Int. J. Miner. Process.

93 (2009) 110–114

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Int. J. Miner. Process.

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i j m i n p r o

Effect of structure-directing agent on AlPO4-n synthesis from aluminum dross

Norihiro Murayama ⁎, Kou Arimura, Nobuaki Okajima, Junji Shibata
Department of Chemical, Energy and Environmental Engineering, Kansai University, 3-3-35, Yamate-cho, Suita-shi, Osaka, 564-8680 Japan

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

Article history: The hydrothermal synthesis of AlPO4-n which is a functional material of aluminophosphate, was conducted
Received 14 June 2008 from two kinds of aluminum dross discharged in an aluminum regeneration factory. The effect of structure-
Received in revised form 20 April 2009 directing agent (SDA) on the formation behavior of AlPO4-n from aluminum dross, the suitable condition to
Accepted 3 July 2009
obtain AlPO4-n efficiently, and the pore structure and gas adsorption property were investigated in this study.
Available online 13 July 2009
AlPO4-5 and AlPO4-34 are mainly formed from aluminum dross as a raw material, and it is possible to make
Keywords:
AlPO4-5 successfully as a main product by adjusting the amount of triethylamine (TEA) as SDA. The gas
Structure-directing agent adsorption amount with AlPO4-5 is the following order; ammonia N dipropylamine N benzene, and it is found
AlPO4-n that this order mainly corresponds with the polarity of molecule among them.
Aluminum dross © 2009 Elsevier B.V. All rights reserved.
Recycle

1. Introduction AlPO4-n and the role of SDA are not clarified adequately. Especially,
no paper is found for the mechanism of AlPO4-n synthesis from
Large quantities of aluminum dross are generated as a waste from aluminum dross.
aluminum production or aluminum recycle processes, and a new In this study, the hydrothermal synthesis of AlPO4-n was carried out
recycle technology for aluminum dross is required. For example, in a from two kinds of aluminum dross. The effect of SDA on the AlPO4-n
melting process of aluminum scraps, the aluminum dross composed formation from aluminum dross and the suitable condition to obtain
of aluminum oxide and aluminum nitride are formed on the surface AlPO4-n efficiently were investigated. Furthermore, the pore structure
between air and melted aluminum. The amount of dross in aluminum and gas adsorption property were studied for the AlPO4-5 obtained
regeneration process is estimated to be over 350,000 t/year in Japan. from aluminum dross.
The aluminum dross discharged in aluminum regeneration factories is
mainly used as a deoxidizer for steel making, but the rest is often
2. Experimental
treated by landfill, because no effective technology is found for the
recycle and reuse methods of aluminum dross. It is difficult to assure a
2.1. Hydrothermal synthesis of AlPO4-n zeolitic materials
disposal site in Japan, and the development of new recycling
technologies is necessary for aluminum dross.
Various wastes such as aluminum dross, residual ash, dust, waste
In our previous study (Murayama et al., 2006a), it has been
solution and so on are exhausted in the recycling process of aluminum
suggested that a functional inorganic material, AlPO4-5 is synthesized
products (Murayama et al., 2006b). The aluminum dross used in this
from aluminum dross as a raw material, as one of effective use of
study, which floats on the surface of molten aluminum in the furnace,
aluminum dross. AlPO4-n (porous aluminophosphate, n:number) is
is generated from various wastes of Al alloys like car bodies, engine
well-known as a zeolitic material having uniform and large pore based
components and aluminum sash. Two kinds of aluminum dross (D-1
on its crystal framework structure. Since a series of AlPO4-n type
and D-2) were used as an aluminum source of AlPO4-n synthesis. The
zeolitic materials was synthesized (Wilson et al., 1982), many
chemical composition of D-1 is a little different from that of D-2. The
researchers (Choudhary et al., 1988; Dong et al., 1992; Newalkar
aluminum dross of D-1 and D-2 was collected from different sampling
et al., 1994; Xu et al., 1989) have studied to apply the AlPO4-n to a
points in the same Al regeneration process, though these are
molecular sieve, a catalyst, an adsorbent and so on.
generated in the same factory in Japan. The lot number of D-2 is
Structure-directing agent (SDA) which mainly acts as a precursor
also the same as the dross used in our previous study (Murayama et al,
and a nucleating material in the formation process of AlPO4-n crystals,
2006a).
is needed to synthesize AlPO4-n, and lower amine like triethylamine
Dried powder of the aluminum dross (14.6 g) was added slowly to
(TEA) is often used as a SDA. However, the formation mechanism of
a 28.2 wt.% phosphoric acid solution of 93.7 g. This mixture was kept
for 1.5 h in the agitation condition with a magnetic stirrer, and then
⁎ Corresponding author. 8.3–13.7 g of TEA which plays a role on SDA, was added to the mixture.
E-mail address: murayama@ipcku.kansai-u.ac.jp (N. Murayama). By a series of operations mentioned above, the composition of mixture

