Fuel 231 (2018) 271–280

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Total Acid Number (TAN) reduction of high acidic crude oil by catalytic T
esterification of naphthenic acids in fixed-bed continuous flow reactor
⁎ ⁎
Bharat Singh Rana, Dong-Woo Cho , Kanghee Cho, Jong-Nam Kim
Clean Fuel Laboratory, Climate Changing Research Division, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon 305-343, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: High acid crude oils contain large amount of naphthenic acids which cause serious corrosion problem in pet-
Acidic crude oil roleum industry. Therefore, the removal of naphthenic acids becomes a great concern and challenge for oil
TPA/γ-Al2O3 catalyst refineries. In this study, the naphthenic acids in high TAN crude oils were removed by esterification with low
Naphthenic acids consumption of methanol using a solid acid catalyst consisting of 12-tungstophosphoric acid (TPA) supported on
Esterification
γ-Al2O3 (TPA/γ-Al2O3) in a fixed-bed up-flow reactor. The catalyst was prepared by conventional wet impreg-
Methanol
nation method, and it possessed 25 wt% TPA with high dispersion, and large pore structure. TPA leaching
Total Acid Number
problem from catalyst support was not observed during the reaction. The effect of various reaction parameters
such as temperature and liquid hour space velocity (LHSV), and methanol to the crude oil ratio on TAN reduction
were investigated in detail to maximize TAN reduction. The results revealed that the TPA/γ-Al2O3 catalyst
effectively removed the naphthenic acids via esterification in high TAN crude oils. The TAN decreased with
increase in methanol/oil mass ratio, reaction temperature, but it increased with increase in LHSV. In a long-term
experiments (up to 100 h) running at a reaction temperature of 250 °C and LHSV of 3 h−1 using 2 wt% methanol
in acidic crude oil, the TANs of acidic crude oil reduced from 2.0 mg KOH/g to a value below 0.5 mg KOH/g
which is an acceptable TAN value of crude oil to process in the refineries without material upgrades.

1. Introduction
The worldwide increasing oil demand and consumption forces many
countries to explore and utilize heavy and inferior crude oil due to the
unavoidable decline of conventional petroleum oil reserves [1]. Heavy
and inferior crude oil is highly acidic compared with conventional
crude oil, which means it has a high total acid number (TAN). Refining
acidic crude oils might be a good choice for some refineries due to the
increased production and relatively lower price [2]. Worldwide, the
high-TAN crude oil production has increased by 0.3% per year in recent
years [3]. The main contributors to different levels of TAN of acidic
crude oil are different concentrations of naphthenic acids, which are the
main components responsible for a variety of serious corrosion pro-
blems in up- and downstream petroleum processing units in which
high-TAN crude oils are processed [4–6].
In the petroleum industry, the term “naphthenic acids” refers to all
carboxylic acids present in crude oil. Naphthenic acids have the general
formula RCOOH, where R represents the naphthene moiety consisting
of cyclopentane and cyclohexane derivatives; the carboxylic acid group
is usually attached through a eCH2 group or chain, containing up to
five or more eCH2 groups, rather than directly to the ring. High-TAN
crude oil has a higher concentration of naphthenic acids based on ASTM
D 664 by potentiometric titration. The obtained values are considered
to be the TAN or neutralization number, expressed in mg of KOH, re-
quired to neutralize the acid component parents in one gram of crude
oil. Crude oils with a TAN > 0.5 mg KOH/g are considered to be acidic
crude oils, whereas crude oils with a TAN > 1 mg KOH/g are con-
sidered to be highly acidic crude oils in the petroleum industry [7,8].
Due to the worldwide acidic crude oil increase, the processing of high-
TAN crude oils before refining, for which new technology is needed, is a
great challenge for the refineries.
To reduce the corrosivity of high-TAN crude oil due to the presence
of naphthenic acids, the petroleum oil refineries use the blending of
low- and high-TAN crude oils, injection of a corrosion inhibitor, and
metallurgy upgrading [9]. However, these approaches are not entirely
satisfactory. Blending of low-TAN crude oil can substantially reduce the
TAN of highly acidic crude oil but is limited by low-TAN crude oil
suppliers, which might reduce the value of low-TAN crude oil. In most
cases, metallurgy upgrading is based on high contents of chromium and
molybdenum that are recognized as corrosion-resistant materials but
are expensive and require high investments, which might increase the
refining costs. Corrosion inhibitors provide good mitigation of

⁎
Corresponding authors.
E-mail addresses: dwcho@kier.re.kr (D.-W. Cho), jnkim@kier.re.kr (J.-N. Kim).

