Applied Catalysis A: General 455 (2013) 164171

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Applied Catalysis A: General

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

Synthesis of biolubricants using sulfated zirconia catalysts

Jinho Oh a , Sungeun Yang a , Chanyeon Kim a , Inchang Choi b , Jae Hyun Kim b ,
Hyunjoo Lee a,
a
b

Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul 120-749, Republic of Korea
GS Caltex R&D Center, Daejeon 305-380, Republic of Korea

a r t i c l e

i n f o

Article history:
Received 5 June 2012
Received in revised form 16 January 2013
Accepted 27 January 2013
Available online xxx
Keywords:
Biomass
Biolubricants
Transesterication
Esterication
Sulfated zirconia

a b s t r a c t
Synthesis of biomass-derived lubricants via esterication, transesterication, and simultaneous reactions
of both was studied by using sulfated zirconia catalysts. Soybean oil or free fatty acids derived from soybean oil were used as a biomass-derived resource for the synthesis of biolubricants. Long chain alcohols
(carbon number 8) or neo-polyols (e.g., 2,2-diethyl-1,3-propanediol, trimethylol propane, pentaerythritol) were used as co-reactants. The structure of the alcohol signicantly affected the conversion and
yield for the esterication with oleic acid. The esters produced showed kinematic viscosity and viscosity
index comparable to commercial lubricants. Various sulfated zirconia catalysts were prepared and were
characterized by X-ray diffraction, NH3 temperature-programmed desorption, BrunauerEmmettTeller
isotherm, and tested for esterication. The type of zirconium precursor demonstrated a signicant effect
on the physical property of the catalyst and its catalytic activity. Interestingly, esters with fully saturated hydrocarbon chains were synthesized from unsaturated free fatty acids regardless of the absence
of hydrogen gas. The sulfated zirconia could be recycled for up to ve repeated reactions without any
degradation. The effects of reaction time and temperature were also investigated.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Developing industrial chemical products from renewable
biomass feedstocks is of increasing importance [1]. Biolubricants
have signicant advantages compared with common lubrication
products; (1) they are environmentally friendly because they are
biodegradable, non-toxic, and carbon-neutral [2,3], (2) it is not necessary to add anti-oxidants, viscosity index improvers, pour point
depressants, emulsion stabilizers, and detergents [46], and (3)
biolubricants have a high viscosity index; their viscosity does not
vary with temperature as much as that of mineral oil, thus, they
can lubricate over a wider temperature range [7].
The main raw materials for biodegradable lubricants are vegetable oils. Synthetic biolubricants can be prepared by esterication
of free fatty acids (FFAs) derived from vegetable oils (path A of
Scheme 1) or by direct transesterication of vegetable oils (path B
of Scheme 1). FFAs can be extracted from vegetable oils by hydrolysis using acid catalysts. When soybean oil is used, a greater amount
of oleic acid and linoleic acid are obtained with a minor amount
of palmitic acid, stearic acid, and linolenic acid [8,9]. These FFAs
can form biolubricants by esterication with alcohols having a long
(typically > C8) alkyl groups or complicated hydrocarbon structure

Corresponding author. Tel.: +82 2 2123 5759; fax: +82 2 312 6401.
E-mail address: azhyun@yonsei.ac.kr (H. Lee).
0926-860X/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apcata.2013.01.032

with more than one hydroxyl groups. Direct transesterication of

vegetable oils with these alcohols can also produce biolubricants.
The reaction for the synthesis of biolubricants can be catalyzed
by homogeneous or heterogeneous acid catalysts. Although the
reaction is faster when a homogeneous acid catalyst such as H2 SO4 ,
p-toluenesulfonic acid, or phosphoric acid is used, it is difcult to
separate the catalyst from the products, and the liquid catalysts
often cause reactor corrosion [10,11]. On the other hand, heterogeneous acid catalysts are non-corrosive, environmentally benign,
and present fewer disposal problems. They are more easily separated from the products, and can be designed to yield higher
activity, selectivity, and longer catalyst lifetimes [12].
Several solid acid catalysts have been reported to produce esters
from vegetable oils to typically produce biodiesel. Amberlyst-15
was reported to be an effective catalyst for esterication, but its
catalytic activity decreased easily at a high temperature of 120 C
[13]. Zeolitic solid acids, such as H-ZSM-5 or H-beta, were also tried
for esterication. However, the use of zeolitic solid acids is limited
because the small pore size of the zeolite hinders the reaction with
bulky organic molecules including various FFAs [14]. FeZn doublemetal cyanide complexes, clay K-10, or ZrOCl2 8H2 O have been
reported to synthesize esters [1519]. But most of these studies
were focused on the reaction with short alcohols such as methanol
to explore their application for biodiesel, so detailed studies for
the application to biolubricants were lacking. Activity, selectivity,
and recyclability for the reaction with various structures of alcohols

