International Conference on Chemical, Agricultural and Medical Sciences (CAMS-2013) Dec. 29-30, 2013 Kuala Lumpur (Malaysia)
Influence of Variation (Ca-Mg)/Al
Molar Ratios on Phase Composition of
Ca-Mg-Al Hydrotalcite
Eddy Heraldy,*, Khoirina Dwi Nugrahaningtyas, Fendry Bangkit Sanjaya, Desi Suci Handayani,
and Yuniawan Hidayat
from Tanjung Jati B CFPP, Jepara, Indonesia. Quantitative
analysis of Mg and Ca in brine water using Atomic
Absorption Spectrophotometer (AAS) Shimadzu AA 630-12.
In a typical synthesis process-depend on (Ca-Mg)/Al molar
ratios, AlCl3.6H2O was added into the brine water solution
slowly under stirring. The solution pH was adjusted to 10 with
0.1 M Na2CO3 solution, heated on 70°C during 1 hour. The
product was centrifuged to recover the white solid at a speed
of 2000 rpm for 20 min. The wet cake was washed with
aquadest until free of ion Chloride (AgNO3 test) and dried
overnight with oven. To investigate the effects of different
(Ca-Mg)/Al molar ratios on the phase composition of the
products, the phase composition of the samples was
characterized via X-ray diffraction (XRD) on a Bruker D8
Advance, while Fourier Transform Infrared Spectroscopy
(FTIR) were used to analyze functional group.
Abstract— Ca-Mg-Al hydrotalcite compounds were successfully
synthesized by a coprecipitation method using brine water and
AlCl3.9H2O as the starting materials. The products were
characterized by X-ray diffraction and Fourier Transform Infrared
Spectroscopy. Results show that Ca-Mg-Al hydrotalcite compounds
can be synthesis in the (Ca-Mg)/Al molar ratio from 0.5; 1.0 and 2.0
respectively. The crystallinity of Ca-Mg-Al hydrotalcite shows the
highest when molar ratio of (Ca-Mg)/Al is 0.5. The (Ca-Mg)/Al
molar ratio is found to greatly affect the product morphology and its
phase. With increasing (Ca-Mg)/Al molar ratio from 0.5 to 2.0, its
crystallinity decreased.
Keywords— Ca-Mg-Al hydrotalcite, brine water, (Ca-Mg)/Al
molar ratio, crystallinity
I. INTRODUCTION
I
N the desalination process at Coal Fired Power Plant
(CFPP), only 40% of sea water can be converted into clean
water, while the remaining of 60% sea water that called brine
water discharged back into the sea as waste. Brine water
discharged is more concentrated than seawater.
On the other hand, hydrotalcite (HT) or layered double
hydroxides (LDH) is known as one of the minerals of interest,
prospective and promising because it can be synthesized easily
and are useful in various applications [1]-[5]. Meanwhile, MgAl hydrotalcite have successfully synthesized from brine water
as in [6]-[7]. Reference [8] was synthesized Ca-Mg-Al
hydrotalcite. With the success as in [8] who has preparation of
Ca-Mg-Al-hydrotalcite by combining calcium, magnesium
and aluminum ions, brine water utilization (without Ca
removal) should be considered further. Therefore, in the
present work, Ca-Mg-Al hydrotalcite have been synthesized
by adjusting (Ca-Mg)/Al molar ratios.
III. RESULTS AND DISCUSSION
A. Analysis of Mg and Ca composition in brine water
The values of Mg and Ca ions were obtained from brine
water are given in Table I.
TABLE I
ANALYSIS RESULT OF Mg AND Ca ION IN BRINE WATER
Results (ppm)
Average
METALS
(ppm)
I
II
III
Ca
Mg
397
3490
415
3599
406
3538
According to Table I, the content of Ca and Mg can be
potentially as a starting material in synthesis of hydrotalcite.