https://doi.org/10.1016/j.fuel.2018.05.074
Received 19 September 2017; Received in revised form 27 March 2018; Accepted 14 May 2018
Available online 29 May 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
B.S. Rana et al.
naphthenic acid corrosion if closely monitored and used for specific
fractions but will affect downstream processing and poison the catalyst
that is used in the refinery.
Reducing the TAN of highly acidic crude oils by removing naph-
thenic acids is considered to be one of the most important processes.
Currently, a number of approaches have been proposed to remove
naphthenic acids from highly acidic crude oil involving the neu-
tralization or caustic washing, solvent extraction, physical adsorption,
thermal decomposition, catalytic decarboxylation, and esterification
[10–13]. However, some of these approaches have drawbacks. For ex-
ample, neutralization or caustic washing might cause serious emulsion
problems, the loss of crude oil products, and environmental pollution.
Solvent extraction techniques require a large amount of solvent and
high-energy consumption due to the multiple steps that are necessary to
separate the solvent. Physical adsorption techniques are usually costly
and applications are limited. Catalytic hydrogenation is commonly used
for industrial distillates or residual oils; it requires the large consump-
tion of hydrogen and large investments in equipment modification.
Therefore, these techniques have not been used for the treatment of
acidic crude oil in industry. Furthermore the catalytic decomposition
employed for deacidification of naphthenic acids has been reported and
seems to be an alternative and effective method to remove naphthenic
acids. Research has mainly focused on the development of base metal
oxides and mixed oxide-based catalysts to improve the reaction speed of
the decomposition of naphthenic acids in the oil fraction or crude oil
[14]. However, naphthenic acids possibly form insoluble metal-organic
components through well-known acid–base neutralization reactions
when using base metal oxide catalysts, which are very difficult to re-
move [15].
In recent years, heterogeneous catalytic esterification with alcohol
has been considered to be an interesting and novel method. It is thought
to be capable of overcoming the disadvantages of homogeneous cata-
lytic esterification and conventional deacidification methods. This
method has been employed for the esterification of naphthenic acids
with alcohol in diesel, the second vacuum fraction, and vacuum gas oil
(VGO) [6,16,17] using SnO/Al2O3, SnO, and Mg-Al hydrotalcite cata-
lysts, respectively. The TAN of diesel oil was lowered from 1.7 mg
KOH/g to < 0.5 mg KOH/g at a reaction temperature of 250 °C, a me-
thanol/oil ratio of 0.010, and LHSV of 1.6 h−1 in a fixed-bed reactor
system. However, catalytic esterification to reduce the TAN of acidic
crude oil has rarely been reported. The Exxon Research and Engineering
Company used esterification to reduce the acidity of petroleum oil
without any catalyst in batch reactor systems [18]; however, this batch
process was not adopted in the industry due to long reaction times.
Wang et al. reported the esterification of naphthenic acids in highly
acidic crude oil using SnO–Al2O3 in a continuous flow fixed-bed reactor
system to lower the TAN [19] The TAN of acidic crude oil was reduced
from 2.8 mg KOH/g to < 0.5 mg KOH/g at optimized conditions: tem-
perature of 300 °C, a methanol to oil ratio of 2 wt%, and a space velo-
city of 2.5 h−1. Thus, very few research has been carried out on re-
grading and esterification of naphthenic acids in acidic crude oil using
solid acid catalysts. More efficient and eco-friendly solid acid catalysts
are needed for the continuous flow reactor system, which is the most
promising solution to this problem.
In the recent years, solid acid catalysts have received considerable
attention in many industrial organic transformations, which is mainly
due to the non-toxicity, non-corrosiveness, less costs, easy handling,
recovery, and reusability [20]. Keggin-type heteropoly acids (HPA),
particularly 12-tungstophosphoric acid (H3PW12O40·xH2O, TPA), are
well known to pass the pure Brønsted acidity and have proven to be
efficient catalysts when applied in acid-catalyzed reactions [21].
However, pure HPAs generally have a very low catalytic reactivity due
to their very low surface area (1–10 m2/g), their solubility in polar
solvents, low thermal stability, and problems with respect to the se-
paration from the reaction mixture. Consequently, by impregnation of
HPAs on suitable high surface area-supported materials, HPAs can be
272
Fuel 231 (2018) 271–280
made more efficient, eco-friendly, and insoluble solid acid catalysts
with high thermal stability and high surface area and are expected to
overcome the above-mentioned problems. The suitable support for
HPAs provides the opportunity to be dispersed over a high surface area,
which increases the catalytic performance [22–24].
Recently, researchers have reported that 12-tungstophosphoric acid
(TPA) supported on acidic or neutral solids, such as SiO2, TiO2, SnO2,
active carbon, ZrO2, Al2O3, SBA-15, SBA-16, KIT-6, MCM-41, kaolin
clay, and H-β zeolite, can be dispersed over the surface and/or in-
troduced inside the pores of these supporting solid materials, thus al-
lowing for a significant increase in the thermal stability and surface
area of TPA in addition to the enhancement of Bronsted acid sites
within the supporting materials [22,24–35]. Therefore, TPA-supported
materials can provide potential heterogeneous acid catalysts with high
catalytic activity for various organic transformation reactions including
esterification reactions [24,33,35,36]. The esterification reactions using
these TPA supported catalysts were only used for lower aliphatic car-
boxylic fatty acid, formic acid, oleic acid, lauric acid, and free fatty
acids with different alcohols such as methanol, ethanol 1-butanol, and
glycerol [32,36]. However, these catalysts were not used for the es-
terification of naphthenic acids that are present in the hydrocarbon
fraction and acidic crude oil to reduce the acidity. In this regard, TPA-
supported catalysts for the organic acid esterification have been proven
to be efficient and eco-friendly solid acid catalysts; approximately
20–30 wt% TPA on suitable support materials leads to the highest ac-
tivity [30,32]. Among the different mesoporous materials, such as
MCM-41 and SBA-16, γ-alumina (γ-Al2O3) is commercially available
and the most important amphoteric material. Based on the combination
of its textural properties, such as surface area, pore volume, and pore
size distribution, it has been directly used as a catalyst and catalyst
support material in the automotive and petroleum industry [37,38].
The objective of this study was to develop an effective and eco-
friendly TPA supported solid acid catalyst which has been used for the
esterification of naphthenic acids in highly acidic crude oil with very
less consumption of methanol to reduce the TAN of acidic crude oil to
an acceptable level for the refinery. The effect of various reaction
parameters on the acid removal, such as reaction temperature, me-
thanol/oil ratio, and LHSV, was investigated using a fixed-bed con-
tinuous up-flow reactor.
2. Experimental section
2.1. Materials and reagents
The naphthenic acids containing various carboxylic acids having
TAN value of 200 mg KOH/g was purchased from Wako Chemical. The
boiling point range of naphthenic acids is 200–450 °C, as given in the
Table 4. The heavy crude oil (Castilla Crude Oil) was received from
Venezuela, the basic properties are given in Table 1. Methanol, 2-pro-
panol and toluene (HPLC grade) were purchased from SAMCHUN
Chemical. 12-Tungstophosphoric acid hydrate, H3[P(W3O10)4]·xH2O
(TPA) was purchased from Sigma-Aldrich and γ-Al2O3 was purchased
from Sasol Germany.
Table 1
Basic physical-chemical properties of Castilla Crude oil used in
this study.
Density, kg/m3 (at 15 °C) 0.9445
API gravity (at 60 °F) 18.2
Kinetic Viscosity in cft (at 40 °C) 139.2
Sulfur content (wt%) 1.53
Pour point (°C) −39.0
Nitrogen content (wt-ppm) 2787
MCR (wt%) 12.03
Salt Contents (PTB) 7.0
Acid Number (mg KOH/g) 0.203
B.S. Rana et al.
Fig. 1. Scheme of the experimental apparatus used for the continuous esterification.
2.1.1. Highly acidic crude oil (High TAN crude oil) preparation
Herein, the synthetic pseudo high acidic crude oil (High TAN crude
oil) as feedstock was prepared by mixing of the required amount of
0.952 g of naphthenic acids and 100 g of heavy crude oil. The me-
chanical stirrer was used for the proper mixing of naphthenic acids in
crude oil. The TAN was determined according to ASTM D664 method,
and reached to a values around 2.0 mg KOH/g. The TAN values of crude
oils having > 1 are to be considered as highly acidic crude oil [3].
2.2. Catalyst preparation
The spherically extruded alumina (γ-Al2O3, Sasol Germany) as me-
soporous support was preheated at 550 °C before use. The γ-Al2O3
supported TPA (25 wt% of TPA) as solid acid heterogeneous catalyst
was prepared by using conventional incipient wetness impregnation
method. In a typical procedure, a solution containing the required
amount of TPA in double distilled water was impregnated onto the
mesoporous γ-Al2O3 support and the excess water was then evaporated
using a rotary evaporator at 80 °C, and after that catalyst was dried at
120 °C in an oven for the overnight and then calcined at 300 °C for 4 h.
The prepared catalyst was denoted as TPA/γ-Al2O3.
2.3. Catalyst characterization
The BET surface area, pore volume, and pore size of the support and
catalyst were obtained with the Micromeritics ASAP-2020 instrument at
77 K using liquid N2. Before the analysis, the catalyst was evacuated at
300 °C for 5 h to remove the adsorbed moisture from the catalyst sur-
face and pores. Mesoporous size distributions were obtained with the
Barret–Joyner–Halenda (BJH) method from the desorption branch of
the isotherms.
Powder X-ray diffraction (XRD) patterns of fresh and used catalysts
were measured using a Rigaku Multiflex diffractometer and CuKα ra-
diation (40 kV, 40 mA).
The acidity of catalyst was determined based on NH3-temperature-
programmed desorption (NH3-TPD) using the Micrimetrics-720 instru-
ment; the catalyst was degassed at 250 °C under He flow for 2 h before
the analysis to remove the water vapor and avoid pore damage from
steaming, which might alter the structure of the catalyst, and cooled to
100 °C. The NH3 gas was adsorbed using 10% NH3 in Ar gas for 1 h. The
TPD (NH3-TPD) studies were carried out in a He stream of 30 ml min−1
273
Fuel 231 (2018) 271–280
by increasing the temperature from 100 to 700 °C at the ramp rate of
10 °C min−1; the temperature was held for two hours to remove
strongly bound species. Subsequently, the sample was cooled to 100 °C
in a He stream.
Thermogravimetric analysis (TGA) was performed using a DuPont
TGA51 thermogravimetric analyzer; 20–30 mg of the sample was
placed in a quartz basket, purged for 20 min at room temperature with
an N2-air mixture, and then heated from room temperature to 1000 °C
at a rate of 10 °C min−1 in the same gas mixture.
Scanning electron micrograph (SEM) images with EDS mapping
were obtained with a Hitachi S-4800 at 2 kV, without metal coating.
To determine the chemical composition of the fresh and used cat-
alysts and possible leaching of TPA from the supported catalyst, X-ray
fluorescence (XRF) analysis was performed using a Primus II (RIGAKU
Co., Japan).
2.4. Reaction procedure
The catalytic esterification of naphthenic acids with methanol in
highly acidic crude oil for the TAN reduction was conducted in a fixed-
bed reactor by using TPA/ γ-Al2O3 as the solid acid catalyst. The con-
tinuous flow fixed-bed reactor system comprises a feed tank with a
mechanical stirrer, feeding pump, furnace, fixed-bed type reactor
(material: SUS 316, inner diameter of 1.2 cm and length of 45 cm), and
gas/liquid separator combined with condenser. The schematic diagram
of the esterification reaction system is shown in Fig. 1.
The highly acidic heavy crude oil and methanol were uniformly
premixed according to a specified ratio at 20–30 °C and then poured
into the feed tank. The feedstocks in the feed tank were constantly
stirred using a mechanical stirrer during the experiment to prevent the
phase separation of the mixture. The catalyst was loaded in the middle
section of the reactor. The remaining spaces of the reactor were filled
with spherical glass beads (2–3 mm). The mixture of the pseudo highly
acidic crude oil and methanol, as the feedstocks, was pumped into the
reactor through the preheating section and heated to the reaction
temperature. The esterification reaction was carried out in the catalyst
bed section at temperatures varying from 175 °C to 300 °C. During the
reaction, produced oil was immediately cooled down to room tem-
perature as mentioned in the reactor system after back pressure reg-
ulator (BPR) to avoid the backward reaction and was collected in the
product container.
B.S. Rana et al. Fuel 231 (2018) 271–280

