogeneous catalysts cannot be
recycled for reuse because they remain in the product. One
technique for removing excess homogeneous catalyst is a
titrative method by which the acid or base catalyst is converted into its salt (38). Because of their ease of separation
and ability to be regenerated, heterogeneous catalysts are
good, clean and cost-effective alternatives for producing
FAMEs and glycerol from vegetable oils. The solid catalyst can be removed by filtration, resulting in a less complex
recovery of biodiesel and glycerol (78,79).
Recovering glycerol from FAME phases was studied by
Saleh et al. (80). The researchers found that an ultrafiltration
technique successfully separated the small amount of glycerol contained in the FAME phase. Temperature significantly
increased water solubility in various commercial biodiesels
(81). Consequently, using higher temperatures increased
glycerol solubility in FAMEs and made the subsequent separations more challenging. Wang et al. (81) reported that using
ceramic membrane separation at 60 C reduced the glycerol
dissolved in FAME; however, this result was achieved only
after removing the methanol.
For glycerol produced by vegetable oil transesterification
with an ionic liquid, the catalyst can be separated from the
product mixture by a crystallization and freezing technique
based on the boiling-point differences between glycerol and
the ionic liquid (72). The glycerol producers using super
Ionic Liquid (ILs) Catalytic Systems

In other works, immidazolium-based ionic liquids and multiphase acidic or basic conditions have been used to produce glycerol from vegetable oil transesterification. High
yields of biodiesel (>98%) were afforded from soybean
oil transesterification when the ionic liquid 1-n-butyl3-methylimidazolium bis (trifluoromethylsulphonyl) imide
(BMI.NTf2 ), alcohols and K2 CO3 or sulphuric acid were
used (72). The lack of a solid catalyst resulted in a clean
process. However, this catalytic process was not practical
because of the high IL cost and difficulty in handling.
Interestingly, Vidya and Chadha (73) reported that
hydrophobic ILs such as [Bmim]PF6 and [Bmim]NTf2
were better media for vegetable oil transesterifications
than the hydrophilic [Bmim]BF4 . They also indicated
that the IL anions strongly affected the catalytic performance of Pseudomonas cepacia lipase (73). Comparing
two hydrophobic ILs, [Bmim]NTf2 performed better than
[Bmim]PF6 . The higher viscosity of [Bmim]PF6 limited
mass transfer of the substrates and products to and from the
enzyme active sites and thus led to lower catalytic activity
(76). Isahak et al. (77) reported that the use of ionic liquids,
namely choline chloride, produced higher-quality biodiesels
and glycerol. The activities of various ionic liquid catalysts
are summarized in Table 7.
TABLE 7
Performance of transesterification reactions using ionic liquids as catalysts
[Bmim]NTf2
[Bmim]PF6
[C3 mim]Cl
N-Methyl-2-pyrrolidone
hydrogen sulphate
Molar ratio
(MeOH:Oil)
Temperature ( C)
Time (h)
Conversion (%)
References
7.5:1
1:1
2:1
70
50
80
80
1.5
24
3
3
>98
98
96
95
(72)
(73)
(74)
(75)
256
critical methanol (SCM) and hydrolysis were not apprehensive of any excess catalyst. However, unreacted triglyceride
remained in the product mixtures. To remove the unreacted material, a solvent extraction method that involves
overnight separation into layers based on weight and polarity
can be used. Otherwise, a centrifugation technique must be
employed to separate the products.
Nanoparticle Catalyst Recovery Processes

Nanoparticle catalysts are difficult to remove using conventional filtration. Polymeric membranes can recover nanoparticle catalysts. The filtration efficiency depends on the membrane size. The nanoparticle catalysts used for vegetable oil
transesterification processes resist separation and recovery.
However, centrifugation has been demonstrated to separate
these catalysts from products at high recovery levels (70).
Homogeneous Catalyst Recovery Processes

The homogeneous catalysts remain in the product after transesterification; therefore, the homogeneous catalysts are not
reusable. However, transition metal homogeneous catalysts
can be recovered by using a zeolite membrane that has a crystalline structure with pores smaller than those of transition
metal catalysts (82). Alternatively, homogeneous catalysts
can be neutralized into salts, and the salts can then be
removed by filtration. Catalyst removal after acid washing
is discussed later.
Heterogeneous Catalyst Recovery Processes

Few studies of heterogeneous catalyst regeneration exist.
Solid-phase heterogeneous vegetable oil transesterification catalysts can generally be recycled a few times
without adverse effects. They can be removed easily from the products by filtration or centrifugation
(42,56,68,83,84). Commonly, the heterogeneous catalysts
are then washed with organic solvent and drying overnight
(8587). Following re-calcination under N2 after an extensive methanol wash, the catalysts are ready for additional
reactions (88,89). Some researchers report that heterogeneous catalysts can be reused without any treatment and
without any significant loss in activity (90).
Supercritical Methanol Recovery Process

