Applied Catalysis A: General 180 (1999) L1L3

Letter

High catalytic activity for synthesis of aniline from phenol and ammonia found on gallium-containing MFI
Naonobu Katada*, Shuji Kuroda, Miki Niwa
Department of Materials Science, Faculty of Engineering, Tottori University, 4-101, Koyama-cho Minami, Tottori 680-8552, Japan Received 2 September 1998; received in revised form 22 September 1998; accepted 2 October 1998

Abstract Gallium-containing zeolitic materials, i.e., MFI-type gallosilicate and gallium-loaded ZSM-5 zeolite, exhibited quite high activity for vapor-phase reaction of phenol and ammonia into aniline. Co-presence of the extra-framework gallium species and the ion-exchange site ascribed to framework gallium or aluminum atom is considered to generate the high activity. # 1999 Elsevier Science B.V. All rights reserved. Keywords: Aniline; Phenol; Ammonia; Gallosilicate; Gallium-loaded ZSM-5; Extra-framework gallium; Solidacid catalysis

1. Introduction Aniline is an important intermediate for pharmaceutical and chemical industries, and has been conventionally produced by reduction of nitrobenzene. In order to suppress the cost for raw material, reductiveamination of phenol on precious metal catalyst [1] and direct amination on solidacid catalysts such as silica alumina [2], titaniazirconia [3] and alumina [4] have been investigated. In the last decade, the latter reaction using a series of modied aluminas has been applied to practical use [5,6]. For this reaction, enhancement of activity of catalyst is still being attempted to carry out the reaction at low temperature under low pressure of ammonia to suppress the catalyst deactivation and cost for utility. Fundamental studies showed that a
*Corresponding author. Tel.: +81-857-31-5684; fax: +81-85731-0881; e-mail: katada@chem.torrori-u.ac.jp

relatively weak acid such as titaniasilica was active for this reaction [7]; zeolites, whose acid property could be understood well and controlled by the structure and composition, have been applied to this reaction [8]. ZSM-5 zeolite was shown to exhibit a high activity [9]. We found that zeolite possessed higher activity than that on ZSM-5, and the high activity was due to relatively weak acid strength [10], which was determined by an improved method of temperature-programmed desorption (TPD) of ammonia [11,12]. In the present study, gallosilicate was examined as a catalyst, and we here report its quite high and stable activity. The active species is speculated on the basis of the structure and chemical property of gallosilicate, which have been claried in our previous paper [13]; a design of active catalyst by loading of such active species, i.e., extra-framework gallium, is demonstrated.

0926-860X/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved. PII: S0926-860X(98)00334-2

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N. Katada et al. / Applied Catalysis A: General 180 (1999) L1L3

2. Experimental Commercially available samples of NaY (Si/Al2 5), H (Si/Al225) and HZSM-5 (Si/Al223.8) were obtained from Catalysts & Chemicals Ind., PQ and Tosoh, respectively. HY zeolite was prepared from the NaY by ion-exchange using ammonium nitrate followed by calcination at 773 K. Hmordenite (JRC-Z-HM15, Si/Al2ca. 15) and alumina (JRCALO4, 161 m2 g1, g-Al2O3) were supplied by Catalysis Society of Japan as reference catalysts. In order to synthesize MFI-type gallosilicate, gallium nitrate and tetra-n-propylammonium bromide were dissolved into an aqueous solution, and this was dropped slowly into a Ludox HS40 silicate solution. Sodium carbonate solution was then added, and sodium hydroxide or sulfuric acid was added to adjust the pH to 9.7. Thus the mixed solution was stirred and heated at 423 K for 72 h in an autoclave. The yielded solid was ltered, washed with water and nally calcined at 813 K for 20 h in owing oxygen. Thus obtained Na-type gallosilicate was converted into H-type by ion-exchange in an ammonium nitrate solution at 343 K for 24 h, followed by calcination in owing oxygen at 813 K for 20 h. Silicalite with MFI structure was synthesized by almost the same method, but no gallium nitrate was used. The chemical composition was analyzed by an inductively coupled plasma (ICP) photoemission spectrometer (Shimadzu ICPS-5000). The sodium content was <0.04 mmol g1 in the H-type gallosilicates, and the contamination of aluminum was conrmed to be less than 102 mmol g1. Impregnation of gallium on various supports was carried out in order to form the extra-framework gallium species. The support material, i.e., HZSM5, silicalite, H, Hmordenite or alumina, was put into an aqueous solution of gallium nitrate, heated on a hot plate, dried and calcined at 813 K for 20 h in owing oxygen. Synthesis of aniline [10] was carried out by a xedbed continuous-ow method under atmospheric pressure. Prior to the reaction, 0.65 g of catalyst was set in a Pyrex reactor (i.d. 8 mm) and treated in owing nitrogen at 773 K for 1 h. Then a mixture of phenol (4.6 mmol h1) and toluene (4.6 mmol h1) was fed by a micro-feeder into a gas ow of nitrogen (124 mmol h1) and ammonia (41.4 mmol h1) at