2.5. Analytical methods Table 2

Physical properties of the catalysts.
The TAN of the feed and product oil was measured using an auto- Catalyst BET Microspore Total Mesoporous Average
matic potentiometer with a glass electrode (Metrohm Titrando Plus surface volume (cm3/ pore volume (cm3/ pore
Model 904, Metrohm Ltd., Switzerland) based on a standard method area g) volume g) diameter
(ASTM D664, standard test method for the acid number of petroleum (m2/g) (cm3/g) (Å)

products by potentiometric titration). A required known amount of feed
and product oil was diluted with 125 ml of the titration solvent (iso-
propanol, toluene, and water in a ratio of 45:50:5 by volume). The
electrode was washed with the titration solvent before use. The
homogenous solution was then titrated using 0.1 N of methanolic po-
tassium hydroxide solution as titrant until it reached an end point. The
TAN is calculated based on the following equation [6]:
TAN (mgKOH /g ) = (A−B ) × M × 56.1/w (1)
where A is the volume of KOH used to reach the equilibrium point, B is
the volume of KOH for blank titration, M is the concentration of the
KOH solution, and w is the sample mass. The accuracy of the method
depends on the mass of the oil used. For a 10 g sample, each sample was
measured twice; the average of two TAN values was then calculated. If
the measurement error of the two TAN values was larger than ± 5%,
additional measurements were performed until the measurement error
was within ± 5% or less. The extent of acid removal was determined
using the following equation:
TANFO−TANPO
Acid Removal = × 100
TANFO (2)
where TANFO refers to the TAN of the feed oil and TANPO refers to the
TAN of the produced oil. It should be noted that the electrode must be
immersed in a buffer solution with pH of 4 (Metrohm US) for a
minimum of 10 min between the measurements. After five measure-
ments, the electrode was washed with 18 MX water and reconditioned
overnight in the electrolyte solution (3.0 M potassium chloride in
ethanol).
The water content after the esterification reaction of the naphthenic
acids was measured by Karl Fischer titration (877 KF Titrino,
Metrohm). Physical and chemical analyses of naphthenic acids were
conducted to obtain information on the carbon number distribution
estimated from the boiling point and chemical mapping. The analysis of
the carbon number and boiling point distributions was conducted using
simulated distillation (SIMDIS) based on the extended ASTM D 2887. In
addition, two-dimensional gas chromatography (GC) with a flame io-
nization detector (2D-GC/FID, Leco GC X GC with LN2-cooled thermal
modulator), 1st Rtx-1 column (length: 60 m, inner diameter: 0.25 mm,
phase film thickness: 0.25 μm), and 2nd Rxi-17Si column (length:
1.2 m, inner diameter: 0.15 mm, phase film thickness: 0.15 μm) was
conducted for chemical mapping. The main oven temperature for GC
was programmed from 40 °C to 300 °C, with a ramp of 2 °C/min, and the
detector temperature was maintained at 300 °C. The sample (0.2 μL)
was injected into the column at a 100:1 split ratio.
The used catalyst was washed with hot toluene, dried, and calci-
nated. The regenerated catalyst was characterized using XRF, TGA,
SEM, and BET surface area analyses.
3. Results and discussion
3.1. Catalyst characterization
The BET surface area, pore volume, and average pore diameter of
the fresh and used TPA/γ-Al2O3 catalysts were analyzed using N2 ad-
sorption-desorption isotherms. The physicochemical properties of the
catalysts are summarized in Table 2. Fig. 2 shows the N2 sorption iso-
therm of the fresh and used TPA/γ-Al2O3 catalysts, which is typical for
type IV due to the mesoporous structure, and a clear step in the ad-
sorption curves at the partial pressure P/P0 of 0.6–0.9 due to well-de-
fined mesoporosity. The BJH pore size distribution calculated from the
TPA/γ- 178.43 0.002 0.392 0.383 68.71
Al2O3
TPA/γ- 116.26 0.013 0.237 0.229 55.66
Al2O3
(use-
d)
Fig. 2. N2 adsorption-desorption isotherm and the corresponding BJH pore-size
distribution (inset) of fresh and used TPA/γ-Al2O3 based catalyst.
desorption branches of the isotherms (Fig. 2, inset) clearly shows that
the catalysts have a narrow pore size distribution with a mean pore
diameter of 68.71 Å for the fresh TPA/γ-Al2O3 catalyst and 55.66 Å for
the used catalyst. It is well known that the surface area, pore volume,
and pore diameter decrease after impregnation of the supported cata-
lyst in which oxides are used as support due to the strong interaction of
TPA with the oxide support material [39]. The decrease of the BET
surface area, pore volume, and pore diameter due to the TPA in-
corporation into the γ-Al2O3 support indicates that the TPA might be
dispersed in the support material [22], which is evidence for the che-
mical interaction between the TPA and support material. The N2
sorption and XRD studies reveal that the impregnation of TPA does not
affect the mesoporosity of the support material. Mesoporous support is
needed, specifically for large molecular reactions, to overcome diffu-
sion limitations and better diffuse large molecules and for lower deac-
tivation by pore blocking.
The XRD patterns of the support material and synthesized catalyst
are shown in Fig. 3. The XRD pattern of the TPA/γ-Al2O3 catalyst
clearly indicates that the synthesized catalyst is the typical γ-phase of
Al2O3 at 2θ of ∼36.5°, 45.9°, and 66.6° corresponding to the (3 1 1),
(4 0 0), and (4 4 0) reflections, respectively [40]. A characteristic peak
of the crystalline phase corresponding to TPA was not observed. The
absence of diffraction peaks due to the crystalline phase of TPA in the
Al2O3 support material could be attributed to the good dispersion of
this phase in the matrix of the γ-Al2O3 support material, forming very
small crystallites, which cannot be detected by XRD [41].
The NH3-TPD is a useful technique to investigate acidic properties
including the amount of acidic sites and acid strength of acidic cata-
lysts. The amount of acidic sites can be determined based on the
amount of desorbed NH3 and the acid strength can be determined based

