Separation Purificationofcrudeglycerol
Separation Purificationofcrudeglycerol
Separation Purificationofcrudeglycerol
net/publication/260189453
CITATIONS READS
22 21,315
5 authors, including:
Some of the authors of this publication are also working on these related projects:
Thermophilic biohydrogen production by attached-biofilm on granular activated carbon (GAC) from palm oil mill effluent View project
All content following this page was uploaded by Wan Nor Roslam Wan Isahak on 11 October 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
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
Separation & Purification Reviews, 44: 250–267, 2015
Copyright © Taylor & Francis Group, LLC
ISSN: 1542-2119 print / 1542-2127 online
DOI: 10.1080/15422119.2013.851696
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 glyc-
erol 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 purifi-
cation 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, partic-
ularly in the fields of hydrogen production, methanol production, pharmaceuticals and food
additives.
Keywords: Crude glycerol, purification, ion exchange resins, separation technique, ultrafiltra-
tion, vacuum distillation
direct use in high-tech applications. To overcome this prob- PRODUCTION OF GLYCEROL FROM
lem, numerous treatments are required to remove impurities. VEGETABLE OIL
Moreover, the manufacturing and pharmaceutical indus-
tries have increasingly demanded high-quality, food-grade The two primary processes for biodiesel production are
glycerol because of its superior physical properties, low hydrolysis and transesterification. Hydrolysis refers to a
contamination and odorlessness (9). chemical reaction in which water molecules are split into
Therefore, an effective, efficient glycerol purification oxygen and hydroxide anions, whereas a biodiesel transes-
process is needed to minimise production costs, minimise terification refers to a reaction that occurs between a triglyc-
industrial waste and maximise the utility of biodiesel indus- eride or fat and an alcohol to form alkyl esters (biodiesel
trial processes. Because of the enormous demand for the fuel) and glycerol (Figure 1). The theoretical stoichiomet-
production of glycerol from biodiesel waste, we have ric ratio of alcohol to lipids for these transesterifications is
thoroughly reviewed vegetable oil transesterification and 3:1. In reality, a 6:1 ratio is necessary to achieve practical
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
hydrolysis as a glycerol synthetic route. Various purifica- yields. The alcohol molecules displace the triglyceride (tri-
tion methods for producing high-purity glycerol are herein acylglycerol) molecules in forming an ester. This process is
discussed, and some glycerol conversion processes are also known as alcoholysis because cleavage of an alcohol
summarized. 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
CHEMICAL COMPOSITION OF CRUDE major problems in catalyst recovery, product separation and
GLYCEROL product purification are encountered (16–18).
Transesterification requires an alcohol. Methanol and
The factors that influence the quality of crude glycerol ethanol are the most frequently used alcohols for biodiesel
derived from biodiesel production processes include cata- transesterification reactions; propanol and butanol are also
lyst type and quantity, recovery methods, unreacted methanol widely employed. For environmentally friendly processes,
and other impurities. For example, a crude glycerol extracted ethanol is chosen because it can be derived from agricul-
from sunflower oil biodiesel had a composition (w/w) of tural products or other renewable resources. Alternatively,
30% glycerol, 50% methanol, 13% soap, 2% moisture, methanol is chosen for its lower cost, high polarity and short
2-3% salts (primarily sodium and potassium) and 2–3% alkyl chain (19).
other impurities (7). In contrast, Hansen et al. (10) reported
glycerol contents of 38 to 96% in a set of 11 crude glyc-
erol samples collected from 7 different Australian biodiesel Hydrolysis Processes
producers. Some of those samples contained more than
Vegetable oil hydrolysis is achieved using an acid or base
14% methanol and 29% ash. Because most biodiesel pro-
catalyst and produces glycerol and free fatty acids or soaps.
duction uses low-grade methanol and homogeneous alka-
Base-catalyzed ester hydrolysis is commonly called saponi-
line catalysts (sodium methoxide or potassium hydroxide),
fication. Both processes are shown in Figure 2. The perfor-
the quality of the afforded glycerol is poor (11). Saman
mances of various vegetable oil hydrolyses are summarized
et al. identified several contaminants in crude glycerol –
in Table 1. In previous studies, Hammond and Inmok (20)
methanol, soaps, catalysts, salts, non-glycerol organic matter
reported that lipase split triglycerides into free fatty acids
and excessive water (12). and glycerol. Their hydrolyses were performed with 17 to
Even when identical feedstocks were employed, the 44% moisture, and water was applied by various suitable
crude glycerol produced from alkali- and lipase-catalyzed techniques, e.g., soaking and spraying.
transesterifications was reported to differ in purity (13). Hydrolysis without a catalyst at 270–350◦ C, 20 MPa and
For biodiesel production that utilized homogeneous alka- a water/oil feed ratio of 50/50 (v/v) afforded approximately
line 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 alter-
natives 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 FIGURE 1 Transesterification process that produces alkyl esters and
different method of removal. glycerol.
252 W. N. R. WAN ISAHAK ET AL.
TABLE 1
Performance of various vegetable oil hydrolytic processes
Type of catalyst/reaction Molar ratio Temperature (◦ C) Time (h) Conversion (%) References
Homogeneous basic
NaOH 6:1 45 0.25 98 (35)
KOH 6:1 60 1 100 (36)
NaOCH3 6:1 60 2 97.1 (37)
Homogeneous acidic
AlCl3 and ZnCl2 24 : 1 110 18 98 (38)
H2 SO4 50 : 1 80 4 97 (39)
H2 SO4 20 : 1 95 20 >90 (40)
H2 SO4 245 : 1 70 4 99 (41)
Trifluoroacetic acid 20 : 1 120 5 98.4 (33)
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
when supported on alumina, metal or zeolites. A compara- Sparingly soluble catalysts such as calcium oxide, sodium
tively high reaction temperature is required to achieve only a methoxide and barium hydroxide have exhibited high activ-
slow reaction rate in acid-catalyzed transesterifications. ities for rapeseed oil transesterification (43). During veg-
Previous studies have reported that vegetable oil transes- etable oil transesterification using calcium oxide, calcium
terification using heterogeneous acid catalysts is not a prac- glyceroxide was produced through the reaction of calcium
tical process because it requires high temperatures, lengthy oxide with glycerol. This by-product created more active
reaction times and large catalyst charges. In addition, syn- sites and thus enhanced the reaction rate (44). The activ-
thesizing the catalysts was reported to be complicated and ities of heterogeneously catalyzed reactions are listed in
uneconomical. Catalyst leaching also presented a risk of Table 3.
product contamination. These drawbacks led to higher sepa-
ration costs and created additional problems we will not dis-
The Supercritical Methanol System
cuss. However, the solid acid catalysts could be regenerated
and reused. Transesterification reactions using basic or acidic cata-
Supported basic heterogeneous catalysts, such as potas- lysts are relatively time-consuming and require complex
sium hydroxide on alumina (KOH/Al2 O3 ), have exhib- separations, resulting in high production costs and energy
ited high activities and basicity (11). One optimized consumption. To overcome these problems, supercritical
KOH/Al2 O3 reaction afforded 90.54% diesel and 9.46% methanol (SCM) has been proposed for catalyst-free veg-
glycerol. Arzamendi et al. (42) reported conversions up to etable oil transesterifications (57–59). Whereas vegetable
99% when sodium hydroxide on alumina (KOH/Al2 O3 ) was oil transesterifications with regular methanol are biphasic
employed. The high conversions resulted from the catalyst’s reactions, the lower dielectric constant of supercritical
high number of active sites and the catalyst’s basicity. methanol results in a one-phase reaction solution. The single
TABLE 3
Various heterogeneous catalytic systems employed in glycerol production
Type of catalyst/reaction Molar ratio Temperature (◦ C) Time (h) Conversion (%) References
Heterogeneous basic
Ca (NO3 ) 2 /Al2 O3 65:1 60 3 94 (45)
CaO/Al2 O3 12:1 65 5 94 (46)
KOH/Al2 O3 15:1 <70 2–3 91.07 (47)
Mg-Al hydrotalcite 65:1 60 5 97 (48)
CaO 12:1 65 3 95 (49)
CaO/ZnO 30:1 60 1 94 (50)
Sulfated zirconia 20:1 120 1 98.6 (51)
Sr-Mg 9:1 60 30 min 97.3 (52)
Alum (KAl (SO4 )2 ·12H2 O) 18:1 170 12 92.5 (53)
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
Heterogeneous acidic
p-Toluenesulfonic acid (PTSA) 10:1 80 2 97.1 (54)
Metal acetates and stearic acid 20:1 60 1 100 (56)
Silicotungstic acid 12:1 150–200 3 9 (55)
phase allows for a short reaction time (60). Compared with Immobilized Enzyme Catalytic System
catalytic processes carried out at atmospheric pressure, the
The transesterification reaction is also performed using
non-catalytic SCM process involves a considerably simpler
enzyme catalysts. Lipase is the most efficient and active
purification step, a lower reaction time and lower energy.
enzyme for the reaction. To immobilize the enzyme, the
In addition, the SCM method is more environmentally
carbodiimide activation method is the most effective. The
friendly.
penicillium expansum lipase (PEL) systems discussed by
In investigating product separation problems, Hawash
Yang et al. (66) and Xu and Ma (67) are summarized in
et al. (61) reported that a non-catalytic transesterification
Table 5.
