Applied Clay Science 33 (2006) 1 – 6 www.elsevier.

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A new application of clay-supported vanadium oxide catalyst to selective hydroxylation of benzene to phenol
Xiaohan Gao, Jie Xu ⁎
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, PR China Received 11 October 2005; received in revised form 13 December 2005; accepted 19 December 2005 Available online 27 January 2006

Abstract The highly selective direct hydroxylation of benzene with hydrogen peroxide to phenol was observed on a clay-supported vanadium oxide catalyst. Under mild reaction conditions at 313 K, high selectivity to phenol of 94% was realized on the claysupported vanadium oxide catalyst at 14% conversion of benzene, comparable with the well-known TS-1 catalyst. On the other hand, vanadium on other supports and other metals on the clay support gave inferior catalytic performances. V–O–Al and V–O–Si bridges in the catalyst may be responsible for the reaction. © 2005 Elsevier B.V. All rights reserved.
Keywords: Clay; Benzene; Phenol; Vanadium

1. Introduction Developing new applications of the natural resources is an interesting field. Clay that is a very versatile material has attracted more attention owing to its wide applications in various field for more than a century (Shimizu et al., 2002; Murray, 2000). The application of clay for catalysts in the organic chemical commenced at the 1970s last century, Pinnavaia et al. reported the hydrogenation of 1-hexene catalyzed by rhodium complexes immobilized in smectites (Pinnavaia and Welty, 1975). Many papers and monographs were published in recent years about the use of clay in the organic syntheses (Campanati and Vaccai, 2001). Clays have a great potential as host compounds for fancy catalysts such as shape selective and asymmetric
⁎ Corresponding author. Tel.: +86 411 84379245; fax: +86 411 84379245. E-mail address: xujie@dicp.ac.cn (J. Xu). 0169-1317/$ - see front matter © 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.clay.2005.12.002

reactions due to the characteristic layer structure and the facile intercalation properties. Some important results in this aspect are indicated (Kun et al., 2001; Bartok et al., 1999; Shimazu et al., 1996). Additional advantage of using clay as support of catalysts is the composition of clay. Clay is mainly made up of tetrahedral silicon dioxide and octahedral alumina and the ratio of the Si / Al is relatively steady (Campanati and Vaccai, 2001), which is similar to molecular sieves. The hydroxylation of alkanes and aromatic compounds is an attractive and challenging subject, especially for the direct hydroxylation of benzene to phenol from economical and environmental point of view, which is an important intermediate for the manufacture of petrochemicals, agrochemicals and plastics (Miyahara et al., 2001). The investigations of direct oxidation of benzene to phenol with various oxidants, such as nitrous oxide (Sobolev et al., 1993; Panov et al., 1992), hydrogen peroxide (Bianchi et al., 2000; Bengoa et al., 1998; Zhang et al., 1996;

