Beruflich Dokumente
Kultur Dokumente
com
a
Center for Functional Nano Fine Chemicals, Chonnam National University, 300 Yongbong-dong, Gwangju 500-757, Republic of Korea
Solar Energy R&D Team, Gwangju Research Center, Korea Institute of Industrial Technology, 1110 Oryong-dong, Gwangju 500-480, Republic of Korea
c
Department of Food and Nutrition, Kwangju Womens University, 165 Sanjeong-dong, Gwangju 506-713, Republic of Korea
Received 1 January 2008; received in revised form 16 February 2008; accepted 20 February 2008
Available online 1 April 2008
Abstract
The removal of free fatty acid (FFA) in waste frying oil by esterication with methanol was conducted using various zeolite catalysts.
The ZSM-5 (MFI), mordenite (MOR), faujasite (FAU), beta (BEA) zeolites, and silicalite were employed with dierent Si/Al molar ratio
in the reaction. The eects of acidic properties and pore structure of the zeolite catalysts were discussed relating to the conversion of the
FFA. The MFI zeolite induced an improvement of the removal eciency of FFA by cracking to the FFA in its pore structure due to its
narrow pore mouth. The catalytic activity for FFA removal was lowered with decreasing of acid strength of the zeolites. The strong acid
sites of zeolites induced the high conversion of FFA comparatively. The acid strength and pore structure of acidic zeolites aected the
catalytic activity in FFA removal.
2008 Elsevier Ltd. All rights reserved.
Keywords: Free fatty acid removal; Esterication; Zeolite; Waste frying oil; Acidity
1. Introduction
Biodiesel is biodegradable and nontoxic, has low emission proles and so is environmentally benecial (Krawczyk, 1996). Biodiesel comprises of long chain, fatty
acid alkyl esters produced from vegetable oils or animal
fats by transesterication of the triglycerides with lower
(Schuchardt et al., 1998; Ma and Hanna, 1999; Barnwal
and Sharma, 2005; Meher et al., 2006).
Conventionally, biodiesel is produced using a homogeneous mineral acid or alkali catalysts. In addition to the
corrosion problems, these homogeneous catalyst-based
processes involve elaborate process steps for removal of
FFAs and water from the feedstock and catalyst from
the products. In acids oils, the amount of FFA varies from
3% to 40% (Srivastava and Prasad, 2000; Ma and Hanna,
1999). However, when the amount of FFAs in the feed*
Corresponding author. Tel.: +82 62 530 0328; fax: +82 62 530 1920.
E-mail address: chung-sea@hanmail.net (K.-H. Chung).
0960-8524/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.02.031
catalysts (Suppes et al., 2004). A range of catalysts including Mg/Al hydrotalcites, alkali nitrate and alkali carbonate-loaded Al2O3, polymer resins, sulfated-tin and
zirconia oxides and tungstated-zirconia have also been
reported (Lopez et al., 2005; Jitputti et al., 2006; Furuta
et al., 2004; Karmee and Chadha, 2005; Mbaraka et al.,
2003). The double-metal cyanide complexes were also
employed in the FFA removal (Sreeprasanth et al., 2006).
The preparation of solid catalysts, however, has a complicated procedure with a high expense.
Zeolites are microporous crystalline solids with welldened structures. Generally they contain silicon, aluminum and oxygen in their framework and cations. Zeolites
are nding applications in many areas of catalysis, generating intense interest in these materials in industrial and academic laboratories. As catalysts, zeolites exhibit appreciable
acid activity with shape selective features not available in
the compositionally equivalent amorphous catalysts. More
recent research on alcoholysis has focused on the use of heterogeneous catalysts (Suppes et al., 2004). Zeolites have
been employed in biodiesel production as a heterogeneous
catalyst. However, esterication of oil has no studied on
zeolites catalysts for FFA removal.
In present study, the direct esterication reaction of the
FFA in waste frying oil with methanol was conducted
using various zeolite catalysts. The acidic properties of
the zeolites with various Si/Al molar ratios were evaluated
using NH3-temperature programmed desorption (TPD)
analysis. The catalytic activity of the zeolite catalysts was
studied on the FFA removal reaction. The eects of acidic
properties and pore structure of the zeolite catalysts were
discussed relating to the conversion of FFA.
2. Experimental
2.1. Preparation of zeolite catalysts
The MFI zeolites were synthesized with a dierent Si/Al
molar ratio through hydrothermal reaction of a synthetic
mixture composed of colloidal silica (Ludox, 40 wt%
SiO2, Aldrich), aluminum hydroxide (64 wt%, Fluka),
potassium hydroxide (80 wt%, Daejung) and deionized
water. The synthetic mixture was aged for 72 h and heated
at 190 C for 48 h. The Si/Al molar ratio of the synthesized
MFI zeolites was 50 and 350, respectively. Other MFI zeolites were purchased from Zeolyst Co.. The Na-type MFI
zeolites were treated with ammonium nitrate (>99 wt%,
Duksan) of 0.5 N at 60 C to exchange its cations to
ammonium ions. H-type MFI zeolites were obtained by
calcining them at 550 C for 6 h in air.
