FuelProcessing Technology 92 (2011) 53–57

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FuelProcessing Technology
jo u rn a l h o m e p a g e : w w w.e ls ev ie r.c o m /lo c a te /fu p ro c

Metaloxides as heterogeneous catalysts foresterification offatty acids obtained from

soybean oil
Vinicius M.Mello,Gabriella P.A.G.Pousa,Mírian S.C.Pereira,Ingrid M.Dias,Paulo A.Z.Suarez ⁎
Laboratório de Materiais e Combustíveis,Instituto de Química,Universidade de Brasília,CP 4478,CEP 70919-970,Brasília-DF,Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The growing demand for renewable energy sources stimulates the development of new technologies for
Received 2 July 2010 biofuelproduction.Biodieselsynthesis by esterification offatty acids is a favorable route,because,differently
Received in revised form 24 August 2010 from transesterification,itdoesnotproduce glycerin and usescheaperraw materials.In thiswork the study of
Accepted 29 August 2010
metaloxides and their performance as Lewis acid catalysts in the esterification offatty acids obtained from
soybean oilpresented promising results in heterogeneous catalysis,with reaction yields as high as 89%.The
Keywords:
Biodiesel
influence ofvariables such as temperature,reaction time and the amountofcatalystin the reaction yield was
Esterification also evaluated.The possibility ofrecycling tin oxide wasalso studied,showing thatitwaspossible to reuse the
Tin catalyst up to ten times withoutsignificantlosses in its catalytic activity.
Aluminum © 2010 Elsevier B.V.Allrights reserved.
Zinc
Heterogeneous catalysis

1.Introduction However this biodiesel production using alkaline basic catalysts

The growing concern around the world regarding fuel supply
security as wellas the emission of polluting and green house gases
stimulatesthe search fornew routesto produce liquid fuels[1].In this
context,biofuelproduction from renewable sources has been pointed
out as an elegant alternative to partially replace petroleum-derived
fuels,being biodiesel,a mixture ofdifferentmethylorethylfatty acid
esters,the most accepted choice for dieselengines [2].Indeed,some
examples ofthe severaladvantages ofthe use ofthis type ofbiofuel
may be cited,particularly the reduction on the emission ofsulfur(SOx)
and carbon (CO and CO2)compoundswhile burning biodieselin diesel
engines and the possibility to use it neat or blended with diesel
without any mechanical change [3].As a result,as in several other
countries around the world,the Brazilian government's incentives to
biodiesel production gave a new boost in the search for different
synthesisroutesand the developmentofnew catalysts,especially after
the creation ofa NationalProgram ofBiodieselProduction (PNPB)[4].
Biodieselcan be produced by transesterification (oralcoholysis)of
oils and fats (from vegetable oranimalsources) orby esterification of
fatty acids. The alcoholysis of oils and fats by homogeneous basic
catalysis using mono-alcohols (usually methanol and ethanol)
producing methyl or ethyl esters and glycerin, shown in Fig. 1, is
the mostcommonly used process for biodieselproduction [5].
⁎ Corresponding author.Tel.:+55 61 31073852.
E-mailaddress:psuarez@unb.br (P.A.Z.Suarez).
has some disadvantages [6,7],such as: (i) the presence of free fatty
acids or water in vegetable oils can be an obstacle to biodiesel
production due to soap formation;hence,high-quality raw materials
are required;(ii) large amounts ofglycerin as wellas mono- and di-
acylglycerides may be formed as by-products, hampering the
production ofbiodieselwith desirable purity.
The esterification process seems to be a good solution to some of
these problems.In thisreaction,shown in Fig.2,there isno formation
ofglycerin orotherglyceride products.Itcan also be performed using
low-coststocksasraw material,such asacid groundsproduced during
edible oilneutralization orfats and oils with high amountoffree fatty
acids,such as those produced by algae,palm-trees or animals.
Many studiesreporton catalyticsystemsbased on Brönsted orLewis
acids,in both homogeneous and two-phase heterogeneous conditions,
as suitable candidates for esterification offatty acids [6–16].Homoge-
neoussystemswith strong mineralacidsare often related to equipment
corrosion problems and difficulty in separating from the products.On
the other hand,heterogeneous systems have lower yields because of
difficulties during reagents phase transition.Therefore,the challenge is
to develop a heterogeneous acid catalyst for the esterification process
thatcombines high activity,easy separation from the products and no
corrosiveness.
The aim ofthis work is the study ofesterification reactions offatty
acidsobtained from soybean oilwith methanol,assisted by Lewisacid
solid metal oxides such as alumina, tin oxide and doped alumina,
which are known to be Lewis acid catalysts for transesterification
reactions [17,18]. The influence of different reaction parameters
(temperature,time,and amountofcatalyst) in the reaction yield was

0378-3820/$ – see front matter © 2010 Elsevier B.V.Allrights reserved.

doi:10.1016/j.fuproc.2010.08.019
54 V.M.Mello et al./ FuelProcessing Technology 92 (2011) 53–57

R1 O
R R1
O O OH
O O
R R2 +
+ 3 HO R OH
O O HO
O
O R R3
O R2 O
R3 O

Oilor fat Alcohol Biodiesel Glycerin

Fig.1.Transesterification oftriacylglycerides.