274
B.S. Rana et al. Fuel 231 (2018) 271–280

Fig. 5. TGA profile of fresh and used TPA/γ-Al2O3 catalysts.

Fig. 3. XRD pattern of γ-Al2O3 support and TPA/γ-Al2O3 catalyst.
and TPA/γ-Al2O3 catalyst are presented in Fig. 4. The desorption tem-
peratures and amount of NH3 desorbed from each of the TPD peaks are
given in Table 3. The TPD profile of the TPA/γ-Al2O3 catalyst shows
two desorption peaks in the temperature range of 100–250 °C (in-
dicating weak acid sites) and 250–700 °C (indicating strong acid sites)
[42]. It was clear from Fig. 4 that weak acid sites of the catalyst (TPA/γ-
Al2O3) surface decreased with the addition of TPA, while increased in
the numbers of strong acid site. The nature of a solid acid catalyst is
mainly determined by the strongest acidic sites on its surface [31].
Thermo-gravimetric analyses of TPA/γ-Al2O3 fresh and used cata-
lyst are shown in Fig. 5. Two distinct regions of weight loss are shown
in the temperature ranges of 50–250 °C and 250–500 °C. The first
weight loss of 1.45% for fresh TPA/γ-Al2O3 catalyst and 2.72% for used
TPA/γ-Al2O3 catalysts in the temperature ranges of 50–250 °C corre-
sponds to desorption and removal of physisorbed water. The second
notable weight loss of 7.63% for fresh TPA/γ-Al2O3 catalyst and 7.73%
for regenerated used TPA/γ-Al2O3 catalysts in the temperature ranges
of 250–500 °C corresponds to the loss of water during the crystallization
of the Keggin ion of TPA. The results are in good agreement with the
reported one [43]. In the case of used catalyst, broad peak at
250–550 °C corresponds to relatively slow weight loss due to release of
Fig. 4. NH3-TPD profile of the γ-Al2O3 support and TPA/γ-Al2O3 catalyst. heavy hydrocarbon from the catalyst surface. In the temperature range
550–750 °C, the slight weight loss in the both fresh and used catalysts
Table 3 are associated with the decomposition of TPA to WO3 and P2Ox species
Acidity of pure-TPA, γ-Al2O3 support and TPA/ γ-Al2O3 catalyst from NH3-TPD. [44]. Herein, TGA analysis of catalyst reveals that the catalyst is stable
Sample Surface acidity (mmol/g NH3) up to 500 °C. This may be due to the formation of strong intermolecular
bonding between the TPA and the γ-Al2O3.
Weak acidity Strong acidity Total SEM with Energy-dispersive X-ray spectroscopy mapping (EDS-
(100–250 °C) (250–700 °C) acidity mapping) of the fresh and used TPA/γ-Al2O3 catalysts was carried out
Pure-TPA 0.224 0.973 1.197 to examine the elemental composition and its distribution (Fig. 6). The
γ-Al2O3 (Pretreated at 0.465 0.231 0.696 SEM with EDS mapping shows the expected elemental constituents: Al,
550 °C) O, P, and W., and the SEM with EDS mapping also indicates that the P
TPA/γ-Al2O3 catalyst 0.309 0.637 0.946 and W elemental species are homogeneous and well distributed on the
γ-Al2O3 surface. Furthermore, EDX measurements were carried out to
determine the chemical composition of the fresh and used catalysts. The
on the desorption temperature. The NH3 molecules adsorbed on the
quantitative analysis of different elements shows that the fresh TPA/γ-
catalyst are desorbed at lower temperature from weakly acidic sites and
Al2O3 catalyst contains 24.51 wt% W, 0.34 wt% P, and 33.58 wt% Al,
at high temperature from strongly acid sites. The γ-Al2O3 support
while the used TPA/γ-Al2O3 catalyst consists of 23.68 wt% W, 0.36 wt%
showed a broad distribution of the desorption peak in the temperature
P, and 30.05 wt% Al. The surface morphology of the fresh and the used
range of 100–700 °C, with a peak maxima at around 230 °C, indicating
catalysts (TPA/γ-Al2O3) is almost same. And from the SEM with EDS
that γ-Al2O3 support have only weak acid sites on the surface. However,
elemental mapping confirms that the surface morphology of fresh and
the TPD profile of pure TPA showed two desorption peak in the tem-
used catalysts indicates TPA species are well dispersed inside the γ-
perature range of 100–250 °C, indicating weak acid sites (mmol/g) and
Al2O3 pores. Further, no separate crystallites of bulk phase of TPA were
250–700 °C with peak maxima at 550 °C, indicating strong acid sites
found in both samples, and this can be also clearly observed by XRD
(mmol/g). The results are in good agreement with the reported one
diffraction pattern. Thus XRD pattern, SEM with EDS elemental map-
[42]. The NH3-TPD profiles of the γ-Al2O3 support material, pure TPA
ping are in good agreement with each other and confirms the uniform