J. Oh et al. / Applied Catalysis A: General 455 (2013) 164171

Glycerol

OH

(B)
O

H2C

Glycerol

O
HC

Biolubricant

(A)

O
H2C

HO

OH

Scheme 1.

should be investigated to explore the potential for the synthesis of

biolubricants.
In this work, biolubricants were synthesized from FFAs or soybean oil and various alcohols using sulfated zirconia. Sulfated
zirconia catalysts were studied as superacids in various industrial
processes such as hydrocarbon isomerization and alkylation, and
their potential for biomass conversion has been actively explored
recently [2024]. The sulfated zirconia was prepared by calcining
various precursors of zirconium propoxide, zirconium hydroxide,
or zirconium oxychloride. The physical properties and catalytic
activity of sulfated zirconia showed large dependence on the type
of zirconium precursor. Long chain alcohols (C8) or neo-polyols as
shown in Scheme 2 were used as co-reactants. The property of the
alcohol affected the activity signicantly as well. Unsaturated FFAs
formed a mixture of unsaturated ester and fully saturated esters
after the reaction with alcohols. In situ hydrogenation occurred
using alcohol as a hydrogen source. Recyclability of the sulfated
zirconia catalysts was tested. The kinematic viscosity and viscosity
index of the esters produced were compared with those of commercial lubricants. Direct transesterication of soybean oil with
various alcohols and simultaneous reaction of esterication and
transesterication were also investigated.
2. Experimental

165

on a Chemisorption Analyzer (BEL-CAT) with bypass mode. The

catalyst (100 mg) was activated at 400 C for 1 h under He ow
(30 ml/min) and then cooled to 50 C. The NH3 ow was maintained for 1 h, and the sample was then ushed with He for 5 min to
remove any physisorbed NH3 . The desorption prole was recorded
by increasing the sample temperature from 50 C to 850 C at a
ramp rate of 10 C/min. The NH3 concentration in the efuent
stream was monitored with a thermal conductivity detector, and
the areas under the peaks were integrated to determine the amount
of desorbed NH3 during TPD. The specic surface area and the pore
volume were determined by N2 adsorptiondesorption isotherm
(Micromeritics Autochem II). The sulfur content was measured
with an elemental analyzer (EA1110, CE Instruments).
2.2. Reaction test
2.2.1. Esterication of free fatty acid with alcohols
Esterication was carried out in a stainless steel autoclave
reactor equipped with 30 ml of Teon liner and a Teon-coated
magnetic stirring bar. A mixture of free fatty acid (6.25 mmol), alcohol (7.5 mmol), and catalyst (100 mg) was charged into the Teon
liner. The mixture was heated at 140 C for 4 h with stirring at
300 rpm. After the reaction, the reaction mixture was cooled to
room temperature, and the catalyst was separated from the reaction mixture by centrifuging. To test the recyclability of the catalyst,
the catalyst was recovered after the reaction by washing three
times with a mixture of hexane and acetone (hexane:acetone = 1:1).
Then the catalyst was dried at 100 C for 24 h. The reaction was
repeated ve times.
The collected liquid product was analyzed with gas chromatography (Younglin, Acme 6000GC) using a DB-1 column
(30 m, 0.25 m ID) and ame ionization detector. The products
were further identied by gas chromatography-mass spectrometry
(GCMS; Agilent 5975C). Nuclear magnetic resonance (NMR; JEOL
JNM-ECP300, 300 MHz) and Fourier-transformed infrared spectroscopy (FT-IR; PerkinElmer, Spectrum 100 FT-IR) were also used
to analyze the products. Kinematic viscosity and viscosity indexes
were measured using ASTM D445 and ASTM D2270 (Cannon instrument company, CAV-2000).