0301-7516/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2009.07.002
 N. Murayama et al. / Int. J. Miner. Process. 93 (2009) 110–114
is set as follows: Al2O3:P2O5:TEA:H2O = 1:1:x:40 (TEA molar ratio
x = 0.5–1.0). This mixture was stirred again for 1.5 h to make an
aluminophosphate gel which is a starting material of AlPO4-n. This
gel-like material was transferred to an autoclave of 200 cm3, and it
was heated at 453 K without agitation for various reaction times
(keeping time at 453 K). The solid cake and mother liquor were
separated by a vacuum filtration. The reaction products were washed
with distilled water, and then dried at 383 K for 12 h.
For the aluminum dross and various reaction products, the crystal
structure was identified by an X-ray diffraction equipment (JDX-3530,
Nihon Denshi Co., Ltd.). The surface texture was observed using a
scanning electron microscope (JSM-5410, Nihon Denshi Co., Ltd.).
Nitrogen adsorption amount was measured by an automatic gas
adsorption equipment (AS1MP-LP2, Quanta-chrome Instruments).
2.2. Gas phase adsorption with AlPO4-n zeolitic materials
For the AlPO4-5 synthesized from D-2 (− 105 μm), a heat
treatment was conducted at 823 K for 3 h in air, in order to remove
TEA in the reaction product (Murayama et al., 2006a) . The heating
rate was set to 5 K/min. This sample after heat treatment was used as
an adsorbent. As an adsorbate gas, ammonia, benzene and dipropy-
lamine were prepared to be about 100 ppm by diluting them with
nitrogen gas. These gases were generated by a bubbling operation of
nitrogen gas into ammonia, benzene and dipropylamine solutions,
respectively. One gram of adsorbent and the diluted gas mentioned
above were introduced into 3 dm3 of tedler-bag, and then the residual
gas concentration was measured with gas detector tubes of 3L, 3La,
121SP, 121, 180 and 180L (Gas Tech Co., Ltd.).
3. Results and discussion
The XRD patterns of two kinds of aluminum dross used in this
study are shown in Figs. 1 and 2. The content of metal aluminum in the
D-1 is about 55%, and it is larger than that in the D-2 (about 45%). In
case of D-1, the peak patterns of Al, Al2O3, MgO and SiO2 (Quartz) are
recognized as a crystalline material. On the other hand, the XRD
diagram of D-2 in Fig. 2 indicates the existence of Al, AlN, Al2O3, MgO
and SiO2, and the XRD intensity derived from SiO2 is extremely high
compared with the D-1. Though SiO2 is an impurity component for the
AlPO4-n synthesis, it is considered that the particles of SiO2 in
Fig. 1. XRD pattern of (a) aluminum dross D-1 and (b) D-1 (−105 µm) after classification.
111
Fig. 2. XRD pattern of (a) aluminum dross D-2 and (b) D-2 (−105 µm) after classification.
aluminum dross can be removed easily with the classification
treatment with a sieve, because a large part of SiO2 in the dross exists
as large cubic particles over 100 μm. So the classification treatment
with a sieve of 105 μm was conducted to the dross. The samples whose
particle size are smaller than 105 μm, are expressed as D-1 (–105 μm)
and D-2 (− 105 μm) in the figures. In case of D-1 and D-1 (− 105 μm),
no difference appears in the XRD patterns before and after the
classification operation, because the content of SiO2 is originally small
in the D-1. Whereas the XRD intensity of SiO2 decreases remarkably
after classification to the D-2 (−105 μm), and it is found that the
removal of SiO2 particles can be achieved with the classification
operation from the D-2, which has a large amount of SiO2 particles.
The chemical composition of two kinds of aluminum dross is
shown in Table 1. These values show the weight percent of acid-
soluble components in the solution dissolved with aqua-regia. The
weight percents of Al in the D-1 and D-2 are 77.5% and 89.1%,
respectively. The aluminum dross, D-1 contains a lot of soluble
components like Ti, Zn, Fe, Mn etc. shown as “Others” in Table 1. There
are insoluble components such as SiO2 in the D-1 and D-2, and the
weight percents of D-1 and D-2 residues after leaching with aqua-
regia are about 40% and 45%, respectively.
According to the report (Wilson et al., 1982), SDA is a very important
factor to form AlPO4-n type zeolitic material, and SDA mainly acts as an
alkaline material, a precursor, a nucleating material and so on in the
AlPO4-n formation process. The hydrophobicity of SDA is also one of the
important factors. The hydrothermal syntheses of AlPO4-n were carried
out by using the aluminum dross D-1, D-1 (–105 μm), D-2 and D-2
(−105 μm) as an aluminum source, and the role of TEA on AlPO4-n
synthesis from aluminum dross was investigated. For example, the XRD
pattern of reaction product obtained from D-2 (−105 μm) is shown in
Fig. 3 as a function of TEA additional amount. In case of TEA ratio x = 1.0
(Fig. 3(a)), the XRD patterns of both AlPO4-5 with 12-membered rings
Table 1
Chemical composition of aluminum dross.
Al Mg Si Ca K Others
Aluminum dross (D-1) 77.5 4.8 0.4 1.3 0.1 15.9
Aluminum dross (D-2) 89.1 3.8 0.2 1.3 0.8 4.8
Solid/liquid ratio: 5 g/200 cm3-aqua-regia.
Residue after leaching: 40% (D-1), 45% (D-2).
112 N. Murayama et al. / Int. J. Miner. Process. 93 (2009) 110–114