275
B.S. Rana et al. Fuel 231 (2018) 271–280

Fig. 6. SEM and corresponding elemental mapping of (a) and (b) TPA/γ-Al2O3 fresh catalyst and (C and D) TPA/γ-Al2O3 used catalyst.

and high dispersion of TPA in a non-crystalline form due to the inter-
action with the support matrix.
3.2. Physical and chemical analysis of naphthenic acid
Before the experiments, physical and chemical analyses of naph-
thenic acids mixture, having TAN value of 200 mg KOH/g (Received
from Wako Chemicals) were conducted to obtain information on the
carbon number distribution estimated from the boiling point and the
chemical mapping. The analyses of the carbon number and boiling
point distributions were conducted using SIMDIST based on the ex-
tended ASTM D 2887 method. The analysis results for the naphthenic
acids used in this study is shown in the Table 4. The boiling point of
naphthenic acids ranges from 213 °C (IBP) to 449 °C (FBP). Compared
with the common fraction of petroleum oil, naphthenic acids consists in
the mixture of jet, kerosene, diesel fuel, fuel oil, and light vacuum gas
Table 4
Boiling point distribution of naphthenic acids using in this study (analyzed by
SIMDIS ASTM D2887 Extended).
Mass% Boiling point (°C) Mass% Boiling point (°C)
oil (LVGO), mainly diesel fuel oil and LVGO hydrocarbon fractions. The
results reveals that most of the naphthenic acids consists in the middle
distillates hydrocarbon fractions. And accordingly choice of the effec-
tive heterogeneous solid acid catalysts becomes more important for
TAN reduction of high acidic crude oils.
In addition, two-dimensional gas chromatography with a flame io-
nization detector (2D-GC/FID; Leco GC X GC with LN2 cooled thermal
modulator) was conducted for chemical mapping. The analysis results
are shown in Fig. 7. It is clear from Fig. 7 that the chemical mapping
showed strong peaks due to cyclo-paraffins with alkyl side chain ending
with carboxylic acids (naphthenic acids), which indicates that
Cycloaliphatic carboxylic acids
(Naphthenic Acids) Acids)
Mono and di-aromatics within NA

0.5 213 50 333.5

1 223.5 55 338.5
5 258.5 60 344
10 276 65 348.5
15 287.5 70 353.5
20 296.5 75 358.5
25 303.5 80 364
30 310.5 85 371
35 316.5 90 379
40 322.5 95 380.5
Fig. 7. Two-dimensional gas chromatogram (GC × GC-FID) of naphthenic acids
45 328 99.5 449
reagent.

276
B.S. Rana et al. Fuel 231 (2018) 271–280

Fig. 8. Effect of reaction temperature on the TAN change of product oil using
TPA/γ-Al2O3 catalyst. Fig. 9. Effect of the LHSV on the TAN change of product oil.

naphthenic acids are mainly derivatives of cyclo-paraffins carboxylic 0.5 mg KOH/g required for the acid removal in the petroleum industry
acids. A weak peak derived from isomers and derivatives of cyclo- when the LHSV was 2–4 h−1 at a reaction temperature of 250 °C. The
paraffin can be observed near the strong group peak of cyclo-paraffins processing at higher LHSVs facilitates more production and less in-
carboxylic acids. The peaks due to aromatics (mono and di-aromatics) vestment costs. The low consumption of methanol and processing at
within the naphthenic acids are grouped together away from that due to lower temperatures are other parameters that can reduce the processing
cyclo-paraffin carboxylic acids. The aromatics within the naphthenic cost and might be economically feasible for the industry. The reaction
acids content is too small compared with that of cyclo-paraffins deri- was also conducted at a lower reaction temperature of 200 °C for 1 wt%
vative carboxylic acids. methanol. The favorable condition for the low consumption of me-
thanol at a LHSV of 1 h−1 is 200 °C, which also leads to a TAN reduction
3.3. Catalytic performance to < 0.5 mg KOH/g and reduces the investment costs. The optimum
LHSV (h−1) at a temperature of 250 °C was determined to be between 3
3.3.1. Effect of the reaction temperature on the TAN reduction and 4 h−1 for 2 wt% methanol; at a temperature of 200 °C it is 1 h−1 for
The effect of the reaction temperature on the TAN reduction of 1 wt% methanol. In both cases, the TAN was reduced to < 0.5 mg KOH/
highly acidic crude oil was studied at temperatures ranging from 175 to g.
300 °C, a fixed LHSV of 5 h−1, and 2 wt% methanol in acidic crude oil
as feedstock represented in Fig. 8. It can be clearly seen from Fig. 8 that
3.3.3. Effect of the methanol concentration in crude oil
the TAN of the produced oil decreases sharply with increasing reaction
The effect of the methanol content in acidic crude oil, varying from
temperature (between 175 °C and 250 °C). At higher temperatures, a
0.5 to 2 wt%, on the acid removal was determined at temperatures of
high TAN reduction was obtained due to the enhanced, subsequent
250 °C and 200 °C for a LHSV of 3 h−1 and 1 h−1, respectively. Fig. 10
endothermic esterification of naphthenic acid with methanol. With
shows that 2 wt% methanol leads to the most effective results at 250 °C
further increasing reaction temperature (> 250 °C), the TAN slowly
for a LHSV of 3 h−1; however, 1 wt% methanol at 200 °C for a LHSV of
decreases due to the attainment of the chemical equilibrium and fast
reaction rate. Palani and Pandurangan also report that an increasing
reaction temperature promotes the removal of water formed as by-
product during the esterification reaction. This water acts as a poison by
adsorption on the hydrophilic sites of the solid acid catalyst; hence, the
removal of the water can improve the catalytic activity with increasing
temperature [45]. The reaction temperature for the esterification of
naphthenic acids in acidic crude oil with 2 wt% methanol should be
higher than 270 °C to reduce the TAN of crude oil to a values < 0.5 mg
KOH/g (the upper limit of low acid crude oil), where LHSV is 5 h−1.
The TAN was reduced < 0.5 mg KOH/g at temperature of 275 °C and
300 °C. In the present study, we achieved the required target for low-
ering of TAN to a values < 0.5 at temperature of < 300 °C. Above the
300 °C, however, the corrosion problem may become more serious on
processing units and the other catalytic systems [46].

3.3.2. The effect of LHSV (h−1)

The effect of different LHSVs on the TAN reduction at 250 °C and
200 °C using 2 and 1 wt% methanol in the acidic crude oil as feedstock,
respectively, were investigated as represented in Fig. 9. The TAN values
of the crude oil increases as the LHSV increases. This means that the
time for the reactant molecules at catalytic active sites is not sufficient Fig. 10. The TAN change of product oil with effect of methanol wt% in acidic
for a reaction to occur. Fig. 9 also shows that the TAN reduced to < crude oil.

277
B.S. Rana et al. Fuel 231 (2018) 271–280

work
work
work
work
work
Reference

Present
Present
Present
Present
Present
[18]

[16]
[17]
[19]
[6]

Stable up to 100 h
Stable up to 60 h
Catalyst stability

–
–
–
–
–
–
–
–
Acid removal (%)

81.00
95.00
89.50

79.25
82.55
80.90

79.25
> 80
Feed TAN (mg KOH/g)

Fig. 11. The TAN changes of product oil as a function of reaction time (h) at
different reaction conditions.