2.1. Preparation of catalysts

Three different types of sulfated zirconia were prepared
with different zirconium precursors. Type 1 was synthesized
from zirconium propoxide with a one-step solgel method [25].
Zr(OCH2 CH2 CH3 )4 solution (5 ml, Aldrich, 70 wt% in 1-propanol)
was mixed with 6.6 ml of 1-propanol (Aldrich, 99.5%). Aqueous sulfuric acid (0.5 M, Duksan) solution was prepared separately, and
9.7 ml of the aqueous sulfuric acid solution was added dropwise
to the solution of Zr(OCH2 CH2 CH3 )4 in 1-propanol with vigorous
stirring for at least 6 h; a gel was formed. The gel was ltered, dried
at 100 C, and calcined at 625 C for 4 h. Type 2 was synthesized
from zirconium oxychloride with a modied two-step procedure.
ZrOCl2 8H2 O (5 ml, Aldrich, 99.5%) was slowly added to 1 M NaOH
(Duksan, 93%) aqueous solution at room temperature with stirring until the pH reached 8. The mixture was then dried at 100 C
for 24 h. The Zr(OH)4 (5.2 g) that had been prepared was mixed
with 4.6 ml of 0.5 M sulfuric acid at room temperature and stirred
overnight. The gel was ltered, dried at 100 C, and calcined at
625 C for 4 h. Type 3 was synthesized with commercial zirconium
hydroxide. Zr(OH)4 (5.2 g, Aldrich, 97%) was mixed with 4.6 ml of
0.5 M sulfuric acid at room temperature and stirred overnight. The
gel was ltered, dried at 100 C, and calcined at 625 C for 4 h.
X-ray diffraction (XRD) patterns of the catalysts were
recorded on a Rigaku Miniex diffractometer. The scanning speed
was 2 /min and the scanning range was over 1070 . NH3
temperature-programmed desorption (NH3 -TPD) was performed

2.2.2. Transesterication of soybean oil with alcohols

Transesterication was carried out in a stainless steel autoclave
reactor equipped with 30 ml of Teon liner and a Teon-coated
magnetic stirring bar. A mixture of soybean oil, alcohol, solvent, and
catalyst was charged into the Teon liner. The mixture was heated
at 140 C for 4 h with stirring at 300 rpm. Simultaneous reaction
of transesterication and esterication was also performed for the
mixture of soybean oil and oleic acid using alcohol (1-octanol or
neopentane glycol or trimethylol propane) and solvent at 140 C for
4 h with stirring at 300 rpm. After the reaction, the reaction mixture
was cooled to room temperature, and the catalyst was separated
from the reaction mixture by centrifuging.
The collected liquid product was analyzed with gas chromatography (Younglin, Acme 6000GC) with a MXT-5 column (0.53 mm,
0.25 m ID) and a ame ionization detector. The products were
further identied by gas chromatographymass spectrometry
(GCMS; Agilent 5975C).
3. Results and discussion
Biolubricants can be produced by esterication of FFA extracted
from vegetable oils (path A of Scheme 1) or direct transesterication
of vegetable oils (path B of Scheme 1). The exact evaluation of the
products of direct transesterication is often very difcult because
of many potential side products. We therefore studied esterication of FFAs with various alcohols to synthesize well-dened ester

166

J. Oh et al. / Applied Catalysis A: General 455 (2013) 164171

OH
HO
OH

n=3, 5, 6, 7
OH
OH

HO

OH

HO

OH

HO

OH

OH

HO

OH

OH

Scheme 2.

products rst, and then used the knowledge obtained to analyze

the products of direct transesterication. Also, vegetable oil feedstock often includes a signicant amount of FFAs, which degrades
transesterication products by saponication when a basic catalyst is used. Sulfated zirconia catalyzes both esterication and
transesterication; therefore, sulfated zirconia is expected to be
a good catalyst to form esters from vegetable oil containing signicant amounts of FFAs. Simultaneous reactions of esterication and
transesterication were performed for the mixture of vegetable oil
and FFA.
3.1. Esterication
When soybean oil is treated with weak acids, various free fatty
acids are easily obtained, including palmitic acid (16:0; the former
indicates the number of carbons, the latter indicates the number
of double bonds), stearic acid (18:0), oleic acid (18:1), linoleic acid
(18:2), and linolenic acid (18:3) [8,9]. Among these acids, oleic acid
and linoleic acid constitute the majority. Synthesis of biolubricants
by esterication was studied by reacting these FFAs with various
alcohols as shown in Scheme 2.
3.1.1. Esterication with various alcohols
The conversion and yield of esterications of C18 saturated
(stearic acid) or unsaturated (oleic acid, linoleic acid, linolenic acid)
aliphatic acids with 1-octanol are shown in Table 1. Figure S1 shows
GC raw data for esterication of oleic acid and 1-octanol. The side
product other than the desired ester product (C17C( O)OC8) was
rarely observed. When the number of double bonds increased,
Table 1
Esterication of free fatty acids with various alcohols. C18 free fatty acids with a different number of double bonds were reacted with 1-octanol. Oleic acid was reacted
with long chain alcohols with various chain lengths and locations of the hydroxy
group. Sulfated zirconia type 1 was used as the catalyst.a
Alcohol