B. Powder XRD characterization of hydrotalcite
The influence of the (Ca-Mg)/Al molar ratios on the phase
composition of products has been investigated by XRD. Fig. 1
shows the XRD pattern of product precipitated from brine
water containing AlCl3.6H2O with different (Ca-Mg)/Al molar
ratio 0.5; 1.0 and 2.0 at 70 °C for 1 h. The XRD pattern of the
Ca-Mg-Al hydrotalcite consists of both sharp and symmetrical
peaks with some asymmetrical peaks at high angle, indicating
good crystallinity [9].
II. EXPERIMENTS
All chemicals: AlCl3.6H2O; Na2CO3; AgNO3; HCl 37%;
LaCl3 and aquadest were analytical grade and used as received
without further purification. Brine water sample were taken
Eddy Heraldy,*, Khoirina Dwi Nugrahaningtyas, Fendry Bangkit Sanjaya,
Desi Suci Handayani, and Yuniawan Hidayat are with Chemistry Department,
Faculty of Mathematics and Natural Sciences, Sebelas Maret University, Jl. Ir.
Sutami 36A Kentingan, Surakarta, Indonesia.
*corresponding author’s; e-mail: [email protected].
http://dx.doi.org/10.15242/IICBE.C1213057
406
3526
74
International Conference on Chemical, Agricultural and Medical Sciences (CAMS-2013) Dec. 29-30, 2013 Kuala Lumpur (Malaysia)
TABLE II
BASAL SPACING ALL SAMPLES
Basal spacing
d003 (2Ɵ)
d006 (2Ɵ)
d009 (2Ɵ)
(Ca-Mg)/Al
molar ratio
0.5
7.63Å (11.6°)
3.87Å (23.4°)
1.0
7.63Å (11.6°)
3.87Å (23.4°)
2.0
7.59Å (11.7°)
3.90Å (23.2°)
Mg/Al
7.63Å (11.6°)
3.87Å (23.4°)
1)
hydrotalcite
Ca/Al
7.60Å (11.7°)
3.86Å (23.4°)
hydrotalcite 2)
1)
JCPDS #89-0460; 2) JCPDS #87-0493
Relative Intensity
c
b
20
30
40
50
60
2.48Å (38.5°)
2.48Å (38.4°)
2.48Å (38.4°)
2.67Å (35.4°)
-
-
2.48Å (23.4°)
As seen from Fig. 2, the intensity of main reflection peaks
of products increased first and then decreased with the
increase of (Ca-Mg)/Al molar ratio, which indicates the
crystallinity of hydrotalcite increased first and then decreased.
It is shown that (Ca-Mg)/Al molar ratio equal 2.0, the intensity
of main reflection peaks of hydrotalcite got broadened and
weakened, which illustrates its crystallinity and grain size
decreased.
At the (Ca-Mg)/Al molar ratio 0.5 and 2.0 agrees well with
the empirical phase composition suggested by the XRD
analysis that was confirmed according to the references
(Johnson and Glasser, 2003; Kameda et al., 2007). However
the (Ca/Mg)/Al molar ratio equal to 1:1, a little of other
hydrotalcite phase generated besides hydrotalcite phase in the
product. It is suspected to be Mg(OH)2 and Al(OH)3 (Fig. 3).
a
10
d132 (2Ɵ)
2.67Å (35.1°)
2.68Å (35.0°)
2.68Å (35.0°)
70
2 theta (degree)
Fig. 1 XRD patterns of hydrotalcite with (Ca-Mg)/Al molar ratio (a)
0.5; (b) 1,0 and (c)2.0
The three intense peaks at 2θ values of 11.6°, 23.4° and
34.9° are characteristic of a layered structure and correspond
to the (003, 006 and 009) reflections respectively. These
values correspond well with the most intense peak at 2θ
between 11.4°-11.7° (d003); 23.0°-23.6° (d006) and 34.9°-35.1°
(d009) [7]. The diffraction peak near 61.0° corresponds to the
(110) crystal plane and also the existence of diffraction peaks
at angles between 61.0 to 62.0° indicates that the interlayer of
hydrotalcite are carbonate anionic. This was confirmed by the
results of the study as in [10]-[13]. In Fig. 2., all reflection
peaks of different products can be easily indexed as d003, d006
and d009 which are consistent with the literature value Mg/Al
hydrotalcite (JCPDS Card No. 89-0460) and d003, d006 and d132
Ca/Al hydrotalcite (JCPDS Card No. 87-0493). While the
basal spacing for all samples are listed in Table II.