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. Nanoparticle Catalytic Systems
Moreover, a high molar ratio of methanol to oil was utilized
(61,62). Although high, the cost of the SCM process could Over the past three years, nanoparticle heterogeneous cat-
be offset because this reaction produces high-purity methyl alysts have been used in vegetable oil transesterifications
esters (99.6%) and glycerol (96.5%) (63). Glycerol produc- to easily separate the catalyst from the glycerol phase.
tion using the SCM technique is summarized in Table 4. The activity and performance was reported to increase
TABLE 4
Transesterification using supercritical methanol (SCM)
Molar ratio
Type of catalyst/reaction (MeOH:Oil) Temperature (◦ C) Time (min) Conversion (%) References
TABLE 5
Performance of transesterification reactions using immobilized enzymes as catalysts
Type of catalyst/reaction Molar ratio Temperature (◦ C) Time (h) Conversion (%) References
Type of catalyst/reaction Molar ratio Temperature (◦ C) Time (h) Conversion (%) References
for nano-sized catalytic particles because of their higher PRODUCTS SEPARATION AND CATALYST
surface area and availability of active sites. Boz et al. RECOVERY STAGE
(68) demonstrated KF-loaded nano-γ-Al2 O3 as a versa-
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
tile catalyst for transesterification. The catalytic perfor- Homogeneous catalysts are the most active catalysts for
mance of various nanoparticle catalysts is summarized in the vegetable oil transesterification reaction. However, the
Table 6. higher residual catalyst amounts associated with these cata-
lysts compared with those encountered in heterogeneous pro-
cesses lead to higher separation costs. Furthermore, unlike
Ionic Liquid (ILs) Catalytic Systems heterogeneous catalysts, homogeneous catalysts cannot be
recycled for reuse because they remain in the product. One
In other works, immidazolium-based ionic liquids and mul- technique for removing excess homogeneous catalyst is a
tiphase acidic or basic conditions have been used to pro- titrative method by which the acid or base catalyst is con-
duce glycerol from vegetable oil transesterification. High verted into its salt (38). Because of their ease of separation
yields of biodiesel (>98%) were afforded from soybean and ability to be regenerated, heterogeneous catalysts are
oil transesterification when the ionic liquid 1-n-butyl-
good, clean and cost-effective alternatives for producing
3-methylimidazolium bis (trifluoromethylsulphonyl) imide FAMEs and glycerol from vegetable oils. The solid cata-
(BMI.NTf2 ), alcohols and K2 CO3 or sulphuric acid were lyst can be removed by filtration, resulting in a less complex
used (72). The lack of a solid catalyst resulted in a clean
recovery of biodiesel and glycerol (78,79).
process. However, this catalytic process was not practical
Recovering glycerol from FAME phases was studied by
because of the high IL cost and difficulty in handling.
Saleh et al. (80). The researchers found that an ultrafiltration
Interestingly, Vidya and Chadha (73) reported that
technique successfully separated the small amount of glyc-
hydrophobic ILs such as [Bmim]PF6 and [Bmim]NTf2
erol contained in the FAME phase. Temperature significantly
were better media for vegetable oil transesterifications
increased water solubility in various commercial biodiesels
than the hydrophilic [Bmim]BF4 . They also indicated
(81). Consequently, using higher temperatures increased
that the IL anions strongly affected the catalytic perfor-
glycerol solubility in FAMEs and made the subsequent sepa-
mance of Pseudomonas cepacia lipase (73). Comparing
rations more challenging. Wang et al. (81) reported that using
two hydrophobic ILs, [Bmim]NTf2 performed better than
ceramic membrane separation at 60◦ C reduced the glycerol
[Bmim]PF6 . The higher viscosity of [Bmim]PF6 limited dissolved in FAME; however, this result was achieved only
mass transfer of the substrates and products to and from the after removing the methanol.
enzyme active sites and thus led to lower catalytic activity For glycerol produced by vegetable oil transesterification
(76). Isahak et al. (77) reported that the use of ionic liquids, with an ionic liquid, the catalyst can be separated from the
namely choline chloride, produced higher-quality biodiesels product mixture by a crystallization and freezing technique
and glycerol. The activities of various ionic liquid catalysts based on the boiling-point differences between glycerol and
are summarized in Table 7. the ionic liquid (72). The glycerol producers using super
TABLE 7
Performance of transesterification reactions using ionic liquids as catalysts
Molar ratio
Type of catalyst/reaction (MeOH:Oil) Temperature (◦ C) Time (h) Conversion (%) References
critical methanol (SCM) and hydrolysis were not apprehen- Nanoparticle Catalyst Recovery Processes
sive of any excess catalyst. However, unreacted triglyceride
Nanoparticle catalysts are difficult to remove using conven-
remained in the product mixtures. To remove the unre-
tional filtration. Polymeric membranes can recover nanopar-
acted material, a solvent extraction method that involves
ticle catalysts. The filtration efficiency depends on the mem-
overnight separation into layers based on weight and polarity
brane size. The nanoparticle catalysts used for vegetable oil
can be used. Otherwise, a centrifugation technique must be
transesterification processes resist separation and recovery.
employed to separate the products.
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 trans- Ionic Liquid Catalyst Recovery Process
esterification; therefore, the homogeneous catalysts are not
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
Few studies of heterogeneous catalyst regeneration exist. Here, glycerol recovery from hydrolysis, saponification and
Solid-phase heterogeneous vegetable oil transesterifica- transesterification reactions is reviewed. Various practical
tion catalysts can generally be recycled a few times methods and techniques have been used for glycerol recovery
without adverse effects. They can be removed eas- and enrichment.
ily 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 Hydrolysis
(85–87). Following re-calcination under N2 after an exten-
sive methanol wash, the catalysts are ready for additional Hydrolysis is divided into two processes: acid-catalyzed
reactions (88,89). Some researchers report that heteroge- hydrolysis and base-catalyzed hydrolysis (saponification).
neous catalysts can be reused without any treatment and The reaction produces two layers of product that can be
without any significant loss in activity (90). 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
Supercritical Methanol Recovery Process removed by filtration. Crude glycerol is obtained from the
lower phase by removing water through vacuum distillation
Catalyst-free supercritical methanol transesterification is (23). An advanced glycerol recovery technique was devel-
performed to increase the reaction rate and thus shorten the oped by modification of an ionic liquid-glycerol mixture to
reaction time. However, the excess SCM required leads to form “deep eutectic solvents” (DES). The synthesized DES
some difficulty in separation. The problem can be overcome was used to extract the glycerol from the biodiesel (92).
by an evaporation and layer separation technique (63).
Transesterification Reaction
Immobilized Enzyme Catalyst Recovery Process
Theoretically, the glycerol of vegetable oil transesterification
Immobilized enzymes are efficient catalysts for vegetable oil constitutes approximately 10% of the products. Typically,
transesterification. However, the production costs are high however, the recovered glycerol constitutes only 9 to 9.6%
and require catalyst reuse. Otherwise, difficulties in han- of the products (Table 8). In an effective biodiesel produc-
dling are the primary problems associates with immobilized tion process, only small amounts of the unreacted starting
enzymes. For reuse, the enzyme is isolated using centrifuga- materials remain in the glycerol phase. Glycerol is also an
tion. The recovered lipase is washed with organic solvents important by-product in soap production. When fats and
and is then ready for another reaction (68,91). oils are saponified by caustic soda in the soap production
GLYCEROL RECOVERY FROM VEGETABLE OIL 257
TABLE 8
gel beds to adsorb glycerol from methanol-free biodiesel
Typical percentages of transesterification products
streams is discussed (108).