723 K of the catalyst bed temperature. The molar ratio of phenol:ammonia:nitrogen:toluene corresponded to 1:9:27:1, and the W/F ratio was 3.7 g-cat h mol1. The products were collected by a methanol trap chilled with a dry iceethanol bath, separated by a gas chromatography (GC) with a column of Unisole 30T/ Uniport HP (2 mm i.d. and 4 m length) operated at 373463 K, and analyzed by an ame ionization detector. 3. Results and discussion Under these conditions, no by-product was generally observed, and the material balance was higher than 80%. The activity is compared by the yield of aniline, as shown in Fig. 1. Aluminosilicates, i.e., HY, H and HZSM-5 zeolites, showed the aniline yield <10% at 0.51 h and <5% at 3.54 h of time on stream. It should be noted that the activities of these zeolites were shown to be much higher than those on

Fig. 1. Catalytic activities on various catalysts after 0.51 (&) and 3.54 h (&) of time on stream.

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Fig. 2. Change in catalytic activity against time on stream of H gallosilicate (*, Si/Ga232) and gallium-loaded ZSM-5 (*: 0, ~: 0.1, &: 0.3, S: 0.5, and }: 1.0 mmol Ga g1).

tional impregnation method of gallium nitrate, and applied them in the reaction. Among the galliumloaded catalysts, only gallium-loaded ZSM-5 showed high catalytic activity, as shown in Fig. 1. Fig. 2 compares the activities on Hgallosilicate (Si/Ga232) and gallium-loaded ZSM-5 with various gallium loadings. The loading of gallium on ZSM-5 drastically enhanced the activity, and the maximum activity, ca. 3540% of the aniline yield at 0.51 h, was obtained with the loading more than 0.3 mmol Ga g1. It is noteworthy that most of the gallium-loaded ZSM-5 showed the fast deactivation, whereas the sample containing 0.3 mmol g1 of gallium exhibited the stable activity. We can now conclude that the gallium-containing zeolitic material with MFI structure has extremely high activity for the synthesis of aniline. Because the gallium-loaded silicalite with MFI structure showed no activity, copresence of the extra-framework gallium species and the ion-exchange site ascribed to the framework trivalent cation is presumably required. References
[1] Y. Ono, H. Ishida, J. Catal. 72 (1981) 121. [2] Y. Asami, J. Watanabe, M. Okada, Sekiyu Gakkaishi 16 (1973) 138. [3] T. Kiyoura, T. Takahashi, Jpn. patent JP 48 067 229 (1973) to Mitsui Toatsu Chemicals Inc. [4] M. Becker, H.M. Sachs, US patent 4 480 127 A (1984) to Halcon SD Group Inc. [5] M. Yasuhara, F. Matsunaga, Eur. patent 321 275 A2 (1989) to Mitsui Petrochemical Industries Ltd. [6] A.A. Schutz, L.A. Cullo, PCT patent WO 9 305 010 A1 (1993) to Aristech Chemical Corp. [7] K. Tanabe, M. Ito, M. Sato, J. Chem. Soc., Chem. Commun. (1973) 676. [8] M. Yamamoto, N. Takamiya, S. Murai, Nippon Kagaku Kaishi (1974) 2135. [9] C.D. Chang, W.H. Lang, Eur. patent 62 542 A1 (1982) to Mobil Oil Corp. [10] N. Katada, S. Iijima, H. Igi, M. Niwa, Stud. Surf. Sci. Catal. 105 (1997) 1227. [11] N. Katada, H. Igi, J.-H. Kim, M. Niwa, J. Phys. Chem. B 101 (1997) 31. [12] M. Niwa, N. Katada, Catal. Surveys Jpn. 1 (1997) 215. [13] T. Miyamoto, N. Katada, J.-H. Kim, M. Niwa, J. Phys. Chem. B 102 (1998) 6738.

g-alumina, amorphous silicaalumina and Hmordenite [10]. In comparison with these, Hgallosilicate with MFI structure showed extremely high activity, ca. 25% of the yield on the sample with 32 of the Si/ Ga2 ratio. As shown in Fig. 2(*), the activity on gallosilicate was almost stable at 24 h of the time on stream. The activity on Hgallosilicate seems to appear with more than 0.30.4 mmol g1 of gallium, namely less than 5060 of the Si/Ga2 ratio. Scanning electron microscopy, X-ray diffraction and nitrogen adsorption isotherm conrmed that these gallosilicates had a well-crystallized MFI structure with high enough volume of micropores. However, the gallium content higher than 0.30.4 mmol g1 was found to result in the formation of considerable amount of extra-framework gallium [13]. On the basis of these ndings, we speculate that the extra-framework gallium cation and/ or gallium oxide particle loaded on the silicate played some specic roles for this reaction. We therefore prepared several catalysts containing the extra-framework gallium by means of the conven-