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Wan Nor Roslam Wan Isahak , Zatil Amali Che Ramli , Manal Ismail , Jamaliah Mohd Jahim
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
To link to this article: http://dx.doi.org/10.1080/15422119.2013.851696
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.
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.
251
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
252
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.
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
Type of catalyst/reaction
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
254
Type of catalyst/reaction
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
TABLE 4
Transesterification using supercritical methanol (SCM)
Type of catalyst/reaction
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
Type of catalyst/reaction
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
Type of catalyst/reaction
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)
TABLE 7
Performance of transesterification reactions using ionic liquids as catalysts
Type of catalyst/reaction
[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.
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).
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)
257
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)
259
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)
(99,139), and the acrolein accumulates in the cold trap during distillation. In addition, glycerol can oxidise to glycerose,
glyceraldehyde and dihydroxyacetone (140).
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
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).
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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