Catalyst-free supercritical methanol transesterification is
performed to increase the reaction rate and thus shorten the
reaction time. However, the excess SCM required leads to
some difficulty in separation. The problem can be overcome
by an evaporation and layer separation technique (63).
Ionic Liquid Catalyst Recovery Process

Ionic liquids are efficient and versatile catalysts because
of their physicochemical properties. Ionic liquids are salts
that consist of easily separated anions and cations. Because
of melting-point differences between the ionic liquids and
remainder of the reaction chemicals, freezing techniques
are common methods for separating ionic liquids from the
products and unreacted starting material (72,73).
CRUDE GLYCEROL RECOVERY PROCESS

Here, glycerol recovery from hydrolysis, saponification and
transesterification reactions is reviewed. Various practical
methods and techniques have been used for glycerol recovery
and enrichment.
Hydrolysis
Hydrolysis is divided into two processes: acid-catalyzed
hydrolysis and base-catalyzed hydrolysis (saponification).
The reaction produces two layers of product that can be
separated by using a separating funnel or by decantation.
Homogenous catalysts can be recovered by neutralization to
salts and centrifugation (22); heterogeneous catalysts can be
removed by filtration. Crude glycerol is obtained from the
lower phase by removing water through vacuum distillation
(23). An advanced glycerol recovery technique was developed by modification of an ionic liquid-glycerol mixture to
form deep eutectic solvents (DES). The synthesized DES
was used to extract the glycerol from the biodiesel (92).
Transesterification Reaction
Immobilized Enzyme Catalyst Recovery Process
Immobilized enzymes are efficient catalysts for vegetable oil
transesterification. However, the production costs are high
and require catalyst reuse. Otherwise, difficulties in handling are the primary problems associates with immobilized
enzymes. For reuse, the enzyme is isolated using centrifugation. The recovered lipase is washed with organic solvents
and is then ready for another reaction (68,91).
Theoretically, the glycerol of vegetable oil transesterification

constitutes approximately 10% of the products. Typically,
however, the recovered glycerol constitutes only 9 to 9.6%
of the products (Table 8). In an effective biodiesel production process, only small amounts of the unreacted starting
materials remain in the glycerol phase. Glycerol is also an
important by-product in soap production. When fats and
oils are saponified by caustic soda in the soap production

TABLE 8
Typical percentages of transesterification products
Products of transesterification
Percentage range (%)
References
Biodiesel
Glycerol
Unreacted products (methanol,
MG, DG, TG)
9091
9.09.6
0.41.0
(11,93,94)
(93,94,95,96,97)
(11,93,98,99)
Note: MG: Monoglyceride, DG: Diglyceride, TG: Triglyceride.
process, glycerol is dissolved in the soap lye and in the crude

soap as an impurity.
Glycerol from fats and oil in soap manufacturing usually comprise approximately 10% of the total products.
Recovering usable materials is vital to the profitability of
any soap production process. Unfortunately, many smalland medium-scale soap producers discard the lye. The specific recovery technique employed is critical to recovering
glycerol from spent soap lye. The liquor that remains after
soap manufacture must be allowed to settle for 20 minutes
after stirring. The clear phase is decanted and discarded,
and the remaining phase is heat treated at 60 C in a conical
flask (100).
The basic and acidic catalysts employed for glycerol production by transesterification are recovered via chemical
treatment. Either sulphuric acid (H2 SO4 ) or sodium hydroxide (NaOH) are used to neutralize the catalysts to salts. For
example, H2 SO4 neutralizes NaOH in glycerol samples to
sodium sulphate (Na2 SO4 ). Fortunately, Na2 SO4 has low solubility in the aqueous glycerol solution, which is saturated
with sodium chloride (NaCl). Indeed, NaCl remains primarily in the glycerol layer (101,102). Hence, the Na2 SO4 salts
can be removed by decantation and filtration.
The highest glycerol yields are obtained by the bleaching
recovery technique (100). Bleaching (alkaline system) both
purifies the glycerol and further saponifies the free triglycerides (103). The amount of recovered glycerol depends
on the recovery point and on the purification stage during
which the technique is utilized (104). The variation in glycerol recovery amounts obtained across the soap industry is
due to the different soap types of lye and methods of treatment employed. For example, during the recovery stages,
glycerol can be lost through washing, graining and desalting. Moreover, if a temperature of 60 C is exceeded during
treatment, side reactions may occur. Glycerol decomposes to
acrolein at higher temperatures (>140 C).
The crude glycerol derived from vegetable oil can
be recovered from the biodiesel phase by centrifugation.
Centrifugation is followed by hydrochloric acid treatment
to convert any contaminant soaps to free acids or salts
(105,106). Methanol and water contaminants are removed
by distillation (107). Afterward, the glycerol layer is neutralized with caustic soda, producing 80% (w/w) crude glycerol.
Next, some glycerol purification processes are presented.
In addition, a recovery technique that employs fixed silica
257
gel beds to adsorb glycerol from methanol-free biodiesel