The MOR zeolite (Si/Al = 10) purchased from Tosoh
Co. was used as a starting material for dealumination. Acetic acid (Wako, 99%) of 6 N was employed in the preparation of the dealuminated MOR zeolite to obtain the MOR
zeolites with dierent Si/Al molar ratio. The parent MOR
zeolite was treated with the acetic acid solution for 5 h.
Reuxing time was enlarged to 12 h in order to remove
7439
500
: HBEA(13)
7440
: HFAU(3)
400
: HMFI(25)
: HMOR(10)
: HFER(6)
300
200
100
0
0
0.2
0.4
0.6
P/P0
Fig. 1. N2 isotherms of the zeolites.
0.8
ratio ()
MFI
25
10-oxygen ring
T max
BET surface
area (m2/g)
5.1 5.5[1 0 0]
5.3 5.6[0 1 0]
413
MOR
10
12-oxygen ring
8-oxygen ring
6.5 7.0[0 0 1]
2.6 5.7[0 0 1]
419
FAU
12-oxygen ring
7.4 7.4[1 1 1]
574
BEA
13
12-oxygen ring
6.6 6.7[1 0 0]
5.6 5.6[0 0 1]
577
HMOR(10)
HMFI(25)
HMFI(50)
HMFI(75)
HMFI(350)
Table 1
Structural and compositional properties of the zeolites
)
Zeolite Si/Al molar Pore topology
Pore size (A
7441
100
200
300
400
500
600
500
600
T max
HMOR(10)
HMOR(13)
HMOR(64)
HMOR(100)
100
200
300
400
Temperature (C)
Fig. 3. NH3-TPD proles of (A) HMFI and (B) HMOR zeolites with
dierent Si/Al molar ratio.
Table 2
Conversion of FFA and NH3-TPD properties on HMFI and HMOR
zeolites with dierent Si/Al molar ratio
Zeolite
Si/Al molar
ratioa ()
Acid amountb
(mmol/g)
Tmaxc
(C)
Conversiond
(%)
HMFI
25
50
75
350
7.9 102
4.5 102
3.8 102
0.5 102
415
395
375
360
80.6
77.1
75.3
60.6
HMOR
10
13
64
100
15.1 102
13.0 102
6.6 102
3.0 102
510
508
450
425
80.9
79.4
76.7
76.5
HFAU(5)
HMFI(25)
silicalite
100
200
300
400
500
Temperature (C)
Fig. 2. NH3-TPD proles of the zeolites.
600
7442
have strong acid sites more than HMFI(25) zeolite exhibited the strongest acid strength among the HMFI zeolites.
3.2. Catalytic activities of the zeolite catalysts in the FFA
removal by esterication
The reaction took place not only esterication but also
transesterication in the study. It was conrmed from the
composition distribution of product and feedstock oil.
The composition of oleic acid and palmitic acid increased
signicantly after the reaction compared with feedstock
oil. It was dened that the linoleic acid in the feedstock disappeared nearly after the reaction. The conversion of FFA
on HMFI(25) with various reaction conditions was evaluated in the esterication of FFA with methanol. The conversion of FFA was slightly improved to 80% with increasing
of reaction temperature, but it exhibited no more increase
at above 60 C. The conversion of FFA also became higher
with increasing of loading amount of HMFI(25) zeolite.
However, it did not show a signicant increase above
1.0 g of catalyst loading. The conversion of FFA increased
with proceeding of reaction and it reached to equilibrium
after 90 min. To compare the catalytic activities of the zeolite catalysts in the FFA removal reaction, the reaction conditions were adjusted as 1.0 g of catalyst loading, 60 C of
reaction temperature, and 3 h of reaction time, hereafter.
Fig. 4 represents the catalytic activities of the FFA
removal reaction on various zeolite catalysts compared to
their acid amounts. The high conversion of FFA appeared
on HMFI(25) and HMOR(10) zeolite catalysts. Silicalite
exhibited a low conversion of FFA in the reaction since
it has only very weak acid site. The order of high conversion has a relation with acid amount of the zeolites excluding HMOR zeolites. Although HMOR(10) has a stronger
acid strength and more acid sites than those of HMFI(25)
zeolite, the conversion of HMOR(10) was similar with that
of HMFI(25). This means that there are other factors
besides the acidic properties in evaluation of FFA removal
activity on the zeolites. MFI zeolite has a small pore size
[1 0 0]) compared with that of MOR zeolite
(5.1 5.5 A
100
acid amount
0.12
60
0.09
40
0.06
20
0.03
0.15
conversion
80
Table 3
Chemical properties of the products obtained from FFA removal by
esterication of FFA in waste frying oil with methanol on the zeolites at
60 C and 3 h reaction time
Property
Waste frying
oil before
FFA removal
Product after
the reaction
on HMFI(25)
Product after
the reaction
on HMOR(10)
Density at 15 C
(kg/m3)
902
885
872
Kinematic viscosity at
40 C (mm2/s)
3.9
2.6
2.5
Acid number
(mg KOH/g)
1.25
0.28
0.25
27
77
81
Silicalite
7443
Kim, H.-J., Kang, B.-S., Kim, M.-J., Park, Y.M., Kim, D.-K., Lee, J.-S.,
Lee, K.-Y., 2004. Transesterication of vegetable oil to biodiesel using
heterogeneous base catalyst. Catal. Today, 315320.