e
Relative Intensity
d
e
c
b
Relative Intensity
d
c
a
b
10
20
30
40
50
60
70
2 theta (degree)
a
10
20
30
40
50
60
Fig. 3 XRD patterns of hydrotalcite with (Ca-Mg)/Al molar ratio
(a) 0.5; (b) 1,0; (c) 2.0, respectively, in comparison with (d) Mg(OH)2
and (e) Al(OH)3
70
2 theta (degree)
Fig. 2 XRD patterns of hydrotalcite with (Ca-Mg)/Al molar ratio
(a) 0.5; (b) 1,0; (c) 2.0, respectively, in comparison with (d) Mg/Al
hydrotalcite and (e) Ca/Al hydrotalcite
http://dx.doi.org/10.15242/IICBE.C1213057
C. FTIR spectroscopy of hydrotalcite
Fig. 4 illustrates the FT-IR spectra of Ca-Mg-Al
hydrotalcite with carbonate anion interlayer and Table III
show comparison of functional group the hydrotalcite
products.
75
International Conference on Chemical, Agricultural and Medical Sciences (CAMS-2013) Dec. 29-30, 2013 Kuala Lumpur (Malaysia)
TABLE III
COMPARISON OF FUNCTIONAL GROUP THE HYDROTALCITE PRODUCTS
Wave number (cn-1)
Functional
(Ca-Mg)/Al molar ratio
group
Reference
0.5
1.0
2.0
c
Relative Transmittance
OH stretching
OH/C=O bending
C-O stretching
O=C-O bending
b
3200
2800
2400
2000
1600
1200
800
b
3469
1633
1361
667
449
551
3442
1627
1363
667
451
561
c
[6], [12], [14], d [15], e[18], f[19]
In summary, Ca-Mg-Al hydrotalcite compounds have been
successfully synthesized by (Ca-Mg)/Al molar ratio
coprecipitation method. The results show that the (Ca-Mg)/Al
molar ratio is found to greatly affect the product morphology
and its phase. With increasing (Ca-Mg)/Al molar ratio from
0.5 to 2.0, its crystallinity decreased.
400
Wavenumber (cm-1)
Fig. 4 The FT-IR spectra of hydrotalcite with (Ca-Mg)/Al molar
ratio (a) 0.5; (b) 1,0 and (c)2.0
As seen from Fig. 4 and Table III shows the broad
absorption bands around 3442-3469 cm-1 are derived from the
O-H stretching vibration of the hydroxyl groups of both the
layers and the intermediate water for the above three
hydrotalcite which are consistent with literature values [12],
[14]-[17]. The absorption bands at near 1627-1643 cm-1 are
originated by the bending mode of interlayer water molecule
with anion interlayer (Hickey et al., 2000; Kloprogge et al.,
2002; Sharma et al., 2007; Heraldy et al., 2009; Zhou et al.,
2011b; and Wang et al.,2012).
All FT-IR spectra of hydrotalcite display the bands at
1361-1364 and 1633-1650 cm-1 are due to the antisymmetric
C-O and C=O stretching vibration mode of interlayer
carbonate that also confirmed according to the references
(Hickey et al., 2000; Yang et al., 2007; Heraldy et al., 2009
and Wang et al., 2012). Furthermore, in the low wave number
region between 400 cm-1 and 1000 cm-1 at around 677 cm-1
show the O=C-O carbonate bending vibration. Peak around
551 cm-1 which is associated with stretching vibration Al-O
[6], [14] and around 448 cm-1 as stretching vibration Mg-O.