streams is discussed (108).
OVERVIEW OF GLYCEROL PURIFICATION

For many years, glycerol has been purified to make it more
useful for various manufacturing activities. Crude glycerol
is obtained as a by-product from three different processes:
soap manufacture, fatty acid production and fatty ester production (109). High-purity glycerol is used commercially in
pharmaceuticals, food processing, lubrication and cosmetics.
For use as animal food, several glycerol purification steps are
required to remove impurities (110).
The purity of crude glycerol obtained from vegetable oil
transesterification depends on three parameters: the type of
catalyst used, the amount of excess alcohol and the conversion achieved (111). The purity ranges of crude glycerol
produced by transesterification using homogeneous catalysts, heterogeneous catalysts and supercritical methanol
(SCM) are 5570%, 7585%, and 96.5%, respectively (112).
Currently, much attention is being focussed on employing green catalytic transesterification processes to convert
bio-renewable vegetable oils to commodity chemicals and
clean fuels. These reactions are performed at lower temperatures and atmospheric pressure using homogeneous or
heterogeneous catalysts and excess methanol. However, the
excessive unreacted methanol presents a problem. Methanol
is dangerous and can adversely affect human health and the
environment. To overcome this problem, the excess methanol
is recovered by processes such as evaporation and recycled
to the reactor for additional transesterification cycles.
Crude glycerol contains 20.2% glycerol, 6.6% fatty acids
(as soap) and 64.3% salt. Thus, 91.1% of crude glycerol
residue consists of components that are potentially useful
for other applications (113). According to van Gerpen et al.
(114), crude glycerol obtained by transesterification is composed of 50 wt.% or less glycerol. The remaining contents
are primarily water, salts, unreacted alcohol and catalyst.
To produce high-quality glycerol, these contaminants must
be removed.
Purification Techniques for Glycerol Synthesized with
Inorganic Catalysts
Recently, crude glycerol separation and purification activities have expanded considerably, and academic institutions
have explored more innovative methods, theories and process
designs in these respects.
Salt Separation
For crude glycerol derived with an alkaline catalyst, treatment begins by neutralization using certain acids. This
technique efficiently removes alkaline matter, including
258
excess catalyst and the abundant soaps formed during transesterification processes employing homogeneous catalysts.
The neutralization separates the reaction mixture into three
phases using a strong- or medium-strength mineral. The
three phases consist of the catalyst in the bottom phase, the
neutralized glycerol and methanol in the middle phase and
the free fatty acids (FFAs) in the top phase (115).
Acids are used to neutralize excess alkaline catalysts,
whereas bases are used to neutralize acidic catalysts.
Sometimes, hydrochloric or sulphuric acid is employed in a
re-neutralization step and produces sodium chloride or potassium sulphate, respectively (97). However, using phosphoric
acid is more environmentally friendly. Phosphoric acid neutralizations produce a phosphate salt that is widely used as
a fertilizer. Sulphuric and hydrochloric acids produce environmentally harmful substances during neutralization. The
amount and concentration of acids used in neutralization
exert major effects on the separation time and the removal
of free fatty acids and salts (116).
Usually, the crude glycerol is reacted with greater than
1 mole of 85 wt.% sulphuric acid. Afterward, sodium borohydride or sodium hydroxide solution is added to neutralize
the excess acid and to remove colored impurities. Hajek
and Skopal (93) demonstrated that sequential neutralizations or saponifications could yield 84% purity glycerol.
Furthermore, Kongjao et al. (117) asserted that acidifying
the crude glycerol with mineral acids (such as sulphuric
acid) converted soap impurities into insoluble fatty acids
according to reaction (1).
RCOONa + H2 SO4 RCOOH + Na+ + SO2
4
(1)
Crystallization or Precipitation
In another separation technique, catalyst salts in solution after acidic treatment are removed by precipitation as
hydroxyapatite (HAP). The co-addition of lime (Ca(OH)2 )
and phosphoric acid to the pre-treated glycerol results in
calcium apatite (Ca5 (PO4 )3 (OH)) formation. This chemical
reaction removes solubilized catalyst from glycerol samples
(98). The reaction and precipitation is driven by calciumion and hydroxide-ion attraction. Separation of the calcium
apatite by gravity or centrifugation removes nearly all of the
excess catalyst.
Methanol Removal and Recycling
Excess un-reacted methanol is a major contaminant in crude
glycerol. High methanol levels are toxic, particularly in animal feeds and pharmaceuticals. Methanol is inherently toxic
but not directly poisonous. Alcohol dehydrogenase enzyme
in the liver converts methanol to formic acid and formaldehyde, which causes blindness by the destruction of the
optic nerve (118). The excess methanol must be removed to
achieve the level deemed safe by the U.S. Food and Drug
Administration (FDA). Brockmann et al. (119) reported
TABLE 9
Standard glycerol characterization methods
Physical properties
Glycerol content
Density
Viscosity
Ash value
Acidity
Moisture content
Heat of combustion
United States
Pharmacopeia
(USP)
ASTM
European
Standard
Method
(EN)
USP 26
D5002-94
D445-96
D0482-03
D1093-98
D4377-00E01
D0240-92
14214
14214
References
(97)
(120)
(110)
(97)
(97)
(97)
(121)
excess methanol removal using a flash evaporation. This