1 h−1 shows comparative results with respect to the TAN reduction to a

4.10
0.59

2.00
2.00
2.00
2.00
2.00
4.2
1.7

2.8

value acceptable for the petroleum industry.

Fig. 10 also shows that 0.5 and 1 wt% methanol result in an effective
acid removal; however, the most effective acid removal is favorable by
T = 300 °C, RT = 2 h Methanol/oil(w/w) = 0.05 4 wt% SnO

using 2 wt% methanol in acidic crude oil as feedstock. It can be noted

T = 280 °C, LHSV = 1.2 h−1 Methanol/oil(w/w) = 0.010

LHSV = 2.5 h−1 Methanol/oil(w/w) = 0.02

that using 1 wt% methanol at a lower LHSV and temperature reduced

LHSV = 5 h−1 Methanol/oil(w/w) = 0.02
LHSV = 3 h−1 Methanol/oil(w/w) = 0.01
LHSV = 1 h−1 Methanol/oil(w/w) = 0.01
LHSV = 1 h−1 Methanol/oil(w/w) = 0.01
LHSV = 3 h−1 Methanol/oil(w/w) = 0.02
T = 250 °C, RT = 7.5 h, Methanol/oil(w/w) = 0.024

the acid removal to an acceptable value to process acidic crude oil in

the petroleum industry. These results are much more effective than the
results reported by Wang et al. using a SnO-Al2O3 catalyst for the es-
Comparative study of esterification of naphthenic acids in acidic crude oil or its fractions over various catalysts.

terification of naphthenic acids in crude oil in a fixed-bed catalytic

reactor system [19], using a SnO catalyst for the esterification of the
second vacuum fraction in a batch reactor system [16], and in the U.S.
patent No. 6251305 using batch reactor system at high temperature for
longer reaction times (without catalyst) [18]. A detailed comparison of
different catalysts is shown in Table 5.
Operating conditions

3.4. Stability of the catalyst

T = 300 °C,
T = 275 °C,
T = 250 °C,
T = 200 °C,
T = 200 °C,
T = 250 °C,

To investigate the catalyst stability as a function of time-on-stream

(TOS), a long-term experiments were conducted under two different
reaction conditions as represented in Fig. 11. It is clear that the activity
Process reactor

of catalyst remains basically unchanged up to near 100 h of time-on-

stream at a reaction temperature of 250 °C and LHSV of 3 h−1 using
Fixed Bed

Fixed Bed
Fixed Bed

Fixed Bed

2 wt% methanol in acidic crude oil as feedstock, where the TAN was
Batch

Batch
Batch

reduced to a value below 0.5 mg KOH/g. Furthermore, the catalyst

stability at a reaction temperature of 200 °C and LHSV of 1 h−1 using
1 wt% methanol in acidic crude oil is unchanged up to 60 h of time-on-
Acidic crude oil (Gryphon Crude)

stream, where the TAN was also reduced to a value below 0.5 mg KOH/
g. However, after 60 h of time-on-stream, the catalyst activity for TAN
reduction was decreased at 200 °C of the reaction temperature. The
Second vacuum fraction

main reason for low long-term catalytic stability as a function of time-

on-stream at low reaction temperature (200 °C) might be attributed to
Acidic crude oil
Acidic crude oil

Acidic crude oil

Dewaxed VGO

slow diffusion rate of the product molecules and the product species
including bulky molecules of asphaltenes which can block pores of the
Feedstock