Products of transesterification Percentage range (%) References
Glycerol from fats and oil in soap manufacturing usu- For use as animal food, several glycerol purification steps are
ally comprise approximately 10% of the total products. required to remove impurities (110).
Recovering usable materials is vital to the profitability of The purity of crude glycerol obtained from vegetable oil
any soap production process. Unfortunately, many small- transesterification depends on three parameters: the type of
and medium-scale soap producers discard the lye. The spe- catalyst used, the amount of excess alcohol and the con-
cific recovery technique employed is critical to recovering version achieved (111). The purity ranges of crude glycerol
glycerol from spent soap lye. The liquor that remains after produced by transesterification using homogeneous cata-
soap manufacture must be allowed to settle for 20 minutes lysts, heterogeneous catalysts and supercritical methanol
after stirring. The clear phase is decanted and discarded, (SCM) are 55–70%, 75–85%, and 96.5%, respectively (112).
and the remaining phase is heat treated at 60◦ C in a conical Currently, much attention is being focussed on employ-
flask (100). ing green catalytic transesterification processes to convert
The basic and acidic catalysts employed for glycerol pro- bio-renewable vegetable oils to commodity chemicals and
duction by transesterification are recovered via chemical clean fuels. These reactions are performed at lower tem-
treatment. Either sulphuric acid (H2 SO4 ) or sodium hydrox- peratures and atmospheric pressure using homogeneous or
ide (NaOH) are used to neutralize the catalysts to salts. For heterogeneous catalysts and excess methanol. However, the
example, H2 SO4 neutralizes NaOH in glycerol samples to excessive unreacted methanol presents a problem. Methanol
sodium sulphate (Na2 SO4 ). Fortunately, Na2 SO4 has low sol- is dangerous and can adversely affect human health and the
ubility in the aqueous glycerol solution, which is saturated environment. To overcome this problem, the excess methanol
with sodium chloride (NaCl). Indeed, NaCl remains primar- is recovered by processes such as evaporation and recycled
ily in the glycerol layer (101,102). Hence, the Na2 SO4 salts to the reactor for additional transesterification cycles.
can be removed by decantation and filtration. Crude glycerol contains 20.2% glycerol, 6.6% fatty acids
The highest glycerol yields are obtained by the bleaching (as soap) and 64.3% salt. Thus, 91.1% of crude glycerol
recovery technique (100). Bleaching (alkaline system) both residue consists of components that are potentially useful
purifies the glycerol and further saponifies the free triglyc- for other applications (113). According to van Gerpen et al.
erides (103). The amount of recovered glycerol depends (114), crude glycerol obtained by transesterification is com-
on the recovery point and on the purification stage during posed of 50 wt.% or less glycerol. The remaining contents
which the technique is utilized (104). The variation in glyc- are primarily water, salts, unreacted alcohol and catalyst.
erol recovery amounts obtained across the soap industry is To produce high-quality glycerol, these contaminants must
due to the different soap types of lye and methods of treat- be removed.
ment employed. For example, during the recovery stages,
glycerol can be lost through washing, graining and desalt-
ing. Moreover, if a temperature of 60◦ C is exceeded during Purification Techniques for Glycerol Synthesized with
treatment, side reactions may occur. Glycerol decomposes to Inorganic Catalysts
acrolein at higher temperatures (>140◦ C). Recently, crude glycerol separation and purification activi-
The crude glycerol derived from vegetable oil can ties have expanded considerably, and academic institutions
be recovered from the biodiesel phase by centrifugation. have explored more innovative methods, theories and process
Centrifugation is followed by hydrochloric acid treatment designs in these respects.
to convert any contaminant soaps to free acids or salts
(105,106). Methanol and water contaminants are removed
Salt Separation
by distillation (107). Afterward, the glycerol layer is neutral-
ized with caustic soda, producing 80% (w/w) crude glycerol. For crude glycerol derived with an alkaline catalyst, treat-
Next, some glycerol purification processes are presented. ment begins by neutralization using certain acids. This
In addition, a recovery technique that employs fixed silica technique efficiently removes alkaline matter, including
258 W. N. R. WAN ISAHAK ET AL.
TABLE 9
excess catalyst and the abundant soaps formed during trans-
Standard glycerol characterization methods
esterification processes employing homogeneous catalysts.
The neutralization separates the reaction mixture into three European
phases using a strong- or medium-strength mineral. The United States Standard
three phases consist of the catalyst in the bottom phase, the Pharmacopeia Method
Physical properties (USP) ASTM (EN) References
neutralized glycerol and methanol in the middle phase and
the free fatty acids (FFAs) in the top phase (115). Glycerol content USP 26 (97)
Acids are used to neutralize excess alkaline catalysts, Density D5002-94 14214 (120)
Viscosity D445-96 14214 (110)
whereas bases are used to neutralize acidic catalysts.
Ash value D0482-03 (97)
Sometimes, hydrochloric or sulphuric acid is employed in a Acidity D1093-98 (97)
re-neutralization step and produces sodium chloride or potas- Moisture content D4377-00E01 (97)
sium sulphate, respectively (97). However, using phosphoric Heat of combustion D0240-92 (121)
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
Recently, Buenemann et al. (123) reported an advanced a negatively charged matrix and exchangeable, mobile and
technology for removing solids from crude glycerol. This positive hydrogen ions (130). The specific linkages and
technique employs microfiltration or ultrafiltration using three-dimensional structures play important roles in adsorb-
ceramic-supported zirconia or alumina filters. The ceramic ing contaminants.
material has a high mechanical resistance and tolerates a Two separate ion exchange resins can be used to exchange
wide range of temperatures and pH values. Theoretically, the cations for hydrogen ions (H+ ) and anions for hydroxyl ions
micro-sized catalysts and salts are easily isolated using these (OH− ). The hydrogen and hydroxyl ions subsequently com-
ceramic-supported zirconia or alumina filter membranes bine to form pure water, as shown in Figure 4. If maintaining
(124). This process has produced high-quality glycerol with- neutrality is desired, Na+ , Ca2+ , K+ or Mg2+ resins can be
out any significant loss in yield. utilized instead of H+ resins. Likewise, Cl− , HCO3 − , SO4 2−
Gomes et al. reported that ceramic membranes made of or NO3 − resins can replace strongly basic OH− resins. The
tubular-type α-Al2 O3 /TiO2 are able to purify glycerol to maximum ion exchange capacity of strong acid cation or
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
high purity levels (125). The microfiltration process pro- strong base anion exchangers is stoichiometric – i.e., the
posed by Gomes et al. consisted of two stages. First, a capacity is based on the equivalents of mobile charge within
3.5-kg mixture was prepared with a mass composition of the particular resins. Thus, one mol of H+ is one equiva-
80% biodiesel, 10% alcohol and 10% glycerol. In the sec- lent. One mole of Ca2+ is two equivalents. Anion and cation
ond stage, the membrane that yielded the best permeate flux exchange resins used together ensure that the ion exchange
and free glycerol retention was identified. This microfiltra- resins capture both free anions and cations from the crude
tion membrane has also been used to filter other micro-sized glycerol sample, maximizing performance. This process has
materials from glycerol (126). Large glycerol streams can produced glycerol of purities higher than 99.2%.
be purified continuously, effectively and economically even In another case, acidic ion exchange resin beads were
with frequent provenance changes. This technique has pro- used to separate fatty acid salts and inorganic salts from
duced technical-grade glycerol (above 99.2 wt.%). glycerol (131). This purification was effective when high-
Saleh et al. (80) reported an ultrafiltration (UF) technique quality resins consisting of 4 to 65 wt.% cross-linker were
for separating crude glycerol from the fatty acid methyl used. Uniformity coefficients no greater than 1.15 were nec-
ester (FAME) phase. This pressure-driven technique was per- essary to ensure that the glycerol passed through the bed
formed using 1-100-nm membranes. Specifically, this UF at a minimum flow rate of 0.3 bead volumes per hour. The
technique removed high-molecular-weight substances, col- gel-type resins in this cross-linker range were more suitable
loidal materials, organic and inorganic molecules. The tech- for the separation of soluble substances than resins with less
nique was employed in several other applications, including than 10% cross-linker. High cross-linking affected separa-
virus prevention and bacteria and waste water recycling tion efficiency. Rezkallah (131) also claimed that the salts
(127). This application can effectively recover and sepa- and colored impurities eluted from the column earlier than
rate crude glycerol from the FAME phase. In the Saleh the glycerol. The afforded glycerol exhibited a considerably
et al. study, adding a small amount of water (approximately lower ion and colored impurity content.
