Int. J. Miner. Process.

93 (2009) 110114

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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
The hydrothermal synthesis of AlPO4-n which is a functional material of aluminophosphate, was conducted from two kinds of aluminum dross discharged in an aluminum regeneration factory. The effect of structuredirecting agent (SDA) on the formation behavior of AlPO4-n from aluminum dross, the suitable condition to obtain AlPO4-n efciently, and the pore structure and gas adsorption property were investigated in this study. AlPO4-5 and AlPO4-34 are mainly formed from aluminum dross as a raw material, and it is possible to make AlPO4-5 successfully as a main product by adjusting the amount of triethylamine (TEA) as SDA. The gas adsorption amount with AlPO4-5 is the following order; ammonia N dipropylamine N benzene, and it is found that this order mainly corresponds with the polarity of molecule among them. 2009 Elsevier B.V. All rights reserved.

Article history: Received 14 June 2008 Received in revised form 20 April 2009 Accepted 3 July 2009 Available online 13 July 2009 Keywords: Structure-directing agent AlPO4-n Aluminum dross Recycle

1. Introduction Large quantities of aluminum dross are generated as a waste from aluminum production or aluminum recycle processes, and a new recycle technology for aluminum dross is required. For example, in a melting process of aluminum scraps, the aluminum dross composed of aluminum oxide and aluminum nitride are formed on the surface between air and melted aluminum. The amount of dross in aluminum regeneration process is estimated to be over 350,000 t/year in Japan. The aluminum dross discharged in aluminum regeneration factories is mainly used as a deoxidizer for steel making, but the rest is often treated by landll, because no effective technology is found for the recycle and reuse methods of aluminum dross. It is difcult to assure a disposal site in Japan, and the development of new recycling technologies is necessary for aluminum dross. In our previous study (Murayama et al., 2006a), it has been suggested that a functional inorganic material, AlPO4-5 is synthesized from aluminum dross as a raw material, as one of effective use of aluminum dross. AlPO4-n (porous aluminophosphate, n:number) is well-known as a zeolitic material having uniform and large pore based on its crystal framework structure. Since a series of AlPO4-n type zeolitic materials was synthesized (Wilson et al., 1982), many researchers (Choudhary et al., 1988; Dong et al., 1992; Newalkar et al., 1994; Xu et al., 1989) have studied to apply the AlPO4-n to a molecular sieve, a catalyst, an adsorbent and so on. Structure-directing agent (SDA) which mainly acts as a precursor and a nucleating material in the formation process of AlPO4-n crystals, is needed to synthesize AlPO4-n, and lower amine like triethylamine (TEA) is often used as a SDA. However, the formation mechanism of

AlPO4-n and the role of SDA are not claried adequately. Especially, no paper is found for the mechanism of AlPO4-n synthesis from aluminum dross. In this study, the hydrothermal synthesis of AlPO4-n was carried out from two kinds of aluminum dross. The effect of SDA on the AlPO4-n formation from aluminum dross and the suitable condition to obtain AlPO4-n efciently were investigated. Furthermore, the pore structure and gas adsorption property were studied for the AlPO4-5 obtained from aluminum dross. 2. Experimental 2.1. Hydrothermal synthesis of AlPO4-n zeolitic materials Various wastes such as aluminum dross, residual ash, dust, waste solution and so on are exhausted in the recycling process of aluminum products (Murayama et al., 2006b). The aluminum dross used in this study, which oats on the surface of molten aluminum in the furnace, is generated from various wastes of Al alloys like car bodies, engine components and aluminum sash. Two kinds of aluminum dross (D-1 and D-2) were used as an aluminum source of AlPO4-n synthesis. The chemical composition of D-1 is a little different from that of D-2. The aluminum dross of D-1 and D-2 was collected from different sampling points in the same Al regeneration process, though these are generated in the same factory in Japan. The lot number of D-2 is also the same as the dross used in our previous study (Murayama et al, 2006a). Dried powder of the aluminum dross (14.6 g) was added slowly to 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 8.313.7 g of TEA which plays a role on SDA, was added to the mixture. By a series of operations mentioned above, the composition of mixture

Corresponding author. E-mail address: murayama@ipcku.kansai-u.ac.jp (N. Murayama). 0301-7516/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.minpro.2009.07.002