FFA

Conversion of
FFA (%)

Product yield
(%)

1-Octanol
1-Octanol
1-Octanol
1-Octanol
Dodecanol
Tetradecanol
Hexadecanol

Stearic acid
Oleic acid
Linoleic acid
Linolenic acid
Oleic acid
Oleic acid
Oleic acid

97.8
90.4
86.3
82.7
88.5
87.3
85.7

93.9b
88.6b
84.6b
81.1b
85.4c
83.2d
81.7e

2-Octanol
3-Octanol
Isooctanol

Oleic acid
Oleic acid
Oleic acid

85.2
31.0
83.6

82.2b
28.1b
82.7b

a
The reaction was performed using 6.25 mmol of free fatty acid, 7.5 mmol of
alcohol, and 100 mg of catalyst at 140 C for 4 h.
b
The desired product was C17C( O)OC8.
c
The desired product was C17C( O)OC12.
d
The desired product was C17C( O)OC14.
e
The desired product was C17C( O)OC16.

the FFA conversion and yield decreased. Hydrogenation of double bonds, in addition to esterication, occurred using 1-octanol
as hydrogen source, thus C18 aliphatic acids with more double
bonds showed less conversion and decreased yield for esterication. This reaction will be discussed in detail in Section 3.1.3. The
effect of chain length was also evaluated by reacting oleic acid
with 1-octanol, 1-dodecanol, 1-tetradecanol, and 1-hexadecanol.
As the chain length increased, the conversion and yield decreased.
However, very long aliphatic alcohols, such as 1-hexadecanol, still
showed high conversion and yield above 80% for esterication. The
location of the hydroxyl group in octanol was varied. 2-octanol and
isooctanol showed relatively high conversion and yield similar to
1-octanol, whereas 3-octanol showed far less conversion and yield.
Steric hindrance seems to have a signicant effect on esterication.
Neo-polyols having more than one hydroxyl group, such as 2,2diethyl-1,3-propanediol, trimethylol propane, and pentaerythritol,
were used for esterication with oleic acid (Table 2). The conversion of oleic acid decreased remarkably with increasing numbers
of hydroxyl groups. The mixtures of partially and fully esteried
products were produced.
Table 3 shows the kinematic viscosity and viscosity index for
the synthesized ester products. The kinematic viscosity increased
as the length of the carbon chain or the number of hydroxyl groups
increased. Viscosity index describes how the viscosity of a lubricant changes with variations in temperature. Many applications
require a lubricant to perform across a wide range of temperatures.
Lubricant with higher viscosity indexes will not vary a great deal in
viscosity over a wide temperature range, and are considered better oils. Compared with commercial products made in ExxonMobil
chemical, the synthesized products showed even better viscosity
properties.
3.1.2. Effect of the catalyst properties
Sulfated zirconia was prepared from various zirconia precursors.
When zirconium propoxide was reacted directly with sulfuric acid,
the prepared catalyst was denoted as type 1 sulfated zirconia. When
zirconium oxychloride was used as a zirconium precursor to produce zirconium hydroxide, and the zirconium hydroxide was then
reacted with sulfuric acid, the catalyst was denoted as sulfated zirconia type 2. When commercial zirconium hydroxide was reacted
Table 2
Esterication of oleic acid with neo-polyols over sulfated zirconia type 1.a
Alcohol

FFA

Conversion of FFA (%)

2,2-Diethyl-1,3-propanediol
Trimethylol propane
Pentaerythritol

Oleic acid
Oleic acid
Oleic acid

92.1b
83.5c
71.3d

a
The reaction was performed using 70 mmol of alcohol and 100 mg of catalyst at
140 C for 4 h.
b
The amount of oleic acid was 126 mmol.
c
The amount of oleic acid was 189 mmol.
d
The amount of oleic acid was 252 mmol.