technique, based on the boiling point of alcohols, removed
nearly 100% of the methanol. In summary, a methanol
removal step is needed to meet the general usage requirements set by international standards (ASTM and EN in
Table 9).
Removal of Solid Contaminants
Heterogeneous catalysts are better suited for glycerol production than homogeneous catalysts. Heterogeneous catalysts afford a considerably cleaner crude glycerol, and
heterogeneous catalysts can be easily removed by simple filtration. The disadvantages of heterogeneous catalysts
include their high cost and difficult syntheses. Homogeneous
catalysts are better focussed. However, neutralizing homogeneous catalysts produce more salt.
Furthermore, years ago, the Wurster and Sanger singleeffect glycerine evaporator was developed to overcome the
salt removal problem (122). The first of the three apparatuses
had a large chamber that functioned to collect salts. After
a neutralization, the entire mixture was dropped into a tank
with a false bottom comprising a filter bed of wire screen
and filter cloth. The crude glycerol was pumped away from
below the false bottom. The salt was washed with lye and
then with water. The wash liquors were pumped back into
the evaporator feed tank.
Depending on the crude glycerol content, this procedure
decreased the salt content to 0.5 to 2.0 wt.% (122). This
method for removing salt was used only in single-effect
evaporations. The second method, which is still extensively
used in small and moderately sized plants, has the evaporator
bottoms connected to salt filters, salt boxes or salt extractors.
For a double-effect evaporator, three salt extractors are typically used. The setup allows for both evaporators to drop salt
while one extractor is emptied. Salt is allowed to accumulate in the evaporator during the time required to steam, dry
and empty its extractor. Furthermore, this second apparatus
allows for the salt to be removed from the evaporators continuously and dyed. The third apparatus utilizes salt drums
and centrifuges for complete salt removal.
Recently, Buenemann et al. (123) reported an advanced

technology for removing solids from crude glycerol. This
technique employs microfiltration or ultrafiltration using
ceramic-supported zirconia or alumina filters. The ceramic
material has a high mechanical resistance and tolerates a
wide range of temperatures and pH values. Theoretically, the
micro-sized catalysts and salts are easily isolated using these
ceramic-supported zirconia or alumina filter membranes
(124). This process has produced high-quality glycerol without any significant loss in yield.
Gomes et al. reported that ceramic membranes made of
tubular-type -Al2 O3 /TiO2 are able to purify glycerol to
high purity levels (125). The microfiltration process proposed by Gomes et al. consisted of two stages. First, a
3.5-kg mixture was prepared with a mass composition of
80% biodiesel, 10% alcohol and 10% glycerol. In the second stage, the membrane that yielded the best permeate flux
and free glycerol retention was identified. This microfiltration membrane has also been used to filter other micro-sized
materials from glycerol (126). Large glycerol streams can
be purified continuously, effectively and economically even
with frequent provenance changes. This technique has produced technical-grade glycerol (above 99.2 wt.%).
Saleh et al. (80) reported an ultrafiltration (UF) technique
for separating crude glycerol from the fatty acid methyl
ester (FAME) phase. This pressure-driven technique was performed using 1-100-nm membranes. Specifically, this UF
technique removed high-molecular-weight substances, colloidal materials, organic and inorganic molecules. The technique was employed in several other applications, including
virus prevention and bacteria and waste water recycling
(127). This application can effectively recover and separate crude glycerol from the FAME phase. In the Saleh
et al. study, adding a small amount of water (approximately
0.06 mass %) improved separation and efficiency (80).
Conversely, a nanofiltration technique was used to remove
1- to 100-nm particles in a high-viscosity separation (128).
Removing Ions and Colored Contaminants by
Adsorption
During the reaction, some catalysts dissolve into the reaction medium as free ions. To remove these free ions,
ion exchange resins have been used. Both column and
batch methods have been investigated (129). Synthetic ion
exchange resins have been produced commercially since the
1960s. Strong acid cation exchange resins and strong base
anion exchange resins, which fully ionise over the entire
pH range, are supported on three-dimensional polystyrene
cross-linked with an agent such as divinylbenzene. To convert the cross-liked polystyrene to a hydrogel with an ion
exchange capability, ionic functional groups are attached
to the polymeric network by a variety of chemical means.
For example, sulphonating a styrene-divinylbenzene copolymer permanently attaches sulphite (-SO3 ) groups, affording
259
a negatively charged matrix and exchangeable, mobile and