Diesel oil

catalyst. Thus, improving the catalyst longevity of TPA/γ-Al2O3 is big

challenge for future applications.
Mg-Al hydrotalcite

3.5. Reaction mechanism

Without Catalyst

TPA/γ-Al2O3

Esterification of naphthenic acids with methanol is an equilibrium,

TPA/Al2O3
SnO/Al2O3

SnO/Al2O3
Catalyst

limited, and electrophilic reaction, which is considered to be relatively

Table 5

SnO

slow and requires the activation by either a suitable catalyst or a higher

reaction temperature to achieve higher acid removal rates. A possible

278
B.S. Rana et al.
Fig. 12. Proposed mechanism for the esterification of naphthenic acids with methanol over TPA/γ-Al2O3 catalyst.
reaction mechanism that is involved in the esterification of naphthenic
acids with methanol over solid acid catalysts (TPA/γ-Al2O3) is shown in
Fig. 12. This esterification reaction follows the Eley–Rideal mechanism,
which takes place between naphthenic acid and protons chemisorbed
on the active site (Bronsted acid sites) of the solid acid catalyst surface
by donating a proton to the carboxylic acid group of naphthenic acids,
resulting in stable carbocation. The carbocation-possessing positive
charge is then nucleophilically attacked by one of the lone pairs of the
oxygen of the methanol to form an unstable intermediate molecule. In
the last step, the elimination of the water molecule from the unstable
intermediate molecule leads to the methyl naphthenate as final product
accompanied by water and the regeneration of the solid acid catalyst.
3.6. Comparative study of the catalysts
The TAN reduction performance of the currently studied catalyst
was compared with that of catalysts reported in the literature for the
esterification of naphthenic acids in acidic crude oils or its fractions
using batch or fixed-bed reactor systems (Table 5). These comparisons
have been performed at optimal reaction conditions for each catalyst. It
can be observed that using a TPA/γ-Al2O3 catalyst results in a larger
TAN reduction, low methanol consumption, lower reaction temperature
and higher space velocity compared with catalysts reported in litera-
ture.
4. Conclusions
The TAN reduction of highly acidic crude oil via continuous ester-
ification of naphthenic acids with methanol was successfully performed
using TPA supported on mesoporous γ-Al2O3 (TPA/γ-Al2O3) as a het-
erogeneous solid acid catalyst in a fixed-bed reactor. In this process, the
TAN of highly acidic crude oil was reduced to a value (below TAN of
0.5) acceptable for the petroleum industry. The reaction temperature,
LHSV, and methanol content in acidic crude oil are the primary factors
affecting the reaction. The optimum reaction conditions for the ester-
ification of naphthenic acids in crude oil in a fixed-bed continuous flow
reactor system were were confirmed. At high space velocity
(LHSV = 5 h−1) of the highly acidic crude oil, reaction temperature
should be higher than 275 °C with methanol concentration of 2 wt% to
achieve TAN reduction to 0.5 mg KOH/g. When the reaction tempera-
ture was decreased to 250 °C, the optimized conditions for LHSV and
methanol condition were 3 h−1 and 2 wt%, respectively. At much lower
reaction temperature, 200 °C, LHSV should be decreased to 1 h−1 to
reduce TAN to 0.5. In addition, catalyst stability test as a function of
time-on-stream was conducted at two different reaction conditions.
Furthermore, the best result of the catalyst stability as a function of
time-on-stream were observed at reaction temperature of 250 °C, LHSV
of 3 h−1 and using 2 wt% methanol in acidic crude as feedstock. Under
this condition, the TAN value could be maintained to be lower than
0.5 mg KOH/g for 102 h of time-on-stream.
279
Fuel 231 (2018) 271–280
The TPA/γ-Al2O3 catalyst promotes the esterification reaction at
lower reaction temperatures and under low consumption of methanol,
as compared to other previous catalysts. In addition, the removal of
water which is side product in the continuous flow reactor and im-
mediate cooling systems improve both the esterification reaction speed
and equilibrium. The TAN reduction of high acidic crude oils with very
low consumption of methanol at moderate temperatures in continuous
flow reactor is a prospectively economically-viable option for extensive
utilization of lower price high TAN Crude oils without material mod-
ifications in existing petroleum refineries.
Acknowledgements
This work was supported by the Industrial Strategic Technology
Development Program (No. 10045068, Title: Development of flow as-
surance and organic acid/calcium removal process for the production of
offshore opportunity crude) of Korea Evaluation Institute of Industrial
Technology funded by the Ministry of Trade, Industry and Energy (MI.
Korea).
References
[1] BP. BP Statistical Review of World Energy June 2015. Br Pet 2015:48. doi:bp.com/
statisticalreview.
[2] Wu B, Li X, Zhu J, Huang Y, Cheng H. Identification of acidic species extracted from
heavy crude oil by fourier transform ion cyclotron resonance mass spectrometry.
Korean J Chem Eng 2014;31:1082–7. http://dx.doi.org/10.1007/s11814-014-
0002-x.
[3] Speight JG. High acid crudes. 1st ed. Oxford: Elsevier, Gulf Professional Publishing;
2014.
[4] Dias HP, Gonçalves GR, Freitas JCC, Gomes AO, De Castro EVR, Vaz BG, et al.
Catalytic decarboxylation of naphthenic acids in crude oils. Fuel 2015;158:113–21.
http://dx.doi.org/10.1016/j.fuel.2015.05.016.
[5] Flego C, Galasso L, Montanari L, Gennaro ME. Evolution of naphthenic acids during
the corrosion process. Energy Fuels 2014;28:1701–8. http://dx.doi.org/10.1021/
ef401973z.
[6] Wang YZ, Sun XY, Liu YP, Liu CG. Removal of naphthenic acids from a diesel fuel by
esterification. Energy Fuels 2007;21:941–3. http://dx.doi.org/10.1021/ef060501r.
[7] ASTM International. ASTM D664–11a: standard test method for acid number of
petroleum products by potentiometric titration. Annu B ASTM Stand 2011:1–7.
http://dx.doi.org/10.1520/D0664-11A.This.
[8] Chakravarthy R, Naik GN, Savalia A, Sridharan U, Saravanan C, Das AK, et al.
Determination of naphthenic acid number in petroleum crude oils and their frac-
tions by mid-fourier transform infrared spectroscopy. Energy Fuels
2016;30:8579–86. http://dx.doi.org/10.1021/acs.energyfuels.6b01766.
[9] Slavcheva E, Shone B, Turnbull A. Review of naphthenic acid corrosion in oil re-
fining. Br Corros J 1999;34:125–31. http://dx.doi.org/10.1179/
000705999101500761.
[10] Nasir Shah S, Mutalib MIA, Pilus RBM, Lethesh KC. Extraction of naphthenic acid
from highly acidic oil using hydroxide-based ionic liquids. Energy Fuels
2015;29:106–11. http://dx.doi.org/10.1021/ef502169q.
[11] Wang Y, Chu Z, Qiu B, Liu C, Zhang Y. Removal of naphthenic acids from a vacuum
fraction oil with an ammonia solution of ethylene glycol. Fuel 2006;85:2489–93.
http://dx.doi.org/10.1016/j.fuel.2006.04.032.
[12] Gaikar VG, Maiti D. Adsorptive recovery of naphthenic acids using ion-exchange
resins. React Funct Polym 1996;31:155–64. http://dx.doi.org/10.1016/1381-
5148(96)00054-5.
[13] Zhang A, Ma Q, Wang K, Liu X, Shuler P, Tang Y. Naphthenic acid removal from
crude oil through catalytic decarboxylation on magnesium oxide. Appl Catal A Gen
B.S. Rana et al.
2006;303:103–9. http://dx.doi.org/10.1016/j.apcata.2006.01.038.
[14] Ding L, Rahimi P, Hawkins R, Bhatt S, Shi Y. Naphthenic acid removal from heavy
oils on alkaline earth-metal oxides and ZnO catalysts. Appl Catal A Gen
2009;371:121–30. http://dx.doi.org/10.1016/j.apcata.2009.09.040.