J. Oh et al. / Applied Catalysis A: General 455 (2013) 164171

167

Table 3
Kinematic viscosity and viscosity index of the esters produced.
Alcohol

Octanol
Dodecanol
Tetradecanol
Hexadecanol
2,2-Diethyl-1,3-propanediol
Trimethylol propane
Pentaerythritol
Branda

Oleic acid
Oleic acid
Oleic acid
Oleic acid
Oleic acid
Oleic acid
Oleic acid

Viscosity index

40 C

100 C

10.3
11.3
19.6
21.0
37.8
147.8
432.7

3.0
3.1
5.0
5.2
5.2
12.3
34.4

Kinematic viscosity (mm2 /s)

EsterexTM A41
EsterexTM P61
EsterexTM TM111
a

Kinematic viscosity (mm2 /s)

FFA

120
184
195
193
45
64
118

Viscosity index

40 C

100 C

14.0
38.0
124

3.6
5.4
11.9

144
62
81

From datasheets for EsterexTM esters, ExxonMobil chemical.

with sulfuric acid, the catalyst was denoted as sulfated zirconia

type 3. As shown in Fig. 1a, all sulfated zirconia had a tetragonal
zirconia phase; the monoclinic phase was rarely observed. When
zirconia was not modied by sulfated groups, the zirconia had a
thermodynamically more stable monoclinic phase. The sulfated
group stabilized the acidic tetragonal phase [20,26]. Although no
signicant difference in crystalline structure was observed among
types 13, the pore texture and acidity depended highly on the
zirconium precursor. Type 1 showed the largest surface area, pore
volume, and acidity, whereas type 3 showed the smallest values for
these properties, as shown in Table 4. But when esterication was
performed using oleic acid and 1-octanol, type 3 demonstrated a
higher conversion and yield than type 2. Chloride existing on the
type 2 catalyst may cause deactivation [27].
The effect of S contents was also investigated for the type 1 catalyst. Fig. 2a revealed that when S content decreased, the monoclinic
phase appeared. The acidity was the highest when 9.7 ml of 0.5 M
sulfuric acid was added during the synthesis whereas the acidic site
density (acidity/surface area) was the highest for 13 ml as shown in
Table 5. The conversion and yield for esterication of oleic acid and
1-octanol showed the highest values when 13.0 ml of 0.5 M sulfuric
acid was added. The amount of S content affected the physicochemical properties of the catalyst and its acidity, leading to different
activity for esterication.
3.1.3. In situ hydrogenation
The product solution from the esterication of oleic acid with
1-octanol contained octyl oleate and fully hydrogenated octyl
stearate (Figure S2). The octyl stearate was puried by vacuum
evaporation at elevated temperature, and 1 H NMR of the puried
product is shown in Figure S3. To conrm this result, the puried
product was also analyzed by FT-IR and attached proton test (APT)
13 C NMR. Oleic acid or linoleic acid with C C double bonds showed
a peak at 3000 cm1 in FT-IR, as shown in Fig. 3a. Stearic acid
with no double bond showed no peak in this range. The puried