positive hydrogen ions (130). The specific linkages and
three-dimensional structures play important roles in adsorbing contaminants.
Two separate ion exchange resins can be used to exchange
cations for hydrogen ions (H+ ) and anions for hydroxyl ions
(OH ). The hydrogen and hydroxyl ions subsequently combine to form pure water, as shown in Figure 4. If maintaining
neutrality is desired, Na+ , Ca2+ , K+ or Mg2+ resins can be
utilized instead of H+ resins. Likewise, Cl , HCO3 , SO4 2
or NO3 resins can replace strongly basic OH resins. The
maximum ion exchange capacity of strong acid cation or
strong base anion exchangers is stoichiometric i.e., the
capacity is based on the equivalents of mobile charge within
the particular resins. Thus, one mol of H+ is one equivalent. One mole of Ca2+ is two equivalents. Anion and cation
exchange resins used together ensure that the ion exchange
resins capture both free anions and cations from the crude
glycerol sample, maximizing performance. This process has
produced glycerol of purities higher than 99.2%.
In another case, acidic ion exchange resin beads were
used to separate fatty acid salts and inorganic salts from
glycerol (131). This purification was effective when highquality resins consisting of 4 to 65 wt.% cross-linker were
used. Uniformity coefficients no greater than 1.15 were necessary to ensure that the glycerol passed through the bed
at a minimum flow rate of 0.3 bead volumes per hour. The
gel-type resins in this cross-linker range were more suitable
for the separation of soluble substances than resins with less
than 10% cross-linker. High cross-linking affected separation efficiency. Rezkallah (131) also claimed that the salts
and colored impurities eluted from the column earlier than
the glycerol. The afforded glycerol exhibited a considerably
lower ion and colored impurity content.
Amberlite-252, a strong acid cationic exchange resin, has
also been employed. Carmona et al. (132) reported that
the macroporous Amberlite could be used for sodium ion
removal from glycerol/water solutions containing high salt
concentrations. This resin was capable of yielding technicalgrade glycerol from many different processes. Purification
using Amberlit-252 was particularly efficient because of its
ability to be regenerated more than five times without any
significant loss of exchange capacity (129).
Distillation as a Single Purification Step
Many years ago, crude glycerol was purified using a simple distillation unit. As a result, the glycerol contained ash,
matter organic non-glycerol, water and soap (108). The
distillation was reported as a successful method for purifying crude glycerol that is similar in composition to the source
of commercial glycerol used today. An illuminating comparison of crude, purified and commercial-grade glycerol is
shown in Table 10. The corresponding analyses were performed based on standard methods: glycerol content ISO
260
KCl in glycerol
solution
K+
Cl
H+
Cl
K+
H+
OH
OH
H+
OH
H+
OH
OH
H+
H+
OH
H2O
FIGURE 4 Schematic representation of ion exchange columns that shows sodium and chloride ions exchange for hydrogen and hydroxyl ions, respectively.
The latter ions combine to form water.
TABLE 10
Characterization of crude, purified and commercial-grade glycerol
Parameter
Glycerol content (%)
Moisture (%)
Ash (%)
Soap (%)
Acidity
pH value
Chloride (ppm)
Color (APHA)
Gross energy (Cal/g)
Crude glycerol
Purified glycerol
Commercial glycerol
References
6080
1.56.5
1.52.5
35
0.71.3
9.811.2
n.d
Dark
36853825
99.199.8
0.110.80
0.054
0.56
0.100.16
6.76.9
1.0
3445
58105831
99.299.98
0.140.29
<0.002
n.a
0.940.07
6.76.8
0.69.5
1.810.3
5832
(97)
(133)
(133)
(19)
(134)
(11)
(133)
(133)
(133)
2879-1975; ash content ISO 2098-1972; and matter organic