O O

R1 + R OH H2O + R R1
HO O

Fatty Acid Alcohol Biodiesel

Fig.2.Esterification offatty acids.

studied through the decrease in the acidity index.An investigation on
the recycling ofa tin oxide catalystwas also undertaken.
2.Experimental
2.1.Materials
Edible soybean oil was purchased from Bunge and used as
received.Reagent grade chemicals were obtained from Aldrich and
used withoutfurther purification.
The fatty acids mixture was obtained through saponification of
soybean oil using sodium hydroxide followed by acidification with
hydrochloricacid.The mixture waswashed with waterand dried with
magnesium sulfate. The composition of this fatty acid mixture,
determined by HPLC using the same method published elsewhere
[14],wasin the range expected forsoybean oil(linoleicacid,52%;oleic
acid,24%;palmitic acid,14%;estearic acid,4%;and other acids,6%).
All catalysts were prepared through a co-precipitation technique
according to a previously published method [17,18].The amountsoftin,
zinc and aluminum present in the catalysts were determined using a
Varian Liberty RL SeriesIIInductively Coupled Plasma-OpticalEmission
Spectrometer (ICP OES).Catalysts’ surface areas were calculated using
the BET method, through nitrogen adsorption isotherms (Quanta-
chrome NOVA 2200e) [19].The average distribution ofpore sizes was
calculated using the BJH method [20].Alladsorption and desorption
isotherms were obtained at the temperature of 77 K. Programmed
desorption temperatures were obtained using a CHEMBET-3000
equipment (American Quantachrome Company).Approximately 0.2 g
ofeach sample was treated (400 °C) for50 min underconstantflow of
helium (80 cm3 m−1) priorto NH3 adsorption.Aftersample purge,the
TPD spectrum was obtained undera temperature increase from 150 °C
up to 800 °C,ata rate of15 °C min−1.
2.2.Esterification
Esterification was carried out in a home-made stainless steel
autoclave.The catalystand the fatty acid mixture were inserted in the
reactor through a valve. Methanol was stored in a stainless steel

Table 1 Table 3
Chemicalanalysis ofthe solids studied in this work. Ammonia desorption temperatures ofthe catalyststudied in this work.

Catalyst Chemicalanalysis (%) Catalyst Desorption temperature (°C) Peak intensity (mV)

Al2O3 SnO ZnO (1) (Al2O3)8(SnO)2 550−800 130

(2) (Al2O3)8(ZnO)2 550–880 70
(1) (Al2O3)8(ZnO)2 80.0 – 20.0
(3) SnO 450–650 3
(2) (Al2O3)8(SnO)2 81.3 18.7 –
(4) Al2O3 250–450 and 500−700 3
(3) SnO – 100 –
(4) Al2O3 100 – –

Table 4
Reaction yields for the differentcatalystundersimilar conditions.Reaction conditions:
4 g ofmethanol;10 g offatty acid;0.1 g ofcatalyst;temperature 160 °C;and reaction
Table 2 time 1 h.
Catalystsurface area ofthe solids studied in this work.
Entry Catalyst Yield (%)
Catalyst Surface area (m2 g−1)
1 No catalyst 32
(1) (Al2O3)8(SnO)2 22 2 (Al2O3)4(ZnO) 50
(2) (Al2O3)8(ZnO)2 33 3 (Al2O3)4(SnO) 61
(3) SnO 15 4 SnO 69
(4) Al2O3 119 5 Al2O3 74
 V.M.Mello et al./ FuelProcessing Technology 92 (2011) 53–57 55

O O
R [M ] CH3OH
OCH3 1

CH3
O R 2 OCH3
M C 4 M
O OH
O

3
RCOOH
OCH3
M
O R H2O

O
Fig.3.Proposed mechanism for the esterification offatty acids catalyzed by Lewis acid metaloxides.