octyl stearate from the esterication also had no peak in this range,
indicating the absence of a C C double bond. Additionally, the
C C double bond would show a negative peak in APT 13 C NMR,
as shown in Fig. 3b for oleic acid. The puried octyl stearate did
not have a negative peak, also conrming the absence of the C C
double bond. The double bond appears to be hydrogenated by
alcohol. When the amount of 1-octanol increased from 1.25 times
of oleic acid to 2, 3 times of oleic acid, the produced amount of octyl
stearate also increased signicantly as demonstrated in table S1.
The ratio of the products was 94% octyl oleate and 6% octyl stearate
for 1.25 times, while the ratio was changed to 88% octyl oleate
and 12% octyl stearate for 2 times and 50% octyl oleate and 50%
octyl stearate for 3 times. Octanal was detected after esterication,
implying that 1-octanol might be dehydrogenated to octanal after
hydrogen transfer. The exact mechanism is not clear yet, but this
result strongly indicates that 1-octanol serves as hydrogen source
for in situ hydrogenation. Hydrogenation using alcohol as the
hydrogen source was also reported previously [2831].
3.1.4. Recyclability of the catalysts
The sulfated zirconia catalyst was tested to check whether the
catalyst could be recycled after esterication. After separation from
the product solution, the catalysts were washed and dried, then
used for the repeated reaction under the same reaction conditions.
When the reaction was repeated ve times, the conversion and
yield showed little difference, as shown in Fig. 4a. The used catalyst
was collected as white powders in the same state as before the reaction, indicating no coke formation during the reaction. XRD results
for the recycled catalysts revealed that the tetragonal phase of zirconia was stable over the repeated reactions, as shown in Fig. 4b.
According to elemental analysis of the catalysts, no sulfur leaching was observed after the repeated reactions (S content: 2.63 wt%
before the reaction, 2.62 wt% after the 1st reaction, 2.63 wt% after
the 2nd reaction, 2.65 wt% after the 3rd reaction, 2.60 wt% after the
4th reaction, 2.58 wt% after the 5th reaction).

Table 4
Physicochemical properties determined from N2 adsorptiondesorption isotherm, an amount of acidic sites measured from NH3 temperature programmed desorption,
conversion and yield when sulfated zirconia catalysts were used for esterication of oleic acid with 1-octanol.a
Catalyst

S content (wt%)

Surface area
(m2 /g)

Pore volume
(cm3 /g)

Amount of acidic
sites (mol/g)

Oleic acid
conversion (%)

C17C( O)OC8
yield (%)

Type 1
Type 2
Type 3

2.61
2.43
2.19

80.4
56.8
40.5

0.13
0.06
0.03

614
445
205

90.4
78.0
85.4

88.6
77.2
83.7

The esterication was performed using 6.25 mmol of oleic acid, 7.5 mmol of 1-octanol, and 100 mg of catalyst at 140 C for 4 h.

168

J. Oh et al. / Applied Catalysis A: General 455 (2013) 164171

Table 5
Physicochemical properties determined from N2 adsorptiondesorption isotherm, an amount of acidic sites measured from NH3 temperature programmed desorption,
conversion and yield when sulfated zirconia type 1 catalysts synthesized with different amounts of sulfuric acid were used for esterication of oleic acid with 1-octanol.a
Amount of added 0.5 M
sulfuric acid

S content
(wt%)

Surface area
(m2 /g)

Pore volume
(cm3 /g)

Amount of acidic
sites (mol/g)

Oleic acid
conversion (%)

C17C( O)OC8
yield (%)

4.0 ml
9.7 ml
13.0 ml
18.0 ml

0.94
2.61
4.33
8.90

103.7
80.4
38.2
36.5

0.15
0.13
0.11
0.10

233
614
497
376

76.8
90.4
97.3
89.6

75.3
88.6
93.7
88.0

The reaction was performed using 6.25 mmol of oleic acid, 7.5 mmol of 1-octanol, and 100 mg of catalyst at 140 C for 4 h.

3.1.5. Effect of reaction parameters

Reaction parameters such as reaction time, reaction temperature, and the amount of reactant were varied, and their effect on
conversion and yield for esterication of oleic acid with 1-octanol
was evaluated, as shown in Fig. 5. Both conversion and yield became
higher, approaching 100% for longer reaction times and higher
reaction temperatures. Sulfated zirconia catalyst has been demonstrated to be very effective for esterication of FFAs with alcohols
having a long alkyl chain. The high conversion and yield were maintained when the amount of oleic acid increased from 6.25 mmol
to 83 mmol. The optimum process condition for the most effective esterication should be easily achieved by manipulating these
reaction parameters.

(a)

Direct transesterication of soybean oil was studied under mild

reaction conditions over sulfated zirconia type 1 catalyst. Figure S4
shows gas chromatography results for analysis of both reactant and
product for direct transesterication of soybean oil with 1-octanol.
A signicant amount of glycerol was observed as a by-product.
Glycerol could easily be removed by extraction with methanol.
Hexane was used as the solvent to enhance miscibility of the reactants [32]. The conversion of soybean oil was 87.7%. When the
soybean oil was assumed to consisted of C18 FFA only (triglyceride with C18 tails), the yield of the ester was calculated as 84.6%.
Direct transesterication occurred effectively, producing the ester
over sulfated zirconia catalysts. When soybean oil was reacted with
neo-polyols such as neopentyl glycol or trimethylol propane, both