non-glycerol (MONG) ISO 2464-1973.
The ash in crude glycerol was primarily sodium catalyst
salts (96). During glycerol recovery, trace amounts of shortand medium-chain fatty acids were retained in the crude
glycerol (106,135). At the high distillation temperature, the
free sodium hydroxide reacted with the fatty acids, forming short- and medium-chain soaps. Higher pH levels, due to
the presence of more sodium hydroxide, resulted in greater
soap formation. Sodium hydroxide also catalyzed glycerol
polymerization to polyglycerol (136).
Many works have explored the distillation of the glycerol phase as a method for removing methanol (137). This
technique operates based on boiling points. Two or more
materials with different boiling points can be separated
using vacuum distillation, and this concept was applied to

glycerol purification. Before distillation, the glycerol was
acidified (134). The success of vacuum distillations depends
on temperature (T) and pressure (P). The crude glycerol was
successfully distilled at 120126 C and 4.0 101 to 4.0
102 mbar, producing 96.6% purity glycerol. The optimum pH for the distillation was less than 5, which obviated
foaming.
This technique is sensitive and must be monitored to avoid
undesirable reactions. Three possible reactions can reduce
the glycerol yield during distillation: polymerization, dehydration and oxidation. The polymerization of glycerol to
polyglycerol occurs readily at high pH values, excess NaOH
concentrations and high temperatures (>200 C) (136,138).
Glycerol dehydrates to acrolein (bp. 52 C) at low pH
(99,139), and the acrolein accumulates in the cold trap during distillation. In addition, glycerol can oxidise to glycerose,
glyceraldehyde and dihydroxyacetone (140).
Recent Industrial Purification Processes

Recently, environmental issues have propelled the refinery
industry to develop new technologies for glycerol purification. Many techniques are combined into a single step or
a limited number of steps to enhance recovery and purification, e.g., soap splitting followed by salt and methanol
removal. Some separation techniques have employed vacuums because of glycerols heat sensitivity (glycerol decomposes at 180 C) (119).
As established methods, thes following technologies may
be used to further enhance the purity of glycerol after
the soap splitting step: fractional distillation, ion exchange,
adsorption, precipitation, extraction, crystallization and dialysis. The most common purification pathway, in sequential
order, is soap splitting, combined methanol/water removal,
fractional distillation, ion exchange (zeolite or resins) and
adsorption (active carbon powder) (120,131). Well-known
companies manufacture glycerol purification equipment. For
example, companies such as Desmetballestra and Buss-SMS
Canzler market ion exchange equipment. Other chemical
companies, such as Rohm & Haas and Lanxess, supply ion
exchange granulates, whereas Norit Company supplies powder and granulated activated carbon as glycerol bleaching
and decolorizing agents (119). Their activated carbon, with
its large surface area and high porosity, adsorbs pigments
and organic matter easily for large glycerol samples. Ion
exchange applications may be performed by either a column or batch technique (129). In addition, higher capacity
ion exchanges that will make high-purity glycerol production
more facile are being developed.
Many glycerol refinement plants exist today. Biodieselbased glycerol is manufactured in various grades by
treatment using single or multiple steps neutralization,
heating, condensing, refluxing and distillation (31,141).
Approximately 9095% of commercial glycerol is purified
to remove most impurities and increase market value. The
residual methanol in crude glycerol is removed easily using
evaporation and can be recycled to reduce the cost of purification. The final purification stage consists in using an
absorber to remove any soluble impurities in glycerol (111).
Purification of glycerol from biodiesel processing using
AMBERSEP BD50 technology (142), which employs an
ion exchange resin, is an effective and innovative process.
The biodiesel industry generates a tremendous amount of
crude glycerol. The crude glycerol that is produced as a byproduct in the transesterification process to make biodiesel
typically contains high levels of salts, stemming from the use
of homogeneous transesterification catalysts such as sodium
methylate (14). Most applications for glycerol require the
elimination of these salts. Indeed, the conventional methods
261
use to purify the crude glycerol are faced with high operating
costs and low efficiency.
For most applications in the food and pharmaceutical
sectors, crude glycerol needs be purified to pharmaceutical
grade. This high-quality grade can be realized by employing a combination of techniquese.g., heating, evaporation,
splitting, decantation, adsorption and vacuum distillation
(143). This combinatory process produces glycerol with a
purity greater than 99.5% from typical crude glycerol, which
contains a mixture of monoglycerides, diglycerides, triglycerides, methanol, water, fatty acid alkyl esters, catalyst and
salts. A flow diagram of a typical glycerol purification is
shown in Figure 5.
EET Corporations patented HEED technology can also
produce high-purity glycerol. This processing equipment
is an economical solution for glycerol purification in the
biodiesel and soap industries. By using EETs technology, crude glycerol from biodiesel and saponification processes can be refined to achieve the USP-grade quality
requirement of 99.7% purity (144). Alternatively, lowercost and intermediate-purity grades can be produced for
direct use or chemical conversion into other compounds
such as propylene glycol and ethylene glycol. In addition, EETs membrane-based technology avoids important
problems associated with stand-alone evaporation and distillation, such as foaming, cross-contamination, corrosion,
limited recovery and high costs in energy, maintenance and
operation.
The robustness of EETs technology allows it to be
applied to neutralized glycerol either before or after
methanol removal and over a range of feed compositions.
Other HEED applications include purification of refined
glycerol that has been distilled or evaporated but nevertheless contains residual salts or organic substances. EETs
glycerol purification process begins with a pre-treatment to
remove solids and fouling organics and to partially remove
color-causing organics.
The HEED (also known as HEEPM) system configuration combines customized automated controls and control
logic to provide the optimal desalting of a particular pretreated crude glycerol. This established technique produces
colorless glycerol with low salt content. The process is considered a good, efficient technique for producing high-purity
glycerol. However, its complicated technology contributes
to high production costs and therefore makes the systems
uneconomical. Efficient technologies need to be developed
to produce high-quality glycerol at a lower cost.
Disposing of crude glycerol is both costly and wasteful.
An applied technology for crude glycerol purification
was introduced by SRS Engineering Company (145).
Incorporated into SRSs high-purity glycerol purification
system (the SRXG-Series distillation column) is an ideal
combination of processing steps. The SRXG-Series system
produces high-purity glycerol without any significant loss in
yield. In summary, these technologies illustrate that investing
262
FIGURE 5 General flow diagram for a high-purity glycerol manufacturing process.
in the development of purification technologies can eliminate disposal costs and provide a new venue for profit in
the form of purified glycerol. The SRS system was able to
purify crude glycerol to technical-grade glycerol (over 97%)
(145). Furthermore, the purification of crude glycerol with
high methanol and water content was successfully performed
by Rototherm mechanically agitated thin-film processors.
These thin-film processors can be operated continuously and
in combination with distillation. They can also be used with
products containing sensitive solids (146).
Cost Estimates for Glycerol Purification Processes