reservoirconnected to the reactorby a valve.Underconstantmagnetic
stirring, the reactor was heated until the desired temperature was
achieved. The temperature was monitored with a thermocouple
inserted in a stainless steel cold finger in contact with the reaction
bulk. At the desired temperature, methanol was introduced in the
reactor and the reaction started.Ata previously determined time,the
reaction wasstopped by turning offthestirring and heating and opening
the reactorvalve,when an instantaneous evaporation ofmethanoland
water occurred.The product was then dried in a rotary evaporator to
ensure complete removalofresidualwaterand methanol.
Reaction yieldswere calculated based on the reduction ofthe acidity
index forproductsascompared with the acidity index forthe initialfatty
acids mixture.All acidity indexes were determined according to the
AOCS Cd3d63 specification [21].Itisimportantto note thatwe made an
1
extensive study of these reactions by H NMR and HPLC in order to
develop the most appropriate spectroscopic method to determine
esterification reaction yields,as published elsewhere [22].During this
study,not only did we confirm the results obtained by this titration
method, but also observed that only methyl fatty acid esters were
formed.
In the catalyst recycling study,tin oxide was recovered from the
products by centrifugation, after which the recovered solid was
washed severaltimes with CH3Cland dried in an oven at 110 °C.All
substrate charging assayswere carried outunderthe same conditions
and procedures as the firstcharge.
3.Results and discussion
The amounts of tin,zinc and aluminum were determined by ICP
emission spectroscopy and the results of the chemical analysis are
shown in Table 1.Itbecomes clear from these data thatthe resulting
solid compositions are in good agreementwith the theoreticalvalues.
Specific BET surface areas for all catalysts studied are listed in
Table 2. The catalyst surface area is commonly influenced by the
preparation method.Itcan be observed thatdoped alumina—catalysts
(1) and (2)—presented a significant decrease in surface area when
compared to pure alumina—catalyst(4).
The range ofNH3 desorption temperatures forallcatalysts studied
is shown in Table 3.Peaks thatappearin lowertemperatures indicate
weaker acid sites, and peaks that appear in higher temperatures
indicate the presence ofstrongeracid sites.Catalyst(4)presented two
peaks(Table 3),one atlowertemperatures(250–450 °C)and another
at higher temperatures (500–700 °C).However it was observed that
the intensity of both peaks was low (around 3 mV),leading to the
conclusion thatcatalyst(4) presents weak acid sites.Itcould also be
observed thatthe strength ofthe acid sites increases when alumina is
doped (see catalysts (1) and (2) in Table 3).Note that the values in
mV for the intensity of the peaks have a direct relation with the
amountofdesorbed ammonia.Although itis notpossible to obtain an
absolute value,these resultsallow usto relatively compare the surface
acidity ofthe differentcatalysts studied here.
Differentmetaloxides were tested as catalysts forthe esterification
reaction. The results obtained for each catalyst used are shown in
Table 4. Although fatty acids are weak Brönsted acids they present
catalytic activity foresterification.Forthisreason,itisusually observed
as a self-catalytic activity.Thus,for comparison reasons,the reaction
was also carried outwithoutany solid catalyst(see entry 1 ofTable 2).
With no catalyst(entry 1 ofTable 4),the formation ofproducts in
low reaction yield wasobserved.Itisimportantto highlightthatallthe
catalyzed reactions presented better yields for esterification when
compared to the auto-catalyzed reaction,being the bestresultsobtained
when pure alumina and tin oxide were used.Note that when pure
alumina was used,a slightly higher yield was achieved.This behavior
can be understood asa resultofthe differentsurface area and acidity of
the solids.Tin oxide and alumina have similar surface acidities butthe
aluminum solid presents largersurface area.The largersurface area for
alumina,which means broader exposure ofthe acid sites,may explain
the better results obtained using this catalyst when compared to tin
Table 5
Reaction yields in differenttimes for selected catalystunder similar conditions.Reaction
conditions:4 g ofmethanol;10 g offatty acid;0.1 g ofcatalyst;and temperature 160 °C.
Entry Reaction Yield (%)
time (h)
Al2O3 SnO (Al2O3)4(SnO)
6 0.5 60 59 53
7 1 74 69 60
8 2 87 86 84
9 3 89 87 86
56 V.M.Mello et al./ FuelProcessing Technology 92 (2011) 53–57

90 100
90
85
80
80
70
Yield (%)

75

Yield (%)
60
70 50
65 40

60 30
Alumina 20
55 Tin Oxide
Doped Alumina/Tin Oxide 10
50
0.5 1.0 1.5 2.0 2.5 3.0 0
1 2 3 4 5 6 7 8 9 10
Reaction Time (h)
Cycle
Fig.4.Reaction yieldsobserved fordifferentreaction timeswith Al2O3;SnO and (Al2O3)4
(SnO).Reaction conditions:160 °C,methanol(4 g),fatty acid (10 g) and catalyst(0.1 g). Fig.5.SnO recycling study (Reaction conditions: 4 g methanol,10 g fatty acid,0.1 g
catalyst;temperature 160 °C;and time 1 h).