2002) have been reported. especially for the hydroxylation of alkanes and aromatic compounds with hydrogen peroxide (Gao and Hua..1 mL per min. except that copper. hydrogen peroxide (30%) was added dropwise through a dropping funnel. which proceeds at the mild conditions. the selectivity to phenol was less than 70% (Lemke et al. iron.4-benzoquinone. Thus. TS-1 was statically crystallized in a Teflon-lined stainless-steel autoclave at 443 K for 5 days. 1983). Clearly. The washed clay was dried at 393 K. Walling. In brief. Peaks of GC chromatogram of the reaction products were assigned to phenol. 2003.. The conversion and the selectivity to phenol were obtained from following equations. The wet clay was carefully washed until no sulfate ion can be detected. 2. manganese. etc. together with Na. Catalyst preparation Clay used in these experiments is composed of chlorite. The TS-1 was prepared using the similar procedure as has been reported (Taramaso et al. The catalysts were prepared by the following procedures. The acetic acid addition was meant to enhance the activity of hydrogen peroxide. Ohtani et al. 1999) since phenol is more reactive than benzene in the reaction. tetraethylorthosilicate (TEOS) was added slowly to a solution of titanium n-butoxide (TBOT) and 25% w / w aqueous solution of tetra-n-propylamminumn hydroxide (TPAOH). dried. and were produced in Inner Mongolia. Characterization The XRD measurement was performed using miniflex (Rigaku) with a CuKα radiation at 0. Xu / Applied Clay Science 33 (2006) 1–6 Kuznetsova et al. Conversionð%Þ phenol þ benzoquinone þ others ¼  100 benzene þ phenol þ benzoquinone þ others Selectivityð%Þ ¼ phenol  100 phenol þ benzoquinone þ others 2. illite. J. washed.. After heating the mixture to 313 K under stirring. The final compositions of TEOS : TBOT : TPAOH : H 2 O were 1 : 0. 3. The GC analyses (Agilent 4890D) of products were performed with an OV-1 capillary column (35 m × 0. 2001. we report the clay-supported vanadium oxide catalyst exhibits the high selectivity in hydroxylation of benzene to phenol. which is higher or comparable to the known best catalyst. and tungsten/clay were calcined at 773 K for 5 h because the precursor of copper. catechol. Further. Gao. chromium. attapulgite. northwest of China. benzene and acetic acid were added into the flask. Hydroxylation of benzene with hydrogen peroxide on various catalysts Table 1 shows the catalytic performances in the hydroxylation of benzene on clay-supported several metal oxide catalysts. 1995).2.1. The clay-supported vanadium oxide was dried at 393 K and calcined at 973 K for 5 h. the solution was further stirred at 313 K for 4 h and then cooled down to room temperature. 100 g of clay was added to a 300 mL of 0. 2. Hydroxylation reaction and products analysis The hydroxylation of benzene to phenol with hydrogen peroxide was performed in a 100 mL four-neck flask. were supported on clay. Therefore we used clay-supported metal oxide catalysts for the hydroxylation of benzene and optimized the reaction conditions.32 mm × 0. and tungsten could decompose under low temperature. 2005). Vanadium is a most widely used element in catalysts. iron.3. 1996). The crystalline solid was centrifuged. taking into account of sensitivity factor of each compound. However. The addition rate was controlled in 0. and filtered...02 steps per second in angle range 2θ = 5 − 90°. While some metal . 2004). and calcined at 773 K for 5 h. and Ti as minor components. and tungsten. molybdenum. or a mixture of oxygen and hydrogen (Niwa et al. The above mixture was heated at 348 K to remove alcohols.. iron. The other metal oxides such as copper. Experimental 2.1. Si / Al = 4 in atomic ratio) as major components. After the complete addition of hydrogen peroxide.2 X. Catalyst. as similarly as vanadium case. Fe.8 μm). together with clay without metal oxide. TS-1. K. as will be shown in this paper. Vanadium oxides were introduced to the dried clay by impregnation method from an aqueous ammonium metavanadate solution. biphenyl and hydroquinone from their retention times of reference samples. There were several reports for the benzene to phenol reaction on vanadium-containing catalysts (Zhang et al. The direct hydroxylation of benzene with hydrogen peroxide to produce phenol was widely attempted as a green process (Clerici. The clay consists of Si and Al (ca. Results and discussion 3. the clay-supported vanadium oxide gave the best conversion and the best yield in these catalysts under the same reaction conditions.25 : 0. stirred for 24 h at room temperature. all soluble basic ions were removed.25 M aqueous sulfuric acid solution. 1975)..25 : 68 in mole ratio. Chen and Lu. molecular oxygen (Miyahara et al. The interaction between metal oxide and clay was estimated from the FT-IR spectra recorded by Tensor 27 (Bruker) at the resolution of 4 cm− 1. 2001. 1. to improve the solubility of the reactants and to minimize the phase transfer problems.. Mn.

% in clay against the conversion and the selectivity to phenol in the hydroxylation of benzene. e The reaction condition: benzene : acetonitrile : TS-1 = 1 : 5 : 0. a The reaction conditions:10 mmol benzene and 30 mmol H2O2 in 6 mL acetonitrile. This shows that the vanadium oxides/clay is not equal to the physical mixture of vanadium and clay. Effect of the amount of vanadium.0 10.3 0 1. Even reported result on TS-1 shows lower selectivity (82%) than the clay-supported vanadium oxide at similar conversion level (entry 8). Table 2 represents the catalytic performances of Vbased catalysts in the oxidation of benzene to phenol. A new matter may be formed in the vanadium oxide/clay catalyst owing to the interaction between vanadium and clay.0 10.13 mol acetone at 335 K for 2 h.0 (mol). at 295 K for 20 h.90 g clay.3% and selectivity of 97% (entry 6) while the clay-supported vanadium oxide gave far higher conversion of 11. Optimization of reaction conditions Reaction conditions were optimized over the claysupported vanadium catalyst. . Vanadium oxide (entry 5) and its physical mixture with clay (entry 4) showed lower conversion and selectivity to phenol than the vanadium oxide/clay catalyst (entry 1).0 10. such as molybdenum and chromium.10 g V2O5 and 0.3 3.7 13.0 10.056 mol of benzene and 0.7%.7 4. 3.3 Selectivity to phenol (%) 100 0 96 89 100 84 100 91 3 Reaction conditions: 0.5 wt.8 7. their selectivities to phenol were far lower.%) 0 10. (1998) The reaction conditions are the same as that of Table 1. the best known catalyst for the reaction. the TS1 catalyst gave the conversion of 5. Under the similar reaction conditions.0 11. c The mixture of 0.3% at 2. at 333 K for 3 h. We conclude from above results that the new matter is formed in clay-supported vanadium oxide due to the interaction between vanadium and clay.1 5.1 5. at 333 K for 8 h. 1.0 Conversion (%) 3. the reaction conditions are same as those of Table 1. as compared with that on TS-1 catalysts as a reference.0 8. J.6 56 Conversion (%) 11.6 Selectivity to phenol (%) 92 48 67 87 87 97 N95 82 Reference This work Chen and Lu (1999) Lemke et al. oxide supported on the clay showed lower conversion of benzene. which may be poison for the hydroxylation of benzene to phenol with hydrogen peroxide. 1. 313 K for 4 h.098 mol of H2O2 (in 30% aqueous solution) in 30 mL of acetic acid.% vanadium loaded Table 2 Catalytic performances of benzene hydroxylation on vanadium-based catalysts Entry 1 2 3 4 5 6 7 8 Catalyst V/clay V/MCM-41 a V/MCM-41 b V2O5 + clay c V2O5 TS-1 TS-1 d TS-1 e Metal in support (wt.3 31. Fig.8 5. which promotes the hydroxylation of benzene with hydrogen peroxide at better or similar catalytic performances than TS-1. Gao. which is responsible for higher conversion of benzene. 1 shows plots of vanadium metal wt.4 3.15 (wt) and benzene : H2O2 = 1.0 10.9 5. d The reaction conditions: 10 mmol benzene and 29 mmol H2O2 in 0.0 10. The conversion of benzene reached at a maximum value of 13. b The reaction conditions: 4 mmol benzene and 4 mmol H2O2 in acetic acid.2.%) 5 Si / V = 25 1. Although V/MCM-41 (entries 2–3) showed somewhat higher conversions of benzene than vanadium oxide/clay catalyst. (2003) This work This work This work Tanev et al.0 g of catalyst weight. (1994) Bhanmik et al. Xu / Applied Clay Science 33 (2006) 1–6 Table 1 Hydroxylation of benzene on various clay-supported metal oxides Precursor of metal oxide Clay alone (NH4)6Mo7O24·4H2O Cr(NO3)3·9H2O Cu(NO3)·3H2O Fe(NO3)·9H2O Mn(CH3COO)2·4H2O H2WO4 NH4VO3 Metal in clay (wt.X. Fig.0 10.