Fig. 3. XRD pattern of reaction products synthesized from aluminum dross D-2 (−105 µm) at (a) x = 1.0, (b) x = 0.9, (c) x = 0.8, (d) x = 0.7 and (e) x = 0.6.

and pore size of 7.3 A (Baerlocher et al., 2001a) and AlPO4-34 with 8-
membered rings and pore size of about 3.8 A (Baerlocher et al., 2001b)
are confirmed as an AlPO4-n type zeolitic material. The peaks derived
from AlPO4-5 are superior to that of AlPO4-34 at x = 0.9 (Fig. 3(a)). In
Fig. 3(c), only AlPO4-5 can be obtained at x = 0.8, and no by-products are
found under this condition. On the other hand, the peaks of AlPO4
(Tridymite) which do not have porous structure, appear in the XRD
patterns at x = 0.7 and 0.6 (Fig. 3(d) and (e)), and the XRD intensity of
AlPO4-5 is also decreasing with decreasing x value. It is found from Fig. 3
that TEA ratio x = 0.8 (Fig. 3(c)) is the suitable additional amount to get
AlPO4-5 from the D-2 (−105 μm).
The surface texture of reaction product obtained from D-2
(−105 μm) is shown in Fig. 4. These photographs (b)–(f) correspond
to the XRD patterns (a)–(e) in Fig. 3, respectively. On the whole, the
particles of aluminum dross D-2 (− 105 μm) show an angular shape,
and uneven structure are also observed on the surface. Under the