While the appearance of peaks around 449-466 cm-1 and 538561 cm-1 which are suspected as stretching vibration Mg-O,
Ca-O and Al-O of products. This is corresponding as in [17]
that mention peaks at around 428-433 cm-1 are stretching
vibration M-O (where M=Mg, Ca and Al). In addition, the
appearance of the new peaks at 848-858 indicated Ca-O
bonding which are consistent according to [17] and [20] who
have varied Ca and Mg in synthesis hydrotalcite. The more Ca
ions in the synthesis due to new peaks will appear around 800
cm-1. Therefore, from spectra analysis in Fig. 4 was shown
Mg-O, Ca-O, Al-O bonding, hydroxyl, C=O and C-O
indicated that the product is Ca-Mg-Al hydrotalcite with
carbonate anion interlayer.
http://dx.doi.org/10.15242/IICBE.C1213057
a
3446
1782
1361
677
451
555
IV. CONCLUSION
a
3600
415-565 a,b,c,d,e,f
M-O stretching
Reference:
4000
3300-3700 a,b,c,d,e
1633-1650 a,b,c,d,e,f
1350-1384 a,b,c,d,e,f
650-690 b,c,e,f
ACKNOWLEDGMENT
We would like to thank to Directorate General of Higher
Education Ministry of National Education Indonesia for
MP3EI research grants.
REFERENCES
[1] T. Kameda, T. Yoshioka, M. Uchida, and A. Okuwaki “Synthesis of
hydrotalcite using magnesium from seawater and dolomite,” Mol. Cryst.
and Liq. Cryst, vol. 341, pp. 341, 407-412, 2000.
[2] J. Orthman, H. Y. Zhu, and G. Q. Lu, “Use of anion clay hydrotalcite to
remove coloured organics from aqueous solutions,” Sep. Purif. Technol.,
vol. 31, pp. 53-59, 2003.
http://dx.doi.org/10.1016/S1383-5866(02)00158-2
[3] N. K. Lazaridis, “ Sorption removal of anions and cations in single batch
systems by uncalcined and calcined Mg-Al-CO3 hydrotalcite,” Water Air
Soil Poll., vol. 146, pp. 127-139, 2003.
http://dx.doi.org/10.1023/A:1023999303895
[4] Z. Tong, T. Shichi, and K. Takagi, “Oxidation catalysis of a manganese
(III) porphyrin intercalated in layered double hydroxide clays,” Mater.
Lett., vol. 57, pp. 2258-2261, 2003.
http://dx.doi.org/10.1016/S0167-577X(02)01206-5
[5] S. J. Santosa, E. S. Kunarti, and Karmanto, “Synthesis and utilization of
Mg/Al hydrotalcite for removing dissolved humic acid,” Appl. Surf. Sci.,
vol. 254, pp. 7612 – 7617, 2008.
http://dx.doi.org/10.1016/j.apsusc.2008.01.122
[6] E. Heraldy, Triyono, S. J. Santosa, K. Wijaya, D. Prasasti, G. Savitri, D.
Hermawan, R. Iwa, and E. H. Suryo, “Hydrotalcite-like synthesis using
magnesium from brine water (Published World Scientific Publishing Co.
Pte. Ltd.),” in Proc. Inter. Conf. Chem. Bio. and Env. Eng., Singapore,
2009, pp. 246-248.
[7] E. Heraldy, Triyono, S. J. Santosa, and K. Wijaya, “Synthesis of Mg/Al
hydrotalcite-like from brine water and its application for methyl orange
removal: a preliminary study,” Makara Sains, vol. 15, no. 1, pp. 9-15,
2011.
[8] L. Gao, G. Teng, J. Lv, and G. Xiao, “Biodiesel synthesis catalyzed by
the KF/Ca-Mg-Al hydrotalcite base catalyst,” Energy Fuels, vol. 24, pp.