(a)
T

T
T

18ml

T
T
Intensity

SZ type1
Intensity

3.2. Direct transesterication and simultaneous reaction

SZ type2

13ml

9.7ml
M M

SZ type3
10

4.0ml

20

30

40
50
2 (degree)

60

70

10

20

30

40
50
2 (degree)

60

70

(b)

(b)

9.7 ml
Signal

Signal

SZ type 1

100

200

13.0 ml

SZ type 2

18.0 ml

SZ type 3

4.0 ml

300

400

500

600

Temperature ( C)
Fig. 1. (a) XRD patterns and (b) NH3 temperature-programmed desorption results
for sulfated zirconia (types 13) catalysts. T means characteristic peaks of zirconia
tetragonal phase.

100

200

300

400

500

600

Temperature ( C)
Fig. 2. (a) XRD patterns and (b) NH3 temperature-programmed desorption results
for different amounts of 0.5 M sulfuric acid added in the synthesis of sulfated zirconia
type 1 catalysts. M means characteristic peaks of zirconia monoclinic phase.

J. Oh et al. / Applied Catalysis A: General 455 (2013) 164171

169

(a)
FFA conversion
Yield for C17C(=O)OC8

Conversion or Yield (%)

100

80

60

2
3
4
Number of repeated reactions

(b)
T
T
T

5th cycle
4th cycle
3rd cycle
2nd cycle
1st cycle
fresh
10
Fig. 3. (a) FT-IR spectra and (b) attached proton test (APT) 13 C NMR spectra of stearic
acid, oleic acid, and the puried product after esterication. The product solution
after esterication was puried by vacuum evaporation at elevated temperature,
removing unreacted 1-octanol and octyl oleate. The puried product (octyl stearate)
had no C C bonds.

partially and fully esteried products were obtained, as shown in

Figure S5.
The effect of various solvents on transesterication of soybean
oil was also studied. The conversion of soybean oil was 87.7% with
hexane. Soybean oil underwent no reaction with THF, whereas
84.8% conversion was achieved with benzene, 86.0% with toluene,
and 87.2% with m-xylene, respectively. These results demonstrate
that a non-polar material can be a good solvent for direct transesterication of soybean oil.
Other types of solid acids such as Amberlyst-15 and silicotungstic acid were also tried for transesterication of soybean oil
without solvents as shown in Table S2. Sulfated zirconia showed
higher yield, and more importantly, it could be recycled whereas
the commercial catalyst such as Amberlyst-15 was degraded completely after one batch of reaction and showed no activity for 2nd
batch. Further detailed research is necessary to rigorously compare
the activity of various solid acids, but our results clearly showed

20

30

40
2

50

60

70

degree)

Fig. 4. (a) Conversion and yield after repeated esterication reactions over sulfated
zirconia type 1 catalysts. Oleic acid (6.25 mmol) and 1-octanol (7.5 mmol) were
reacted over type 1 catalyst (100 mg) at 140 C for 4 h. (b) XRD patterns of fresh
and recycled catalysts.

that sulfated zirconia is a very promising catalyst for biolubricant

synthesis.
Whereas base catalysts cause saponication in the presence
of FFA during transesterication of vegetable oils, degrading the
quality of the oils produced, acid catalysts can accelerate both esterication and transesterication simultaneously [3336]. A one-pot
reaction was conducted in the presence of soybean oil and oleic
acid over sulfated zirconia catalysts. This simultaneous reaction
was performed at 140 C for 4 h, and 5.6 wt% of the catalyst, compared with the weight of the soybean oil, was used. The conversion
of soybean oil and oleic acid and the yield for the ester were relatively high, as veried by GC in Figure S6. Table 6 also shows that the
yield for octyl stearate could reach 87.7% by increasing the amount
of catalyst to 10 wt% of soybean oil. Oleic acid was converted more
easily than soybean oil, as indicated by the higher conversion of

Table 6
Effects of the amount of catalyst in simultaneous reaction with 1-octanol.a
Amounts of catalystb

Oleic acid conversion (%)

Soybean oil conversion (%)

C17C( O)OC8 yield (%)c

1.0 wt%
5.6 wt%
10.0 wt%

72.5
97.4
100

64.2
70.6
74.8

69.2
83.7
87.7

a
b
c

The reaction was performed using 1.8 g of soybean oil, 1.6 g of oleic acid, 6 ml of 1-octanol, 4 ml of hexane at 140 C for 4 h.
The wt% was compared with the weight of soybean oil.
The yield was calculated assuming that soybean oil consists of C18 FFA tails only.