oxide.Besides,although alumina doped with tin oxide—catalyst (1)— oxide,which were also the least acidic solids.This behavior can be
and zinc oxide—catalyst(2)—presented similarresults forsurface area, explained by the more effective coordination ofthe intermediatesand
loweryieldswere observed forthose catalystswhen compared with tin the produced esterspeciesto the higherLewisacid centers.When the
oxide and aluminum oxide,as can be depicted in Table 4. coordination ofthe formed methylfatty acid esterishighly efficient,it
It was already observed that catalytic systems based on tin (II) is more difficult to perform the last step of the catalytic cycle and,
maltolate complex displays high catalytic activity in both esterification thus,the continuity ofthe catalysis is compromised.
and transesterification reactions [14]. The mechanism proposed for Differentreaction parameters were studied in the presence oftin
transesterification and esterification reactions in the presence oftin(II) oxide,pure alumina and alumina doped with tin oxide.Table 5 and
maltolate complex is based on the coordination of the acylglycerides Fig.4 show the influence of temperature in reaction yields with all
(mono,di,ortri)orthe fatty acidsatthe metalcentervia the oxygen of three catalysts. It became clear from Fig. 4 that, for the studied
the carbonylgroup,followed by a nucleophilic attack ofthe alcoholat conditions,the reaction achieves equilibrium in the range from 85 to
the carbonylcarbon.Aftera sequence ofsteps,the new esteris formed 90% reaction yield after 3 h.
and decoordinates from the metal center [14,23].It is important to The influence of temperature and the catalyst amount in the
remark that it was observed that the tin(II) catalytic active species is esterification yieldswasalso assessed.Asseen in Table 6,higheryields
formed after protonolysis promoted by the alcohol, displacing one are achieved by increasing the temperature and the catalyst amount
maltolate ligand and leading to an unsaturated maltolate-alkoxy species for both catalysts (Al2O3 and SnO).
[14,23].We believe thatthe catalytic mechanism forthe heterogeneous A study on catalyst recycling was also carried out for tin oxide,
systems studied here based on Lewis metaloxides are similar to those whose results are presented in Fig.5.The loss ofcatalystmass in each
published for Sn(II) and also with the mechanisms accepted in the recovery was minimal and after ten substrate charges the catalytic
literature forSn(IV)[24],asproposed in Fig.3.Methanolreactswith the activity wasalmostmaintained the same.Thisresultstrongly suggests
metaloxide (intermediate 2),producing metoxide and hydroxylgroups thatthe heterogeneoustin oxide catalystisnotdeactivated during the
(intermediate 3).Thus,the fatty acid reacts with the hydroxylgroup esterification reaction and also thatno leaching takes place.
producing water,which leavesthe metalcenter,leading to intermediate
4.Intramolecularattack on the carbonylgroup by the metoxide ligand
4.Conclusion
produces the desired ester and restores the starting metal oxide
(intermediate 1).
In summary, the results obtained using different catalysts in
As already highlighted,among the different solids studied in this
esterification offatty acids with methanollead us to conclude thatall
work the mostactive catalysts foresterification were alumina and tin
metaloxides presented good catalytic activity.The decreasing order
for catalysts activities is: Al2O3 N SnO N (Al2O3)8(SnO)2 N (Al2O3)8
Table 6
(ZnO)2. This can be explained by the different surface textures
Reaction yields atdifferent temperatures and catalyst mass.
(acidity and area) ofthe studied catalysts.It was also observed that
Entry Temperature (°C)a Yield (%) after 3 h the reaction achieved equilibrium with a yield ranging from
SnO Al2O3 80% to 90% according to the reaction system.Itwasalso observed that
tin oxide can be recycled up to ten timeswithoutsignificantloss in its
10 140 50 57
11 160 69 74 activity.
12 180 82 90 The high yields,easy separation from products and good recycling
resultsshow thatthe metaloxidesstudied,especially alumina and tin
Catalystmass (g)b Yield (%)
oxide,strongly indicates thatthese oxides have a good potentialto be
SnO Al2O3 used to obtain biodieselfrom acid stocks.
13 0.05 35 69
14 0.1 69 71
15 0.2 71 74 Acknowledgements
a
Reaction conditions:4 g ofmethanol;10 g offatty acid;0.1 g ofcatalyst;and reaction
time 1 h.
Financial support from CNPq, FINEP, Finatec, FAP-DF, FBB,
b
Reaction conditions: 4 g of methanol; 10 g of fatty acid; temperature 160 °C; and CTPETRO, CTAGRO and CTENERG are gratefully acknowledged.
reaction time 1 h. Authors express their appreciation for fellowships granted by CNPq.
 V.M.Mello et al./ FuelProcessing Technology 92 (2011) 53–57
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