Some information for crude glycerol purification by different methods was provided and discussed in this subtopic.
However, not much paper published in cost estimation for
this process. Posada et al. (2011) was reported the glycerol purification achieved up to 98 wt.% by combination of
neutralization, centrifugation, evaporation and column distillation (147). During the purification process, methanol at
99 wt.% is recovered and thus for the economic assessment, two scenarios were analyzed. In the first scenario,
the obtained methanol is considered as a process waste.
In the second scenario the methanol is considered as a
co-product that could be recycled to the transesterification
process and an economic value is given to this stream. The
lowest cost for glycerol purification was obtained under the
second scenario conditions (0.149 USD/kg). In other work,
the enrichment process of crude glycerol was performed
via chemical extraction and physical adsorption processes
by Hunsom et al. (148). For the whole enrichment process, based on equal quantity of crude glycerol, it was
noticed that the adsorption process was cheapest process
(5.72 USD/L crude glycerol) while a combined process of

chemical extraction with n-C3 H7 OH and adsorption was the
most costly (17.1 USD/L crude glycerol).
Glycerol Conversion to Other Chemicals

Recently, numerous papers have been published on the
direct utilization of glycerol. For example, glycerol can be
converted into value-added products by pyrolysis, steam
gasification or catalytic treatment. Glycerol can be catalytically converted into many other liquid products, including
acetaldehyde, acrolein, formaldehyde and hydroxyacetone.
Buhler et al. (149) reported the production of methanol,
acetaldehyde, acrolein, allyl alcohol, acetone, ethanol, carbon dioxide, carbon monoxide and hydrogen from glycerol
under supercritical conditions.
Additionally, Kunkes et al. (150) reported the conversion
of glycerol to syngas (H2 , CO, CO2 ) using Re on Pt/C as
a catalyst. The syngas was subsequently used to produce
a series of alcohols (151,152). Thiruchitrambalam (153)
reported that glycerol can be completely converted into H2 rich syngas through pyrolysis at 800 C in a fixed-bed reactor.
Cortright et al. (154) reported H2 production from the aqueous phase carbohydrate reforming of glycerol over Pt/Al2 O3
catalysts. In this reaction, hydrogen (H2 ) was afforded in
64.8 mol% yield. Buhler et al. (149) produced allyl alcohol, acetaldehyde, acrolein, methanol, CO, CO2 and H2 by
treating glycerol under supercritical conditions. However, a
low glycerol conversion (0.431 wt.%) was reported in this
work.
Chaudhari and Bakhshi (155) converted glycerol to
hydrogen by steam gasification. The steam gasification was
performed at steam flow rates of 2.5, 5.0, and 10 g/h
at 600 and 700 C. The glycerol flow rate was 4 g/h.