170

J. Oh et al. / Applied Catalysis A: General 455 (2013) 164171

(a)
Conversion or Yield (%)

100

90.2

80

98.2

98.0

96.3

was conrmed by GCMS. Esterication of oleic acid and transesterication of soybean oil occurred simultaneously when the
neo-polyols were used.

100

100

98.2

88.4

4. Conclusion

73.6
71.8

60
43.8
FFA conversion
Yield for C17C(=O)OC8

42.9

40
0

10

12

14

16

18

Reaction time (h)

100

(b)
Conversion or Yield (%)

100

94.2
90.2
92.5

80.2
80
70

98.2

84.4

90

88.4

76.4
83.1
78.3

74.9

60

FFA conversion
Yield for C17C(=O)OC8

Sulfated zirconia catalysts were used for the synthesis of biolubricants, and demonstrated to be effective catalysts with high
yields. Esterication of FFAs with alcohols having long alkyl chains
or with neo-polyols produced oils with kinematic viscosity and viscosity indexes comparable to those of commercial lubricants. The
structural features of alcohols such as alkyl chain length, number
of double bonds, and number/location of hydroxyl groups had a
signicant effect on the catalytic activity. When sulfated zirconia
was prepared from various zirconia precursors, the catalyst prepared from zirconium propoxide via one-step solgel process had
the largest surface area and acidity with the highest conversion
for esterication. The effect of sulfur amount was also evaluated.
Interestingly, in situ hydrogenation occurred during esterication
of unsaturated FFAs without H2 , producing the fully saturated ester,
as conrmed by FT-IR, APT 13 C NMR, and 1 H NMR. The alcohol coreactant is considered as the hydrogen source. The sulfated zirconia
catalysts were stable for up to ve repeated reactions. Conversion
and yield approaching 100% could be obtained easily by controlling reaction parameters such as reaction time and temperature.
Direct transesterication of soybean oil and simultaneous reaction of esterication and transesterication for the mixture of FFA
and soybean oil were successfully performed over sulfated zirconia
catalysts with various alcohols.

50
100

80

120

140

160

180

Acknowledgements

Temperature ( C)
This work was supported by the Basic Science Research Program
(2010-0009174) and the Global Frontier R&D Program on Center for
Multiscale Energy System (2011-0031575) through the National
Research Foundation of Korea funded by the Ministry of Education,
Science and Technology, and GS Caltex R&D Center.

Conversion or Yield (%)

(c) 100
90.4

90.9 89.8

88.6

89.3 88.6

90
80

88.3 87.0
78.7

83.7
80.4
75.4

70
60

FFA conversion
Yield for C17C(=O)OC8

50
0

20

40

60

80 100 120 140 160 180

Amount of oleic acid (mmol)

Fig. 5. Effects of (a) reaction time, (b) reaction temperature, and (c) the amount of
reactant for esterication of oleic acid with 1-octanol over sulfated zirconia type 1
catalyst. Oleic acid (6.25 mmol) was reacted with 1-octanol (7.5 mmol) over type 1
catalyst (100 mg) at 140 C for case (a), and the same amount was reacted for 4 h for
case (b). The ratio of alcohol to FFA was 1.2 and the amount of catalyst was 100 mg
at 140 C for 4 h for case (c).

oleic acid in Table 6. Esterication of oleic acid with 1-octanol was

preferred over transesterication of soybean oil with 1-octanol.
As shown in Figure S7, simultaneous reaction with neo-polyol
was also tried. In the case of neopentyl glycol, the conversions
of oleic acid and soybean oil were 99.2% and 58.8%, respectively.
The identication of the products, neopentyl glycol mono-C18
and neopentyl glycol di-C18, was conrmed by GCMS. In case of
trimethylol propane, the conversions of oleic acid and soybean oil
were 97.2% and 52.7%, respectively. The identication of the products, trimethylol propane di-C18 and trimethylol propane tri-C18,

Appendix A. Supplementary data

Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.apcata.2013.01.032.
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