Fig. 4. Surface structure of (a) D-2 (− 105 µm) and reaction products synthesized from it at (b) x = 1.0, (c) x = 0.9, (d) x = 0.8, (e) x = 0.7 and (f) x = 0.6.
 N. Murayama et al. / Int. J. Miner. Process. 93 (2009) 110–114 113

optimum condition (x = 0.8) to get AlPO4-5 (Fig. 4(d)), the reaction

product indicates hexagonal structure based on the AlPO4-5 forma-
tion. Large particles over 10 μm can be found partially, due to good
crystal growth of AlPO4-5 in the reaction product. In case of x = 1.0
(Fig. 4(b)), there are both many cubic particles and slight amount of
hexagonal particles. It is considered that these cubic crystals are
related to the formation of AlPO4-34. At x = 0.9 (Fig. 4(c)), many fine
particles are coagulated on the hexagonal AlPO4-5 particles. Whereas
fine particles with high aspect ratio such as whisker are found on the
hexagonal particles at x = 0.7 (Fig. 4(e)). The particle surface is
covered with the needle-like particles, which may be derived from
AlPO4 (Tridymite) with decreasing x value (Fig. 4(f)).
The time course of XRD intensity of AlPO4-n at TEA ratio x = 1 is
shown in Fig. 5. As shown in Fig. 3, the formations of both AlPO4-5 and
AlPO4-34 are respectively confirmed under this synthetic condition.
The peak of AlPO4-5 is already identified for 0 h of reaction time, and
then both peaks of AlPO4-5 and AlPO4-34 appear after 1 h. These
intensities have almost the same strength in the reaction time from
1 h to 6 h. The XRD intensity of AlPO4-5 shows the maximum point for
3 h of reaction time, and the intensity is gradually decreasing with an
increase in reaction time after 3 h. On the other hand, the XRD
intensity of AlPO4-34 is especially increasing after 12 h. This result
implies that the AlPO4-34 formation becomes predominant with an
increase in reaction time at TEA ratio x = 1.
The effect of the kind of aluminum dross and the impurity
Fig. 6. XRD pattern and surface structure of reaction products obtained from aluminum
component on the formation behavior of AlPO4-n type zeolitic dross (D-2).
materials was investigated. Fig. 6 indicates the XRD pattern and SEM
photograph of the reaction product synthesized from D-2, in order to
clarify the removal effect of SiO2 particles with the classification The relation between additional amount of TEA and XRD intensity
treatment. The XRD pattern of AlPO4-5 is confirmed, but its intensity is of AlPO4-n is shown in Fig. 7. The region in which AlPO4-5 can be
not so large. The peaks of aluminum phosphate salt (AlPO4) are obtained from D-1 (−105 μm) as a main product, is different from that
recognized simultaneously as a by-product. On the other hand, the of D−2 (− 105 μm). The maximum XRD intensity of AlPO4-5 is located
particle size of the reaction product in the SEM photograph is about at x = 0.6 in case of D-1 (−105 μm), and the maximum value is also
1 μm, and the AlPO4-5 crystal growth is not remarkable compared located at x = 0.8 for D-2 (−105 μm). When the TEA ratio is over 0.7
with the other reaction products from D-2 (−105 μm) in Fig. 4(b)–(f). for the synthesis from D-1 (−105 μm) and the TEA ratio is over 0.9 for
It is considered that these phenomena concerning by-product and that from D-2 (−105 μm), AlPO4-5 and AlPO4-34 are co-crystallized,
crystal growth are mainly caused by the existence of SiO2 particles in respectively. It is considered that these differences in the range of
the aluminum dross D-2, though the reason is not clarified yet. From AlPO4-5 formation are mainly caused by the composition and
these results, it is possible to produce AlPO4-5 effectively by applying a chemical form of aluminum, the content of impurity component in
classification to remove SiO2 particles. the aluminum dross. According to other reports about the AlPO4-n
synthesis from reagent (Concepción et al., 1996), AlPO4-34 tends to be
formed as predominant crystal species with an increase in Mg content
and additional amount of TEA, compared with AlPO4-5. The result
in Fig. 7 is well corresponding to the above report. It is found that