0.06 mass %) improved separation and efficiency (80). Amberlite-252, a strong acid cationic exchange resin, has
Conversely, a nanofiltration technique was used to remove also been employed. Carmona et al. (132) reported that
1- to 100-nm particles in a high-viscosity separation (128). the macroporous Amberlite could be used for sodium ion
removal from glycerol/water solutions containing high salt
concentrations. This resin was capable of yielding technical-
Removing Ions and Colored Contaminants by grade glycerol from many different processes. Purification
Adsorption using Amberlit-252 was particularly efficient because of its
During the reaction, some catalysts dissolve into the reac- ability to be regenerated more than five times without any
tion medium as free ions. To remove these free ions, significant loss of exchange capacity (129).
ion exchange resins have been used. Both column and
batch methods have been investigated (129). Synthetic ion
Distillation as a Single Purification Step
exchange resins have been produced commercially since the
1960s. Strong acid cation exchange resins and strong base Many years ago, crude glycerol was purified using a sim-
anion exchange resins, which fully ionise over the entire ple distillation unit. As a result, the glycerol contained ash,
pH range, are supported on three-dimensional polystyrene matter organic non-glycerol, water and soap (108). The
cross-linked with an agent such as divinylbenzene. To con- distillation was reported as a successful method for purify-
vert the cross-liked polystyrene to a hydrogel with an ion ing crude glycerol that is similar in composition to the source
exchange capability, ionic functional groups are attached of commercial glycerol used today. An illuminating com-
to the polymeric network by a variety of chemical means. parison of crude, purified and commercial-grade glycerol is
For example, sulphonating a styrene-divinylbenzene copoly- shown in Table 10. The corresponding analyses were per-
mer permanently attaches sulphite (-SO3 ) groups, affording formed based on standard methods: glycerol content – ISO
260 W. N. R. WAN ISAHAK ET AL.
KCl in glycerol
solution
K+ Cl–
H+ OH–
Cl–
K+
OH–
H+ H+
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
OH– OH–
H+
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
2879-1975; ash content – ISO 2098-1972; and matter organic using vacuum distillation, and this concept was applied to
non-glycerol (MONG) – ISO 2464-1973. glycerol purification. Before distillation, the glycerol was
The ash in crude glycerol was primarily sodium catalyst acidified (134). The success of vacuum distillations depends
salts (96). During glycerol recovery, trace amounts of short- on temperature (T) and pressure (P). The crude glycerol was
and medium-chain fatty acids were retained in the crude successfully distilled at 120–126◦ C and 4.0 × 10−1 to 4.0
glycerol (106,135). At the high distillation temperature, the × 10−2 mbar, producing 96.6% purity glycerol. The opti-
free sodium hydroxide reacted with the fatty acids, form- mum pH for the distillation was less than 5, which obviated
ing short- and medium-chain soaps. Higher pH levels, due to foaming.
the presence of more sodium hydroxide, resulted in greater This technique is sensitive and must be monitored to avoid
soap formation. Sodium hydroxide also catalyzed glycerol undesirable reactions. Three possible reactions can reduce
polymerization to polyglycerol (136). the glycerol yield during distillation: polymerization, dehy-
Many works have explored the distillation of the glyc- dration and oxidation. The polymerization of glycerol to
erol phase as a method for removing methanol (137). This polyglycerol occurs readily at high pH values, excess NaOH
technique operates based on boiling points. Two or more concentrations and high temperatures (>200◦ C) (136,138).
materials with different boiling points can be separated Glycerol dehydrates to acrolein (bp. 52◦ C) at low pH
GLYCEROL RECOVERY FROM VEGETABLE OIL 261
(99,139), and the acrolein accumulates in the cold trap dur- use to purify the crude glycerol are faced with high operating
ing distillation. In addition, glycerol can oxidise to glycerose, costs and low efficiency.
glyceraldehyde and dihydroxyacetone (140). 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 employ-
Recent Industrial Purification Processes ing a combination of techniques—e.g., heating, evaporation,
Recently, environmental issues have propelled the refinery splitting, decantation, adsorption and vacuum distillation
industry to develop new technologies for glycerol purifica- (143). This combinatory process produces glycerol with a
tion. Many techniques are combined into a single step or purity greater than 99.5% from typical crude glycerol, which
a limited number of steps to enhance recovery and purifi- contains a mixture of monoglycerides, diglycerides, triglyc-
cation, e.g., soap splitting followed by salt and methanol erides, methanol, water, fatty acid alkyl esters, catalyst and
removal. Some separation techniques have employed vacu- salts. A flow diagram of a typical glycerol purification is
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
in the development of purification technologies can elimi- (5.72 USD/L crude glycerol) while a combined process of
nate disposal costs and provide a new venue for profit in chemical extraction with n-C3 H7 OH and adsorption was the
the form of purified glycerol. The SRS system was able to most costly (17.1 USD/L crude glycerol).
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 Glycerol Conversion to Other Chemicals
by Rototherm mechanically agitated thin-film processors.
These thin-film processors can be operated continuously and Recently, numerous papers have been published on the
in combination with distillation. They can also be used with direct utilization of glycerol. For example, glycerol can be
products containing sensitive solids (146). converted into value-added products by pyrolysis, steam
gasification or catalytic treatment. Glycerol can be catalyt-
ically converted into many other liquid products, including
acetaldehyde, acrolein, formaldehyde and hydroxyacetone.
Cost Estimates for Glycerol Purification Processes
Buhler et al. (149) reported the production of methanol,
Some information for crude glycerol purification by differ- acetaldehyde, acrolein, allyl alcohol, acetone, ethanol, car-
ent methods was provided and discussed in this subtopic. bon dioxide, carbon monoxide and hydrogen from glycerol
However, not much paper published in cost estimation for under supercritical conditions.
this process. Posada et al. (2011) was reported the glyc- Additionally, Kunkes et al. (150) reported the conversion
erol purification achieved up to 98 wt.% by combination of of glycerol to syngas (H2 , CO, CO2 ) using Re on Pt/C as
neutralization, centrifugation, evaporation and column dis- a catalyst. The syngas was subsequently used to produce
tillation (147). During the purification process, methanol at a series of alcohols (151,152). Thiruchitrambalam (153)
99 wt.% is recovered and thus for the economic assess- reported that glycerol can be completely converted into H2 -
ment, two scenarios were analyzed. In the first scenario, rich syngas through pyrolysis at 800◦ C in a fixed-bed reactor.
the obtained methanol is considered as a process waste. Cortright et al. (154) reported H2 production from the aque-
In the second scenario the methanol is considered as a ous phase carbohydrate reforming of glycerol over Pt/Al2 O3
co-product that could be recycled to the transesterification catalysts. In this reaction, hydrogen (H2 ) was afforded in
process and an economic value is given to this stream. The 64.8 mol% yield. Buhler et al. (149) produced allyl alco-
lowest cost for glycerol purification was obtained under the hol, acetaldehyde, acrolein, methanol, CO, CO2 and H2 by
second scenario conditions (0.149 USD/kg). In other work, treating glycerol under supercritical conditions. However, a
the enrichment process of crude glycerol was performed low glycerol conversion (0.4–31 wt.%) was reported in this
via chemical extraction and physical adsorption processes work.
by Hunsom et al. (148). For the whole enrichment pro- Chaudhari and Bakhshi (155) converted glycerol to
cess, based on equal quantity of crude glycerol, it was hydrogen by steam gasification. The steam gasification was
noticed that the adsorption process was cheapest process performed at steam flow rates of 2.5, 5.0, and 10 g/h
GLYCEROL RECOVERY FROM VEGETABLE OIL 263
at 600 and 700◦ C. The glycerol flow rate was 4 g/h. 4. Transparency Market Research. (2013) Glycerol Market by Source
Approximately 80% conversion was achieved when a steam (Biodiesel, Fatty Acids & Fatty Alcohols), by Applications (Personal
flow rate of 10 g/h at 700◦ C was used. Chaudhari and Care, Alkyd Resins, Polyether Polyols, Others), Downstream
Opportunities (Propylene Glycol, Epichlorohydrin, 1, 3 Propanediol
Bakhshi (155) illustrated that the steam gasification of glyc- and Others)—Global Industry Analysis, Size, Share, Trends, Growth
erol does not produce liquid product at 600 and 700◦ C in a and Forecast, 2012–2018. [http://www.biodieselmagazine.com/
fixed-bed reactor. In contrast, Stein and Antal (156) demon- articles/9004/report-glycerol-market-expected-to-reach-2-1-billion-
strated that steam gasification of glycerol afforded acrolein in-2018] (accessed May 14, 2013)
and acetaldehyde liquid products at 600–675◦ C in a laminar 5. Croy, C. and Dotson, K. (1995) Glycerine. INFORM, 6: 1104–1118.