645-651, 2010.
http://dx.doi.org/10.1021/ef900800d
[9] M. A. Ulibarri, I. Pavlovic, C. Barriga, M. C. Hermosin, and J. Cornejo,
“Adsorption of anionic species on hydrotalcite-like compounds: effect of
interlayer anion and cristallinity,” Appl. Clay Sci., vol. 18, pp. 17-27,
2001.
http://dx.doi.org/10.1016/S0169-1317(00)00026-0
[10] C. A. Johnson, C. A., and F. P. Glasser, “Hydrotalcite-like minerals
(M2Al(OH)6(CO3)0.5.XH2O, where M= Mg, Zn, Co, Ni) in the
environment: synthesis, characterization and thermodynamic stability,”
Clay. Clay Miner., vol 51, no. 1, pp. 1-8, 2003.
http://dx.doi.org/10.1346/CCMN.2003.510101
76
International Conference on Chemical, Agricultural and Medical Sciences (CAMS-2013) Dec. 29-30, 2013 Kuala Lumpur (Malaysia)
[11] T. Kameda, T. Yoshioka, F. Yabuuchi, M., Uchida, and A. Okuwaki,
“Preparation of a hydrotalcite-like compound using calcined dolomite
and polyaluminum chloride,” J. Mat. Sci., vol. 42, pp. 2194–2197, 2007.
http://dx.doi.org/10.1007/s10853-007-1543-8
[12] Z. Yang, K. Choi, N. Jiang, and S. Park, “Microwave synthesis of
hidrotalcite by urea hydrolysis,” Bull.Korean Chem., vol. 28, pp. 11,
2007.
[13] J. Lal, M. Sharma, S. Gupta, P. Parashar, P.Sahu, and D. D. Garwal,
“Hydrotalcite: a novel and reusable solid catalyst for one-pot synthesis
of 3,4-dihydropyrimidinones and mechanistic study under solvent free
conditions, J. Mol. Catal. A: Chem., vol. 352, pp. 31-37. 2012.
http://dx.doi.org/10.1016/j.molcata.2011.09.009
[14] L. Hickey, J. T. Kloprogge, and R. L. Frost, “The effects of various
hydrothermal treatments on magnesium-alumunium hydrotalcites, J.
Mater. Sci., vol. 35, pp. 4347-4353, 2000.
http://dx.doi.org/10.1023/A:1004800822319
[15] S. K. Sharma, P. K. Kushwaha, V. K. Srivastava, S. D. Bhatt, and R. V.
Jasra, “Effect of hydrothermal conditions on structrual and textural
properties of synthetic hydrotalcite of varying Mg/Al ratio,” Ind. Eng.
Chem. Res., vol. 46, pp. 4856-4865, 2007.
http://dx.doi.org/10.1021/ie061438w
[16] H. Y. Zeng, Y. J. Wang, Z. Feng, K. Y. You, C. Zhao, J. W. Sun, and P.
L. Liu, “Synthesis of propylene glycol monomethyl ether over Mg/Al
hydrotalcite catalyst,” Catal. Lett,, vol. 137, pp. 94-103, 2010.
http://dx.doi.org/10.1007/s10562-010-0335-y
[17] J. Zhou, Z. X. Xu, S. Qiao, Q. Liu, Y. Xu, and G. Qian, “Enhanced
removal of triphosphate by MgCaFe-Cl-LDH: synergism of precipitation
with intercalation and surface uptake,” J. Hazard. Mater., vol. 189, pp.
586-594, 2011.
http://dx.doi.org/10.1016/j.jhazmat.2011.02.078
[18] J. T. Kloprogge, L. Hickey, and R. L. Frost, “Synthesis and
Spectroscopic Characterisation of Deuterated Hydrotalcite,” J. Mat. Sci.
Lett., vol. 21, no. 8, pp. 603-605, 2002.
http://dx.doi.org/10.1023/A:1015655018529
[19] S. Wang, J. Huang, and F. Chen, 2012, Study On Mg-Al Hydrotalcites
Flame-Retardant Paper Preparation, Bio Resources,7(1): 997-1007,
2012.
[20] S. Gupta, D. D. Agarwal, and S. Banerjee, “Synthesis and
Characterization of Hydrotalcite: Potential Thermal Stabillizers for
PVC,” Indian J. Chem., vol. 47A, no. 7, pp. 1004-1008, 2008.
http://dx.doi.org/10.15242/IICBE.C1213057
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