Fig. 5. Time course of XRD intensity of AlPO4-n obtained from aluminum dross D-2 Fig. 7. Relation between additional amount of TEA and XRD intensity of AlPO4-n at
(− 105 µm). 453 K for 12 h.
114 N. Murayama et al. / Int. J. Miner. Process. 93 (2009) 110–114
AlPO4-5 can be synthesized from aluminum dross by adjusting TEA
additional amount, in order not to form AlPO4-34 as a by-product.
When AlPO4-n is used as a catalyst or an adsorbent, the pore
structure and gas adsorption property of AlPO4-n are important
characteristics determining the performance of functional materials.
The pore structure of AlPO4-5 obtained from D-2 (−105 μm) and D-1
was measured. These AlPO4-5 samples were heat-treated at 823 K to
remove TEA in the pore of AlPO4-5 (Murayama et al., 2006a). Fig. 8
shows the pore size distribution of reaction products. These curves are
calculated with the Saito–Foley model (SF model). As shown in this
figure, no differences are found between 2 samples. The pore size
distribution curves are very sharp in the range from 6 A to 15 A, and
they have the maximum value at about 9 A, respectively. The pore size
calculated with SF model (9 A) is a little smaller than that of AlPO4-5
(7.3 A). It is found that the AlPO4-5 products have uniform pore based
on its crystal structure.
The gas adsorption of ammonia, benzene and dipropylamine was
conducted by using the AlPO4-5 synthesized from D-2 (− 105 μm)
after heat treatment at 823 K. Initial concentrations of the above 3
gases are prepared to be about 100 ppm. As shown in Fig. 9, the
adsorption velocity is greatly fast in case of ammonia, and the
ammonia concentration becomes almost 0 ppm for 5 min. The polar
Fig. 8. Pore size distribution of reaction products with SF model.
Fig. 9. Adsorption velocity of various gases with AlPO4-5 obtained from aluminum dross
D-2 (− 105 µm).
molecule with lone electron pair like ammonia and water can be
adsorbed easily on the Al site in AlPO4-5 crystal structure by the
coordination (Kustanovich and Goldfarb, 1991). It is also found that
benzene is adsorbed physically in the pore of AlPO4-5. The benzene
concentration shows about 46 ppm for 10 min, and then the
concentration does not change after 10 min. On the other hand, the
dipropylamine is captured in the pore of AlPO4-5, and the equilibrium
concentration is about 15 ppm for 15 min. Dipropylamine has polarity
and it is also elliptic and long molecule. The molecular size is
estimated to be 9.3 A × 2.3 A. Compared with the pore size of AlPO4-5
(7.3 A), dipropylamine is larger molecular to a long axis direction.
From this result, it is possible to adsorb dipropylamine with long
elliptic-like molecule in the pore of AlPO4-5. The order of gas
adsorption amount with AlPO 4 -5 is as follows: ammo-
nia N dipropylamine N benzene. The above order is also the same as
the polarity of molecule among them (Dipole moment: ammonia
(1.47D) N dipropylamine (1.07D) N benzene (0D)).
4. Conclusion
As one of effective uses of aluminum dross, the syntheses of AlPO4-n
type zeolitic materials were conducted by using aluminum dross as
a raw material. The effect of TEA on the AlPO4-n formation was
investigated in this study.
In using aluminum dross as a raw material, AlPO4-5 and AlPO4-34
are mainly formed, and it is possible to make AlPO4-5 successfully as
predominant crystal species by adjusting TEA additional amount. The
classification to remove SiO2 particles is effective to produce AlPO4-5
from aluminum dross containing SiO2 as an impurity component. The
gas adsorption amount with AlPO4-5 is the following order:
ammonia N dipropylamine N benzene, and it is considered that this
order mainly corresponds with the polarity of molecule among them.
Acknowledgement
This work was supported by ESPEC Foundation for Global
Environment Research and Technology, Japan.
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