6. Mohtar, Y., Tang, T.S., and Salmiah, A. (2001) Quality of basic
flow reactor. oleochemicals produced in Malaysia. INFORM, 12: 529–536.
High-purity glycerol can be reacted with oleic acid 7. Ash, M. and Ash, I. (2004) Handbook of Preservatives. Synapse Info.
to form monoacylglycerols and diacylglycerols, which are Resources: New York.
widely used as biolubricant additives (157–161). One acyl- 8. Ooi, T.L., Leong, W.L., and Radzuan, J. (1993) Potential source of
sterols from a palm kernel oil methyl ester residue of an oleochemical
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
22. Bhatkhande, B.S. and Samant, S.D. (1998) Ultrasound assisted 43. Gryglewicz, S. (1999) Rapeseed oil methyl esters preparation using
PTC catalyzed saponification of vegetable oils using aqueous alkali. heterogeneous catalysts. Bioresour. Technol., 70: 249–253.
Ultrason. Sonochem., 5: 7–12. 44. Kouzu, M., Tsunomori, M., Yamanaka, S., and Hidaka, J. (2010) Solid
23. Satyarthi, J.K., Srinivas, D., and Ratnasamy, P. (2010) Hydrolysis of base catalysis of calcium oxide for a reaction to convert vegetable oil
vegetable oils and fats to fatty acids over solid acid catalysts. Appl. into biodiesel. Adv. Powder Technol., 21: 488–494.
Catal. A: Gen., 391: 427–435. 45. Benjapornkulaphong, S., Ngancharussrivichai, C., and Bunyakiat, K.
24. Khuwijitjaru, P., Fujii, T., Adachi, S., Kimura, Y., and Matsuno, R. (2008) Al2 O3 supported alkali and alkali earth metals oxides for trans-
(2004) Kinetics on the hydrolysis of fatty acid esters in subcritical esterification of palm kernel and coconut oil. Chem. Eng. J., 145:
water. Chem. Eng. J., 99:1–4. 468–474.
25. Minami, E. and Saka, S. (2006) Kinetics of hydrolysis and methyl 46. Zabeti, M., Wan Daud, W.M.A., and Aroua, M.K. (2009)
esterification for biodiesel production in two-step supercritical Optimization of the activity of CaO/Al2 O3 catalyst for biodiesel pro-
methanol process. Fuel, 85: 2479–2483. duction using response surface methodology. Appl. Catal. A: Gen.,
26. King, J.W., Holliday, R.L., and List, G.R. (1999) Hydrolysis of 366: 154–159.
soybean oil in a subcritical water flow reactor. Green Chem., 1: 47. Noiroj, K., Intarapong, P., Luengnaruemtchai, A., and Jai-In, S. (2009)
261. A comparative study of KOH/Al2 O3 and KOH/NaY catalysts for
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
27. Alenezi, R., Leeke, G.A., Santos, R.C.D., and Khan, A.R. (2009) biodiesel production via transesterification from palm oil. Renew
Hydrolysis kinetics of sunflower oil under subcritical water condi- Energy, 34: 1145–1150.
tions. Chem. Eng. Res. Des., 87: 867–873. 48. Georgogianni, K.G., Katsoulidis, A.P., Pomonis, P.J., and
28. Holliday, R.L. and King, J.W. (1997) Hydrolysis of vegetable oil in Kontominas, M.G. (2008) Transesterification of soybean frying
sub- and supercritical water. Ind. Eng. Chem. Res., 36: 932. oil to biodiesel using heterogeneous catalysts. Fuel Proc. Technol.,
29. Ma, F., Clements, L.D. and Hanna, M.A. (1998) The effects of cat- 90: 671–676.
alyst, free fatty acids, and water on transesterification of beef tallow. 49. Liu, X., He, H., Wang, Y., Zhu, S., and Piao, X. (2007b)
Amer. Soc. Agri. Eng., 41: 1261–1264. Transesterification of soybean oil to biodiesel using CaO as a solid
30. Isahak, W.N.R.W., Ismail, M., Jahim, J.M., Salimon, J., and Yarmo, base catalyst. Fuel, 87: 216–221.
M.A. (2012a) Characterization and performance of three promis- 50. Ngamcharussrivichai, C., Totarat, P., and Bunyakiat, K. (2008) Ca and
ing heterogeneous catalysts in transesterification of palm oil. Chem. Zn mixed oxide as a heterogeneous catalyst for transesterification of
Papers, 66: 178–187. palm kernel oil. Appl. Catal. A: Gen., 341: 77–85.
31. Knothe, G., Van Gerpen, J., and Krahl, J. (2005) The Biodiesel 51. Garcia, C.M., Teixeira, S., Marciniuk, L.L., and Schuchardt, U.
Handbook; AOCS Press: Champaign, Illinois. (2008b) Transesterification of soybean oil catalyzed by sulfated zir-
32. Jeromin, L., Johannisbauer, W., Blum, S., Sedelies, R., Moormann, conia. Bioresour. Technol., 99: 6608–6613.
H., Holfoth, B., and Plachenka, J. (1996) Glycerol water mixture from 52. Yoosuk, B., Krasae, P., Puttasawat, B., Udomsap, P., Viriya-Empikul,
hydrolysis of natural fats and oils passed through plate type separa- N., and Faungnawakij, K. (2010) Magnesia modified with strontium
tor, fat particles returned to hydrolysis reaction, liquid filtered through as a solid base catalyst for transesterification of palm olein. Chem.
membrane. U.S. Patent No. 5527974A, June 18, 1996. Eng. J., 162: 58–66.
33. Miao, X., Li, R., and Yao, H. (2009) Effective acid-catalyzed 53. Aderemi, B.O. and Hameed, B.H. (2009) Alum as a heterogeneous
transesterification for biodiesel production. Energy Convers. Mgmt., catalyst for the transesterification of palm oil. Appl. Catal. A: Gen.,
50: 2680–2684. 370: 54–58.
34. Hajek, M., Skopal, F., and Machek, J. (2006) Determination of free 54. Guan, G., Kusakabe, K., Sakurai, N., and Moriyama, K. (2008)
glycerol in biodiesel. Eur. J. Lipid Sci. Technol., 108: 666–669. Transesterification of vegetables oil to biodiesel fuel using acid
35. Leung, D.Y.C. and Guo, Y. (2006) Transesterification of neat and used catalysts in the present of dimethyl ether. Fuel, 88: 81–86.
frying oil: Optimization for biodiesel product. Fuel Proc. Technol., 87: 55. Serio, M.D., Tesser, R., Dimiccolli, M., Cammarota, F., Nastasi, M.,
883–890. and Santacesaria, E. (2005) Synthesis of biodiesel via homogeneous
36. Dias, J.M., Alvim-Ferraz, M.C.M., and Almeida, M.F. (2008) lewis acid catalyst. J. Mol. Catal. A: Chem., 239: 111–115.
Camparison of the performance of different homogeneous alkali cata- 56. Alsalme, A., Kozhecnikova, E.F., and Kozhevnikov, I.V. (2008)
lysts during transesterification of waste and virgin oils and evaluation Heteropolyacids as catalyst for liquid-phase esterification and trans-
of biodiesel quality. Fuel, 87: 3572–3578. esterification. Appl. Catal. A: Gen. 349, 170–176.
37. Rashid, U., Anwar, F., Moser, B.R., and Ashraf, S. (2008) Production 57. Demirbas, A. (2002) Biodiesel from vegetable oils via transesterifica-
of sunflower oil methyl esters by optimized alkali-catalyzed methanol- tion in supercritical methanol. Energy Conversion Management, 43:
ysis. Biomass Bioenergy, 32: 1202–1205. 2349–2356.
38. Soriano, Jr., N.U., Venditti, R., and Argyropolous, D.S. (2008) 58. Demirbas, A. (2003) Biodiesel fuels from vegetable oils via catalytic
Biodiesel synthesis via homogeneous Lewis acid-catalyzed transes- and non-catalytic supercritical alcohol transesterifications and other
terification. Fuel, 88: 560–565. methods: A survey. Energy Conver. Mgmt., 44: 2093–2109.