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is set as follows: Al2O3:P2O5:TEA:H2O = 1:1:x:40 (TEA molar ratio x = 0.51.0). 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 ltration. 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 identied 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 m), 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 dipropylamine 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. 2. XRD pattern of (a) aluminum dross D-2 and (b) D-2 ( 105 m) after classication.

aluminum dross can be removed easily with the classication treatment with a sieve, because a large part of SiO2 in the dross exists as large cubic particles over 100 m. So the classication treatment with a sieve of 105 m was conducted to the dross. The samples whose particle size are smaller than 105 m, are expressed as D-1 (105 m) and D-2 ( 105 m) in the gures. In case of D-1 and D-1 ( 105 m), no difference appears in the XRD patterns before and after the classication operation, because the content of SiO2 is originally small in the D-1. Whereas the XRD intensity of SiO2 decreases remarkably after classication to the D-2 ( 105 m), and it is found that the removal of SiO2 particles can be achieved with the classication 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 acidsoluble 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 aquaregia 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 m), D-2 and D-2 ( 105 m) 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 m) 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 Aluminum dross (D-1) Aluminum dross (D-2) Fig. 1. XRD pattern of (a) aluminum dross D-1 and (b) D-1 (105 m) after classication. 77.5 89.1 Mg 4.8 3.8 Si 0.4 0.2 Ca 1.3 1.3 K 0.1 0.8 Others 15.9 4.8

Solid/liquid ratio: 5 g/200 cm3-aqua-regia. Residue after leaching: 40% (D-1), 45% (D-2).

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Fig. 3. XRD pattern of reaction products synthesized from aluminum dross D-2 (105 m) 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 8membered rings and pore size of about 3.8 A (Baerlocher et al., 2001b) are conrmed 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 m). The surface texture of reaction product obtained from D-2 ( 105 m) 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 m) show an angular shape, and uneven structure are also observed on the surface. Under the

Fig. 4. Surface structure of (a) D-2 ( 105 m) 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.

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optimum condition (x = 0.8) to get AlPO4-5 (Fig. 4(d)), the reaction product indicates hexagonal structure based on the AlPO4-5 formation. Large particles over 10 m 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 ne particles are coagulated on the hexagonal AlPO4-5 particles. Whereas ne 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 conrmed under this synthetic condition. The peak of AlPO4-5 is already identied 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 component on the formation behavior of AlPO4-n type zeolitic 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 classication treatment. The XRD pattern of AlPO4-5 is conrmed, but its intensity is not so large. The peaks of aluminum phosphate salt (AlPO4) are recognized simultaneously as a by-product. On the other hand, the particle size of the reaction product in the SEM photograph is about 1 m, and the AlPO4-5 crystal growth is not remarkable compared with the other reaction products from D-2 ( 105 m) in Fig. 4(b)(f). It is considered that these phenomena concerning by-product and crystal growth are mainly caused by the existence of SiO2 particles in the aluminum dross D-2, though the reason is not claried yet. From these results, it is possible to produce AlPO4-5 effectively by applying a classication to remove SiO2 particles.

Fig. 6. XRD pattern and surface structure of reaction products obtained from aluminum dross (D-2).

The relation between additional amount of TEA and XRD intensity of AlPO4-n is shown in Fig. 7. The region in which AlPO4-5 can be obtained from D-1 (105 m) as a main product, is different from that of D2 ( 105 m). The maximum XRD intensity of AlPO4-5 is located at x = 0.6 in case of D-1 ( 105 m), and the maximum value is also located at x = 0.8 for D-2 ( 105 m). When the TEA ratio is over 0.7 for the synthesis from D-1 ( 105 m) and the TEA ratio is over 0.9 for that from D-2 ( 105 m), AlPO4-5 and AlPO4-34 are co-crystallized, respectively. It is considered that these differences in the range of AlPO4-5 formation are mainly caused by the composition and chemical form of aluminum, the content of impurity component in the aluminum dross. According to other reports about the AlPO4-n synthesis from reagent (Concepcin 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 ( 105 m).

Fig. 7. Relation between additional amount of TEA and XRD intensity of AlPO4-n at 453 K for 12 h.

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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 m) 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 SaitoFoley model (SF model). As shown in this gure, 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 m) 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

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: ammonia 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 classication 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. References
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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 m).