Approximately 80% conversion was achieved when a steam
flow rate of 10 g/h at 700 C was used. Chaudhari and
Bakhshi (155) illustrated that the steam gasification of glycerol does not produce liquid product at 600 and 700 C in a
fixed-bed reactor. In contrast, Stein and Antal (156) demonstrated that steam gasification of glycerol afforded acrolein
and acetaldehyde liquid products at 600675 C in a laminar
flow reactor.
High-purity glycerol can be reacted with oleic acid
to form monoacylglycerols and diacylglycerols, which are
widely used as biolubricant additives (157161). One acylglycerol synthesis reported was the esterification of glycerol
with lauric acid to form glycerol laurate (162). These compounds possess high potential for use as biolubricants.
CONCLUSIONS
In this review, we discovered that crude glycerol can be
easily recovered from biodiesel by centrifugation or gravitational settling. However, the challenge is purification of this
crude glycerol to food-grade glycerol. For most applications,
glycerol needs to be free of impurities particularly catalysts, salts and soap to avoid the formation of unwanted
by-products during manufacturing. Currently, the glycerol
purification process is expensive and is plagued with handling and separation problems. Many methods have been
employed to purify glycerol, including neutralization, splitting, heating, ultrafiltration, ion exchange chromatography
and vacuum distillation. The combination of more than one
of these techniques can successfully yield pharmaceuticalgrade glycerol, and recovered and purified glycerol has
been converted into many valuable products, e.g., methanol,
hydrogen, 1,3-propanediol, glycerol tert-butyl ether (GTBE).
FUNDING
The authors thank Universiti Kebangsaan Malaysia (UKM)
for funding this project under research grant number UKMGUP-BTK-08-14-306/Dana Lonjakan, LRGS/BU/2011/
USM-UKM/PG/02, DPP-2013-056 and DIP-2012-022.
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This article was downloaded by: [Universiti Kebangsaan Malaysia], [Wan Isahak]

On: 11 October 2014, At: 00:22

Separation & Purification Reviews

Recovery and Purification of Crude Glycerol from

& Mohd Ambar Yarmo

Department of Chemical Engineering and Process, Faculty of Engineering and Built

PLEASE SCROLL DOWN FOR ARTICLE

Separation & Purification Reviews, 44: 250267, 2015

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Recovery and Purification of Crude Glycerol from

Received 19 August 2011, Accepted 30 September 2013.

Crude glycerol production from biodiesel conversion is

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GLYCEROL RECOVERY FROM VEGETABLE OIL

CHEMICAL COMPOSITION OF CRUDE

PRODUCTION OF GLYCEROL FROM

FIGURE 1 Transesterification process that produces alkyl esters and

W. N. R. WAN ISAHAK ET AL.

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Homogeneous Catalytic Systems

FIGURE 2 Hydrolytic processes: a) acid-catalyzed hydrolysis and b)

The most active catalysts, alkaline metal alkoxides such

GLYCEROL RECOVERY FROM VEGETABLE OIL

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Sparingly soluble catalysts such as calcium oxide, sodium

Basic scheme for biodiesel and glycerol production.

W. N. R. WAN ISAHAK ET AL.

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Immobilized Enzyme Catalytic System

phase allows for a short reaction time (60). Compared with

The transesterification reaction is also performed using

GLYCEROL RECOVERY FROM VEGETABLE OIL

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PRODUCTS SEPARATION AND CATALYST

for nano-sized catalytic particles because of their higher

Homogeneous catalysts are the most active catalysts for

Ionic Liquid (ILs) Catalytic Systems

W. N. R. WAN ISAHAK ET AL.

Nanoparticle Catalyst Recovery Processes

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Homogeneous Catalyst Recovery Processes

Heterogeneous Catalyst Recovery Processes

Supercritical Methanol Recovery Process

Ionic Liquid Catalyst Recovery Process

CRUDE GLYCEROL RECOVERY PROCESS

Theoretically, the glycerol of vegetable oil transesterification

GLYCEROL RECOVERY FROM VEGETABLE OIL

Percentage range (%)

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Note: MG: Monoglyceride, DG: Diglyceride, TG: Triglyceride.

process, glycerol is dissolved in the soap lye and in the crude

gel beds to adsorb glycerol from methanol-free biodiesel

OVERVIEW OF GLYCEROL PURIFICATION

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W. N. R. WAN ISAHAK ET AL.

excess methanol removal using a flash evaporation. This

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GLYCEROL RECOVERY FROM VEGETABLE OIL

Recently, Buenemann et al. (123) reported an advanced

a negatively charged matrix and exchangeable, mobile and

W. N. R. WAN ISAHAK ET AL.

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2879-1975; ash content ISO 2098-1972; and matter organic

Separation & Purification of Crude Glycerol

Separation & Purification of Crude Glycerol