39. Zhang, Y., Dube, M.A., Mclean, D.D., and Kates, M. (2003) Biodiesel 59. Kusdiana, D. and Saka, S. (2001) Kinetics of transesterification in
production from waste cooking oil: 1. Process design and technologi- rapeseed oil to biodiesel fuels as treated in supercritical methanol.
cal assessment. Bioresour. Technol., 89: 1–16. Fuel, 80: 693–698.
40. Zheng, S., Kates, M., Dube, M.A., and McLean, D.D. (2006) Acid- 60. Han, H., Cao, W., and Zhang, J. (2005) Preparation of biodiesel from
catalyzed production of biodiesel from waste frying oil. Biomass soybean oil using supercritical methanol and CO2 as co-solvent. Proc.
Bioenergy, 30: 267–272. Biochem., 40: 3148–3151.
41. Wang, Y., Ou, S., Liu, P., Xue, F., and Tang, S. (2006) Comparison of 61. Hawash, S., Kamal, N., Zaher, F., Kenawi, O., and El Diwani, G.
two different processes to synthesize biodiesel by waste cooking oil. (2009) Biodiesel fuel from jatropha oil via non-catalytic supercritical
J. Mol. Catal. A: Chem., 252: 107–112. methanol transesterification. Fuel, 88: 579–582.
42. Arzamendi, G., Campo, I., Arguinarena, E., Sanchez, M., Montes, 62. Marulanda, V.F., Anitescu, G., and Tavlarides, L.L. (2010)
M., and Gandia, L.M. (2007) Synthesis of biodiesel with hetero- Investigations on supercritical transesterification of chicken fat for
geneous NaOH/alumina catalysts: Comparison with homogeneous biodiesel production from low-cost lipid feedstocks. Journal of
NaOH. Chem. Eng. J., 134: 123–130. Supercritical Fluids, 54: 53–60.
GLYCEROL RECOVERY FROM VEGETABLE OIL 265
63. Demirbas, A. (2009) Biodiesel from waste cooking oil via 83. Trimm, D.L. (2001) The regeneration or disposal of deactivated
base-catalytic and supercritical methanol transesterification. Energy heterogeneous catalysts. Appl. Catal. A: Gen., 212: 153–160.
Convers. Mgmt., 50: 923–927. 84. Li, E., Xu, Z.P., and Rudolph, V. (2009) MgCoAl-LDH derived het-
64. Eun-Seok, S., Jung-won, L., Hong-Shik, L., and Youn-Woo, L. (2008) erogeneous catalysts for the ethanol transesterification of canola oil to
Transesterification of RBD palm oil using supercritical methanol. J. biodiesel. Appl. Catal. B; Environment 88, 42–49.
Supercrit. Fluids, 44: 356–363. 85. Yoo, D.W., Han, J.H., Nam, S.H., Kim, H.J., Kim, C., and Lee,
65. Wang, L., He, H., Xie, Z., Yang, J., and Zhu, S. (2007) J.K. (2006) Efficient transesterification by polymer-supported zinc
Transesterification of the crude oil of rapeseed with NaOH in super- complexes: Clean and recycleable catalysts. Inorganic Chemistry
critical and subcritical methanol. Fuel Proc. Technol., 88: 477–481. Communications, 9: 654–657.
66. Yang, Z., Zhang, K.P., Huang, Y., and Wang, Z. (2010) Both 86. Liu, X., He, H., Wang, Y., and Zhu, S. (2007a) Transesterification
hydrolytic and transesterification activities of Penicillium expansum of soybean oil to biodiesel using SrO as a solid base catalyst. Catal.
lipase are significatly enhanced in ionic liquid [BMIm][PF6 ]. J. Mol. Comm., 8: 1107–1111.
Catal. B: Enzym., 63: 23–30. 87. Nordin, N.A.M., Adnan, N.F., Hamzah, N., Isahak, W.N.R.W.,
67. Xie. W. and Ma. N. (2010) Enzymatic transesterification of soybean Ayatillah, A., Salimon, J. and Yarmo, M.A., and Kamaruddin, R.A.
by using immobilized lipase on magnetic nano-particles. Biomass (2012) Comparison of different heterogeneous catalysts for the
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
Bioenergy, 34: 890–896. estolides synthesis from oleic acid. Adv. Mater. Res., 364: 288–292.
68. Boz, N., Nebahat, D., and Dilhan, M.K. (2009) Conversion of biomass 88. Liu, Y., Lotero, E., Goodwin, Jr., J.G., and Mo, X. (2007c)
to fuel: Transesterification of vegetable oil to biodiesel using KF Transesterification of poultry fat with methanol using Mg-Al hydro-
loaded nano γ-Al2 O3 as catalyst. Appl. Catal. B: Environ., 89: talcite derived catalysts. Appl. Catal. A: Gen., 331: 138–148.
590–596. 89. Lourenco, W. C. F., Macret, R., and Cielo, J. E. (2012) Process for the
69. Isahak, W.N.R.W., Ismail, M., Yarmo, M.A., Jahim, J.M., and purification of crude glycerol. U.S. Patent 2012/0245398 A1, March
Salimon, J. (2010b) Transesterification of palm oil by using nano CaO 16, 2011.
as a catalyst. World Appl. Sci. J., 9: 17–22. 90. Shu, Q., Zhang, Q., Xu, G., Nawaz, Z., Wang, D., and Wang, J. (2009)
70. Wang, L. and Yang, J. (2007) Transesterification of soybean oil with Synthesis of biodiesel from cottonseed and methanol using a carbon-
nano-MgO or not in supercritical and subcritical methanol. Fuel, 86: based solid acid catalyst. Fuel Proc. Technol., 90: 1002–1008.
328–333. 91. Xu, G.-Z, Zhang, B.-L., Liu, S.-Y., and Yue, J.Z. (2006) Study
71. Reddy, C.R.V., Oshel, R., and Verkade, J.G. (2006) Room- on immobilized catalyzed transesterification reaction of Tung oil.
temperature conversion of soybean oil and poultry fat to biodiesel Agricultural Sciences in China, 25: 859–864.
catalyzed by nanocrystalline calcium oxides. Energy Fuels, 20: 92. Hayyan, M., Farouq, S.M., Hasyim, M.A., and AlNashef, I.M. (2009)
1310–1314. A novel technique for separating glycerine from palm oil-based
72. Lapis, A.A.M., de Oliviera, L.F., Neto, B.A.D., and Dupont, J. (2008) biodiesel using ionic liquids. Fuel Proc. Technol., 91: 116–120.
Ionic liquid supported acid/base-catalyzed production of biodiesel. 93. Hajek, M. and Skopal, F. (2010) Treatment of glycerol phase formed
Chem. Sus. Chem., 1: 759–762. by biodiesel production. Bioresour. Technol., 101: 3242–3245.
73. Vidya, P. and Chadha, A. (2009) The role of different anions in ionic 94. Baabad, M. and Ismail, M. (2008) Biodiesel production using potas-
liquids on Pseudomonas cepacia lipase catalyzed transesterification sium based heterogeneous catalyst on γ-alumina support. Proceedings
and hydrolysis. J. Mol. Catal. B: Enzymatic, 57:145–148. on 15th Regional Symposium on Chemical Engineering (RSCE)
74. Wang, B., Yang, L.M., and Suo J.S. (2003) Ionic liquid-regulated in conjunction with the 22nd Symposium of Malaysian Chemical
sulfamic acid: chemoselective catalyst for the transesterification of Engineers (SOMChe), Impiana KLCC Hotel & Spa, Kuala Lumpur,
β-ketoesters. Tetrahedr. Lett., 44: 5037–5039. Malaysia, December 2–3, 2008, 911–916.
75. Ziyauddin, S.Q., Krishna, M.D., Malhari, D.B., and Bhalchandra, 95. Duncan J. (2003) Cost of biodiesel production. Energy Efficiency
M.B. (2009) Bronsted acidic ionic liquid as an efficient and reusable and Conservation Authority, 1–26. http://www.globalbioenergy.org/
catalyst for transesterification of β-ketoesters. Catal. Comm., 10: uploads/media/0305_Duncan_-_Cost-of-biodiesel-production.pdf
833–837. (accessed July 20, 2012).