[15] Oh H-Y, Park J-H, Rhee Y-W, Kim J-N. Decarboxylation of naphthenic acid using
alkaline earth metal oxide. J Ind Eng Chem 2011;17:788–93. http://dx.doi.org/10.
1016/j.jiec.2011.05.024.
[16] Wang YZ, Liu YP, Liu CG. Removal of naphthenic acids of a second vacuum fraction
by catalytic esterification. Pet Sci Technol 2008;26:1424–32. http://dx.doi.org/10.
1080/10916460701272229.
[17] Li X, Zhu J, Liu Q, Wu B. The removal of naphthenic acids from dewaxed VGO via
esterification catalyzed by Mg-Al hydrotalcite. Fuel Process Technol
2013;111:68–77. http://dx.doi.org/10.1016/j.fuproc.2013.01.016.
[18] Esterification of acidic crudes. U.S. Pat. No. 6251305, 2001.
[19] Wang YZ, Li JY, Sun XY, Duan HL, Song CM, Zhang MM, et al. Removal of naph-
thenic acids from crude oils by fixed-bed catalytic esterification. Fuel
2014;116:723–8. http://dx.doi.org/10.1016/j.fuel.2013.08.047.
[20] Melero JA, Iglesias J, Morales G. Heterogeneous acid catalysts for biodiesel pro-
duction: current status and future challenges. Green Chem 2009;11:1285. http://
dx.doi.org/10.1039/b902086a.
[21] Okuhara T, Mizuno N, Misono M. Catalysis by heteropoly compounds—recent de-
velopments. Appl Catal A Gen 2001;222:63–77. http://dx.doi.org/10.1016/S0926-
860X(01)00830-4.
[22] Brahmkhatri V, Patel A. 12-Tungstophosphoric acid anchored to SBA-15: an effi-
cient, environmentally benign reusable catalysts for biodiesel production by ester-
ification of free fatty acids. Appl Catal A Gen 2011;403:161–72. http://dx.doi.org/
10.1016/j.apcata.2011.06.027.
[23] Rafiee E, Eavani S. Heterogenization of heteropoly compounds: a review of their
structure and synthesis. RSC Adv 2016;6:46433–66. http://dx.doi.org/10.1039/
C6RA04891A.
[24] Pires LHO, de Oliveira Jr. AN, Monteiro OV, Angélica RôS, da Costa CEF, Zamian
JR. Esterification of a waste produced from the palm oil industry over 12-tung-
stophosforic acid supported on kaolin waste and mesoporous materials. Appl Catal
B Environ 2014;160-161:122–8. http://dx.doi.org/10.1016/j.apcatb.2014.04.039.
[25] Bala DD, Misra M, Chidambaram D. Single step esterification of algae oil using
mesoporous solid acid catalyst. Fuel 2014;117:1093–5. http://dx.doi.org/10.1016/
j.fuel.2013.10.031.
[26] Shikata S, Nakata SI, Okuhara T, Misono M. Catalysis by heteropoly compounds. 32.
Synthesis of methyl tert-butyl ether catalyzed by heteropolyacids supported on si-
lica. J Catal 1997;166:263–71. http://dx.doi.org/10.1006/jcat.1997.1502.
[27] Kamiya Y, Ooka Y, Obara C, Ohnishi R, Fujita T, Kurata Y, et al. Alkylation-acy-
lation of p-xylene with γ-butyrolactone or vinylacetic acid catalyzed by hetero-
polyacid supported on silica. J Mol Catal A Chem 2007;262:77–85. http://dx.doi.
org/10.1016/j.molcata.2006.08.055.
[28] Khder AERS. Preparation, characterization and catalytic activity of tin oxide-sup-
ported 12-tungstophosphoric acid as a solid catalyst. Appl Catal A Gen
2008;343:109–16. http://dx.doi.org/10.1016/j.apcata.2008.03.027.
[29] Oliveira CF, Dezaneti LM, Garcia FAC, de Macedo JL, Dias JA, Dias SCL, et al.
Esterification of oleic acid with ethanol by 12-tungstophosphoric acid supported on
zirconia. Appl Catal A Gen 2010;372:153–61. http://dx.doi.org/10.1016/j.apcata.
2009.10.027.
[30] Patel A, Singh S. A green and sustainable approach for esterification of glycerol
using 12-tungstophosphoric acid anchored to different supports: kinetics and effect
of support. Fuel 2014;118:358–64. http://dx.doi.org/10.1016/j.fuel.2013.11.005.
[31] Kulkarni MG, Gopinath R, Meher LC, Dalai AK. Solid acid catalyzed biodiesel
280
Fuel 231 (2018) 271–280
production by simultaneous esterification and transesterification. Green Chem
2006;8:1056. http://dx.doi.org/10.1039/b605713f.
[32] Hoo PY, Abdullah AZ. Direct synthesis of mesoporous 12-tungstophosphoric acid
SBA-15 catalyst for selective esterification of glycerol and lauric acid to mono-
laurate. Chem Eng J 2014;250:274–87. http://dx.doi.org/10.1016/j.cej.2014.04.
016.
[33] Khayoon MS, Hameed BH. Single-step esterification of crude karanj (Pongamia
pinnata) oil to fatty acid methyl esters over mesostructured SBA-16 supported 12-
molybdophosphoric acid catalyst. Fuel Process Technol 2013;114:12–20. http://dx.
doi.org/10.1016/j.fuproc.2013.03.014.
[34] Narkhede N, Patel A. Biodiesel production by esterification of oleic acid and
transesterification of soybean oil using a new solid acid catalyst comprising 12-
tungstosilicic acid and zeolite. Ind Eng Chem Res 2013;52:13637–44. http://dx.doi.
org/10.1021/ie402230v.
[35] Altiokka MR, Akbay E, Him Z. Impregnation of 12-tungstophosphoric acid on tonsil:
An effective catalyst for esterification of formic acid with n-butyl alcohol and ki-
netic modeling. J Mol Catal A Chem 2014;385:18–25. http://dx.doi.org/10.1016/j.
molcata.2014.01.011.
[36] Lacerda ODS, Cavalcanti RM, De Matos TM, Angélica RS, Da Rocha Filho GN,
Barros IDCL. Esterification of oleic acid using 12-tungstophosphoric supported in
flint kaolin of the Amazonia. Fuel 2013;108:604–11. http://dx.doi.org/10.1016/j.
fuel.2013.01.008.
[37] Zhang J, Chen J, Ren J, Sun Y. Chemical treatment of γ-Al2O3 and its influence on
the properties of Co-based catalysts for Fischer-Tropsch synthesis. Appl Catal A Gen
2003;243:121–33. http://dx.doi.org/10.1016/S0926-860X(02)00541-0.
[38] Silva-Rodrigo R, Hernández-López F, Martinez-Juarez K, Castillo-Mares A, Melo
Banda JA, Olivas-Sarabia A, et al. Synthesis, characterization and catalytic prop-
erties of NiMo/Al2O3-MCM-41 catalyst for dibenzothiophene hydrodesulfurization.
Catal Today 2008;130:309–19. http://dx.doi.org/10.1016/j.cattod.2007.10.001.
[39] Armatas GS, Katsoulidis AP, Petrakis DE, Pomonis PJ. Synthesis and acidic catalytic
properties of ordered mesoporous alumina–tungstophosphoric acid composites. J
Mater Chem 2010;20:8631. http://dx.doi.org/10.1039/c0jm01283a.
[40] Hosseini SNM. Synthesis and characterization of different γ-Al2O3 nanocatalysts for
methanol dehydration to dimethyl ether. Int J Chem React Eng
2012;10:1542–6580. http://dx.doi.org/10.1515/1542-6580.3072.
[41] Méndez FJ, Llanos A, Echeverría M, Jáuregui R, Villasana Y, Díaz Y, et al.
Mesoporous catalysts based on Keggin-type heteropolyacids supported on MCM-41
and their application in thiophene hydrodesulfurization. Fuel 2013;110:249–58.
http://dx.doi.org/10.1016/j.fuel.2012.11.021.
[42] Liu J, Lei J, He J, Deng L, Wang L, Fan K, et al. Hydroprocessing of jatropha oil for
production of green diesel over non-sulfided Ni-PTA/Al2O3 catalyst. Sci Rep
2015;5:11327. http://dx.doi.org/10.1038/srep11327.
[43] Kamalakar G, Komura K, Kubota Y, Sugi Y. Friedel-Crafts benzylation of aromatics
with benzyl alcohols catalyzed by heteropoly acids supported on mesoporous silica.
J Chem Technol Biotechnol 2006;81:981–8. http://dx.doi.org/10.1002/jctb.1488.
[44] Newman AD, Brown DR, Siril P, Lee AF, Wilson K. Structural studies of high dis-
persion H3PW12O40/SiO2 solid acid catalysts. Phys Chem Chem Phys
2006;8:2893–902. http://dx.doi.org/10.1039/b603979k.
[45] Palani A, Pandurangan A. Esterification of acetic acid over mesoporous Al-MCM-41
molecular sieves. J Mol Catal A Chem 2005;226:129–34. http://dx.doi.org/10.
1016/j.molcata.2004.09.017.
[46] Qu DR, Zheng YG, Jing HM, Yao ZM, Ke W. High temperature naphthenic acid
corrosion and sulphidic corrosion of Q235 and 5Cr1/2Mo steels in synthetic re-
fining media. Corros Sci 2006;48:1960–85. http://dx.doi.org/10.1016/j.corsci.
2005.08.016.