Knothe, G., 2005. Dependence of biodiesel fuel properties on the
structure of fatty acid alkyl esters. Fuel Process. Technol. 86, 1059
1070.
Knothe, G., Krahl, J., Van Gerpen, J., 2005. The Biodiesel Handbook.
AOCS Press, Champaign, IL.
Krawczyk, T., 1996. Biodiesel Alternative fuel makes inroads but
hurdles remain. INFORM 7, 801829.
Liu, Y., Lotero, E., Goodwin Jr., J.G., Lu, C., 2007. Transesterication of
triacetin using solid Brnsted bases. J. Catal. 246, 428433.
Lopez, D.E., Goodwin Jr., J.G., Bruce, D.A., Lotero, E., 2005. Transesterication of triacetin with methanol on solid acid and base catalysts.
Appl. Catal. A: Gen. 295, 97105.
Lonyi, F., Valyon, J., 2001. On the interpretation of the NH3-TPD
patterns of H-ZSM-5 and H-mordenite. Micropor. Mesopor. Mater.
47, 293301.
Ma, F., Hanna, M.A., 1999. Biodiesel production: a review. Bioresour.
Technol. 70, 115.
Marchetti, J.M., Miguel, V.U., Errazu, A.F., 2007a. Possible methods for
biodiesel production. Renew. Sustain. Energy Rev. 11, 13001311.
Marchetti, J.M., Miguel, V.U., Errazu, A.F., 2007b. Heterogeneous
esterication of oil with high amount of free fatty acids. Fuel 86, 906
910.
Mbaraka, I.K., Radu, D.R., Lin, V.S.-Y., Shanks, B.H., 2003. Organosulfonic acid-functionalized mesoporous silicas for the esterication of
fatty acid. J. Catal. 219, 329336.
Meher, L.C., Sagar, D.V., Naik, S.N., 2006. Technical aspects of biodiesel
production by transesterication a review. Renew. Sustain. Energy
Rev. 10, 248268.
Miyamoto, Y., Katada, N., Niwa, M., 2000. Acidity of b zeolite with
dierent Si/Al2 ratio as measured by temperature programmed
desorption of ammonia. Micropor. Mesopor. Mater. 40, 271281.
Park, J.W., Kim, J.-H., Seo, G., 2002. The eect of pore shape on the
catalytic performance of zeolites in the liquid-phase degradation of
HDPE. Polym. Degrad. Stabil. 76, 495501.
Rimer, J.D., Kragten, D.D., Tsapatsis, M., Lobo, R., Vlachos, D., 2004.
Growth mechanisms of silicalite-1. Stud. Surf. Sci. Catal. 154, 317
324.
Roboson, H., Lillerud, K.P., 2001. Veried Syntheses of Zeolitic Materials. Elsevier, Amsterdam, pp. 225227.
Schuchardt, U., Sercheli, R., Vargas, R.M., 1998. Transesterication of
vegetable oils: a review. JBCS 9, 199210.
Sreeprasanth, P.S., Srivastava, R., Srinivas, D., Ratnasamy, P., 2006.
Hydrophobic, solid acid catalysts for production of biofuels and
lubricants. Appl. Catal. A: Gen. 314, 148159.
Srivastava, A., Prasad, R., 2000. Triglycerides-based diesel fuels. Renew.
Sustain. Energy Rev. 4, 111133.
Suppes, G.J., Dasari, M.A., Doskocil, E.J., Mankidy, P.J., Go, M.J.,
2004. Transesterication of soybean oil with zeolite and metal
catalysts. Appl. Catal. A: Gen. 257, 213223.
Takagaki, A., Toda, M., Okamura, M., Kondo, J.N., Hayashi, S.,
Domen, K., Hara, M., 2006. Esterication of higher fatty acids by a
novel strong solid acid. Catal. Today 116, 157161.
Tesser, R., Di Serio, M., Nastasi, M., Santacesaria, E., 2005. Kinetics of
oleic acid esterication with methanol in the presence of triglycerides.
Ind. Eng. Chem. Res. 44, 79787982.
Van Gerpen, J. Shanks, B., Pruszko, R., 2004. Biodiesel Production
Technology. Biodiesel Analytical Methods. National Renewable
Energy Laboratory, Midwest Research Institute, Batelle.
Vicente, G., Martinez, M., Aracil, J., 2004. Integrated biodiesel production: a comparison of dierent homogeneous catalysts systems.
Bioresour. Technol. 92, 297305.