76. Huddleston, J.G., Visser, A.E., Reichert, W.M., Willauer, H.D., 96. Thompson, F.C. and He, B. (2006) Characterization of crude glycerol
Broker, G.A., and Rogers, R.D. (2001) Characterization and compar- from biodiesel production from multiple feedstocks. Appl. Eng. Agri.,
ison of hydrophilic and hydrophobic room temperature ionic liquids 22: 261–265.
incorporating the imidazolium cation. Green Chem., 3: 156–164. 97. Isahak, W.N.R.W., Ismail, M., Yarmo, M.A., Jahim, J.M., and
77. Isahak, W.N.R.W., Ismail, M., Jahim, J.M., Salimon, J., and Yarmo, Salimon, J. (2009) Crude glycerol purification and treatment for biol-
M.A. (2011a) Transesterification of palm oil by using ionic liq- ubricant preparation. Proceedings on 16th Regional Symposium on
uids as a new potential catalyst. Trends in Appl. Sci. Res, 6: Chemical Engineering (RSCE), University of Santo Tomas, Manila,
1055–1062. Philippines, December 1–2, 2009.
78. Ramos, L.P. and Wilhelm, H.M. (2005) Current status of biodiesel 98. Chuang-Wei, C., Dasari, M.A., Sutterlin, W.R., and Suppes, G.J.
development in Brazil. Appl. Biochem. Biotechnol, 121: 807. (2006) Removal of residual catalyst from simulated biodiesel’s crude
79. Kim, H.J., Kang, B.S., Kim, M.J., Park, Y.M., Kim, D.K., Lee, J.S., glycerol for glycerol hydrogenolysis to propylene glycol. Ind. Eng.
and Lee, K.Y. (2004) Transesterification of vegetable oil to biodiesel Chem. Res., 45: 791–795.
using heterogeneous base catalyst. Catal. Today, 93: 315–320. 99. Hedtke, D. (1996) Glycerine processing. In Bailey’s Industrial Oil
80. Saleh, J., Tremblay, A.Y., and Dube, M.A. (2010) Glycerol removal and Fat Products: Industrial and Consumer Non-edible Products from
from biodiesel using membrane separation technology. Fuel, 89: Oils and Fats; Hui, Y.H., ed.; John Wiley & Sons, Inc.: New York, 5:
2260–2266. 275–308.
81. Wang, Y., Wang, X., Liu, Y., Ou, S., Tan, Y., and Tang, S. (2009) 100. Israel, A.U., Obot, I.B., and Asuquo, J.E. (2007) Recovery of glycerol
Refining of biodiesel by ceramic membrane separation. Fuel Proc. from spent soap lye by product of soap manufacture. E-Journal of
Technol., 90: 422–427. Chemistry, 5: 940–945.
82. Gallego, I., Mallada, R., Urriolabeitia, E.P., Navarro, R., Menendez, 101. Helmold, V.P. (1993) Sodium sulfate. Ulmann’s encyclopedia of
M., and Santamaria, J. (2004) Selective separation of homogeneous industrial chemistry. Fifth edition, vol. A24. VCH Verlagsgesellschaft,
catalysts using silicate membranes. Inorganica Chimica Acta, 357: Federal Republic of Germany, pp. 355-368. How to make biodiesel
4577–4581. [cited March 2009] http://www.make-biodiesel.org/catalyst/
266 W. N. R. WAN ISAHAK ET AL.
102. Thomas, F.C. (1983) Sodium sulfates. In Kirk-Othmer Encyclopedia 124. Skerlos. S.J., Rajagopalan, N., DeVor, R.E., Kapoor, S.G., and
of Chemical Technology, Third edition, Vol. 21; Kirk, R.E., and Angspatt, V.D. (2001) Microfiltration polyoxyalkylene metalnetwork-
Othmer, D.F., eds.; John Wiley & Sons, Inc.: New York. ing fluid lubricant additives using aluminium oxide membranes. J.
103. Igile, G. (1995) Lye Treatment and Glycerin Recovery. Paterson Man. Sci. Eng. Trans., 123: 692–699.
Zochonis Industries Plc.: Aba, Nigeria, 24. 125. Gomes, M.C.S., Pereira, N.C., and De Barros, S.T.D. (2010)
104. Igile, G. (1993) Manual on Glycerin Recovery. Paterson Zochonis Separation of biodiesel and glycerol using ceramic membranes. J.
Industries Plc.: Aba, Nigeria, 3. Membrane Sci., 352: 271–276.
105. Haas, M.J., McAloon, A.J., Yee, W.C., and Foglia, T.A. (2005) A pro- 126. Jeromin, L., Bernhard, G., Reinhard, B., and Volkmat, J. (1998)
cess model to estimate biodiesel production costs. Bioresour. Technol., Process for the production of diglycerol. U.S. Patent No.
97: 671–678. 5710350, January 20, 1998.
106. Ooi, T.L., Yong, K.C., Dzulkifly, K., Wan Yunus, W.M.Z., and 127. Wang, L., Xudong, W., and Ken-ichi, F. (2008) Effects of opera-
Hazimah, A.H. (2001) Crude glycerine recovery from glycerol residue tional conditions on ultrafiltration membrane fouling. Desalination,
waste from a palm kernel oil methyl ester plant. J. Oil Palm Res., 13: 229: 181–191.
16–22. 128. Marcus, Y., SenGupta, A.K. and Marinsky, J.A. (2004) Ion Exchange
107. Foidl, N., Foidl, G., Sanchez, M., Mittelbach, M., and Hackel, S. and Solvent Eextraction. A Series of Advances; Volume 17; Marcus,
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
(1996) Jatropha curcas L. as a source for the production of biofuel Y., SenGupta, A.K., and Marinsky, J.A., eds.; Marcel Dekker: New
in Nicaragua. Bioresour. Technol. 58: 77–82. York, 1–474.
108. Yong, K.C., Ooi, T.L., Dzulkefly, K., Wan Yunus, W.M.Z., and 129. Rohm and Haas Company. (1990) Ion Exchange Resins Laboratory
Hazimah, A.H. (2001) Characterization of glycerol residue generated Guide (IE-85b). Author: Philadelphia, PA.
from a palm kernel oil methyl ester plant. J. Oil Palm Res., 13: 1–6. 130. Claudio, A.T., Rodrigo, R., and Ceullar, J. (2008) Sulfonation of
109. Wang, Z., Zhuge, J., Fang, H., and Prior, B.A. (2001) Glycerol pro- mesoporous poly(styrene-co-divinylbenzene) beads: Effect of the pro-
duction by microbial fermentation: A review. Biotechnol. Adv., 19: portion of isomers on their cation exchange capacity. React. Funct.
201–223. Polym., 68: 1325–1336.
110. Kerr, B.J., Honeyman, M., Lammers, P., and Hoyer, S. (2007) Feeding 131. Rezkallah, A. (2008) Method for purification of glycerol. U.S. Patent
Bioenergy Co-products to Swine; Iowa State University: Ames, Iowa. No. 20080249338, October 9, 2008.
111. Bourney, L., Casanave, D., Delfort, B., Hillion, G., and Chodorge, 132. Carmona, M., Valverde, J., and Perez, A. (2008). Purification of
J.A. (2005) New heterogeneous process for biodiesel production: glycerol/water solutions from biodiesel synthesis by ion exchange:
A way to improve the quality and the value of the crude glycerin sodium removal Part 1. J. Chem. Technol. Biotech., 84: 738–744.
produced by biodiesel plants. Catal. Today, 106: 190–192. 133. Mohtar, Y., Tang, T.S., and Salmiah, A. (1998) Characteristics and
112. Kusdiana, D. and Saka, S. (2004) Effects of water on biodiesel fuel properties of commercial fatty acids from some Malaysian manufac-
production by supercritical methanol treatment. Bioresour. Technol., turers. PORIM Technology, 21: 21–34.
91: 289–295. 134. Chitra, P., Venkatachalam, P. and Sampathrajan, A. (2005).
113. Ooi, T.L., Yong, K.C., Hazimah, A.H., Dzulkefly, K., and Wan Yunus, Characterization and purification of crude glycerol recovered from
W.M.Z. (2004) Glycerol residue—A rich source of glycerol and transesterification of Jatropha curcas oil. Madras. Agric. J., 92:
medium chain triglycerides. J. Oleo Sci., 53: 29–33. 241–243.
114. Van Gerpen, J., Shanks, B., Pruszko, R., Clements, D., and Knothe, 135. Mittelbach, M., and Remschmidt, C. (2004) Biodiesel—The compre-
G. (2002) Biodiesel Production Technology: August 2002–January hensive handbook; University of Michigan: Ann Arbor, MI.
2004: related information: work performed by Iowa State University. 136. Garti, N., Aserin, A., and Zaidman, B. (1981) Polyglycerol ester:
National Renewable Energy Laboratory, U.S. Department of Energy: optimization and techno-economic evaluation. JAOCS, 58: 878–883.
Colorado. 137. Potthast, R., Chung, C., and Mathur, I. (2009) Purification of glycerin
115. Addison K. (2006) Separating Glycerine/FFAs. Homemades Project obtained as a bioproduct from the transesterification of triglycerides
2006, Journey to Forever. http://journeyforever.org/biodiesel_ in the synthesis of biofuel. U.S Patent No. AC07C2980FI, May 28,
glycerin.html (accessed March 12, 2011). 2009.
116. Banavali, R.M., Hanlon, R.T., and Schultz, A.K. (2009) Method 138. Ikuya, N., Shigeo, O., and Kazuo, M. (1990) Production of high-purity
for purification of glycerol from biodiesel production. U.S. Patent diglycerol. Japan Patent No. 2169536A2, June 29, 1990.
No. 2009/0048472 A1, February 19, 2009. 139. Monick, J.A. (1960) Trihydric and polyhydric alcohol. In Alcohol,
117. Kongjao, S., Damronglerd, S., and Hunsom. M. (2010) Purification of their chemistry, properties and manufacture; Monick, J.A. ed.;
crude glycerol derived from waste used-oil methyl ester plant. Korean Reinhold Book Corporation: New York, 365–445.
J. Chem. Eng., 27: 944–949. 140. Jungermann, E. (1991) Chemical reactions of glycerin. In Glycerin, A
118. Dasari, M. (2007) Crude glycerol potential described. Feedstuffs, 79: Key Cosmetic Ingredient; Jungermann, E. and Sonntag, N.O.V., eds.;
1–3. Marcel Dekker Inc.: New York, 97–112.
119. Brockmann, R., Jeromin, L., Johannisbauer, W., Meyer, H., Michel, 141. Rodrigo, R.K. and Walker, R.H. (2008) Treated biodiesel glycerin.
O., and Plachenka, J. (1987) Glycerol distillation process. U.S. Patent U.S. Patent No. 20080214679, September 12, 2008.
No. 4655879, April 7, 1987. 142. Rohm and Haas Company. Glycerol Purification from Biodiesel
120. Garcia, E., Laca, M., Perez, E., Garrido, A., and Peinado, J. (2008a) Processing with AMBERSEPTM BD50 Technology. http://www.
New class of acetal derived from glycerin as a biodiesel fuel compo- amberlyst.com/glycerol.html (accessed February 2009).
nent. Energy Fuels, 22: 4274–4280. 143. Aiken, J.E. (2006) Purification of glycerin. U.S. Patent No.
121. Dmytryshyn, S.L., Dalai, A.K., Chaudari, S.T., Mishra, H.K., and 7126032 B1, October 24, 2006.
Reaney, M.J. (2004) Synthesis and characterization of vegetable 144. Glycerol purification. EET Corporation website. http://www.eetcorp.
oil derived esters: evaluation for their diesel additive properties. com/heepm/glycerine.html (accessed May 2009).
Bioresour. Technol., 92: 55–64. 145. SRS International. Glycerine purification. http://www.srsbiodiesel.
122. Wurster, O.H. (1936) The recovery of crude glycerine. Oil & Soap, com/GlycerinPurification.aspx (accessed October 2009).
13: 246–253. 146. Ramtox Corporation (2008) Glycerin purification and recovery sys-
123. Buenemann, T., Oudejans, J.C., Gamba, P., and Rampi, A. tem. Ramtox Corporation Newsletter 1, 1-2. http://www.ramtox.com/
(1991). Process for purifying crude glycerol. U.S. Patent No. html/biofuel.html (accessed May 23, 2012).
4990695, February 5, 1991.
GLYCEROL RECOVERY FROM VEGETABLE OIL 267
147. Posada, J. A., Higuita, J. C. and Cardona, C. A. (2011) Optimization 155. Chaudhari, S.T. and Bakhshi, N.N. (2002). Steam gasification from
on the use of crude glycerol from the biodiesel to obtain poly- chars and bio-oil. In Report to Bioenergy Development Program
3-hydroxybutyrate. World Renewable Energy Congress, 8–13 May Renewable Energy Branch; Natural Resources Canada: Ottawa,
2011, Linkoping, Sweden. Canada, 396–436.
148. Hunsom, M., Saila, P., Chaiyakam, P., and Kositnan, W. (2013) 156. Stein, Y.S. and Antal Jr., M.J. (1983) A study of the gas-phase
Comparison and combination of solvent extraction and adsorp- pyrolysis of glycerol. J. Anal. Appl. Pyrol., 4: 283–296.
tion for crude glycerol enrichment. Int. J. Renew Energy Res. 3: 157. Isahak, W.N.R.W., Ismail, M., Nordin, N.M., Jahim, J.M., and Yarmo,
364–372. M.A. (2011). Synthesis, characterization and catalytic performance
149. Buhler, W., Dinjus, E., Ederer, H. J., Kruse, A., and Mas, C. (2002) of H3 SiW12 O40 /SiO2 prepared by sol-gel technique. J. Nanotech.,
Ionic reactions and pyrolysis of glycerol as competing reaction path- Article ID 507692, 1–6.
ways in near and supercritical water. J. Supercritical Fluids, 22: 158. Isahak, W.N.R.W., Ismail, M., Nordin, N.M., Hamzah, N., Khadijeh,
37–53. B.G., Jahim, J.M., and Yarmo M.A. (2012b). Synthesis and character-
150. Kunkes, E.L., Simonetti, D.A., Dumesic, J.A., Pyrz, W.D., Murillo, ization of silicotungstic acid nanoparticles via sol gel technique as a
L., Chen, J.G., and Buttrey, D.J. (2008) The role of rhenium in catalyst in esterification reaction. Adv. Mater. Res., 364: 266–271.
the conversion of glycerol to synthesis gas over carbon supported 159. Isahak, W.N.R.W., Ismail, M., Nordin, N.M., Adnan, N.F., Jahim,
Downloaded by [Universiti Kebangsaan Malaysia], [Wan Isahak] at 00:22 11 October 2014
platinum–rhenium catalysts. J. Catal., 260: 164–177. J.M., Salimon, J., and Yarmo, M.A. (2012c). Selective synthesis of
151. Simonetti, D.A., Kunkes, E.L., and Dumesic, J.A. (2007) Gas- glycerol monoester with heteropoly acid as a new catalyst. Adv. Mater.
phase conversion of glycerol to synthesis gas over carbon- Res., 545: 373–378.
supported platinum and platinum–rhenium catalysts. J. Catal., 247: 160. Hamzah, N., Nordin, N.M., Isahak, W.N.R.W., Kassim, M.B., and
298–306. Yarmo, M.A. (2013) Study on effect recyclability of Ru/bentonite-
152. Soares, R.R., Simonetti, D.A., and Dumesic, J.A. (2006) Glycerol TiO2 catalysts in glycerol hydrogenolysis reaction using x-ray photo-
as a source for fuels and chemicals by low-temperature catalytic electron spectroscopy (XPS). Adv. Mater. Res., 620: 289–294.
processing. Angew. Chem. Int. Ed., 45: 3982–3985. 161. Amin, I.A., Yarmo, M.A., Yusoof, N.I.N., Nordin, N.A.M., and
153. Thiruchitrambalam, V. (2004) Hydrogen and Syn gas Production from Isahak, W.N.R.W. (2013) Synthesis of alkyl polyglucoside from
Glycerol Using Pyrolysis and Steam Gasification. Master’s Thesis. dextrose-decanol in the presence of silicotungstic acid sol-gel catalyst.
University of Saskatchewan. Malays. J. Anal. Sci., 17, 91–100.
154. Cortright, R.D., Davda, R.R., and Dumesic, J.A. (2002) Hydrogen 162. Wibowo, T.Y., Abdullah, A.Z., and Zakaria, R. (2010) Orani-
from catalytic reforming of biomass-derived hydrocarbons in liquid montmorillonites as catalysts for selective synthesis of glycerol
water. Nature, 418: 964–967. monolaurate. Appl. Clay Sci., 50: 280–281.