When the amount of the catalyst is over 0.% increased beyond 2.%.3 14. 0.2 5. 3. J. Xu / Applied Clay Science 33 (2006) 1–6 Table 3 Effect of the ratio of addition of hydrogen peroxide on benzene Hydrogen peroxide/benzene (mol / mol) 2. At higher temperature.1 90.0 0.8 94.25 g or larger.8 93.056 mol of benzene and 0.7 Selectivity (%) 96. Fig. 2. 313 K for 4 h.4 X.00 g. The effect of the variation in the molar ratio between hydrogen peroxide and benzene is described in Table 3. in clay and decreased with further increase of vanadium wt.4 1.0 Reaction conditions: the different ratio of hydrogen peroxide on benzene in 30 mL of acetic acid. It can be seen that the conversion of the substrate reached a plateau when the amount of the catalyst is 0. D V2O5.5% of vanadium in clay. Gao.5% of vanadium in clay. at lower temperature the reason is that phenol has a more activity than benzene.2 1. 4.5%.0 g of catalyst weight.6 Conversion (%) 13. Effect of the reaction temperature. which is responsible for the decrease of the conversion of reactant and the selectivity of product. There are two bands in the spectra of the mechanical mixture of V2O5 and the clay (Fig. 4C).1 11. 2.8 1. as shown in Fig. Fig. 3. Fig.5% of vanadium in clay. Reaction conditions: 0. Fig. the best yield of phenol was obtained at temperature of about 313 K. As is clearly seen. B clay. Reaction conditions: 0. the excessive vanadium oxide decomposes more hydrogen peroxide to oxygen and water.4.5%).5%. The volume of benzene remained while that of H2O2 changed. 2. 1. The optimum vanadium content is about 2. IR spectra of sample A V/clay (2. C the mixture of clay and V2O5. The band at 1154 cm− 1 is attributed to the clay (Fig. .098 mol of H2O2 (30%) in 30 mL of acetic acid.056 mol of benzene and 0. 313 K for 4 h. respectively. 2. 2. 3 illustrated the influence of the amount of the catalyst from 0. the excessive catalyst decomposes more hydrogen peroxide to oxygen and water. The conversion of benzene increased as the increasing ratio of hydrogen peroxide on benzene and reached the best value at the ratio of hydrogen peroxide on benzene about 1.25 g. The reactions were conducted in the temperature range from 293 to 333 K.098 mol of H2O2 (30%) in 30 mL of acetic acid.3. the fall of the selectivity is owing to a possible decomposition of hydrogen peroxide that led to the by-product formation. Effect of the amount of the catalyst.05 to 1.9 94. 4B) and the band at 1024 cm− 1 is assigned to Fig. As the vanadium wt.5 13.25 g of catalyst weight. 4 shows the IR spectra of the samples between 1400 and 900 cm− 1. at different temperature for 4 h. Characterization of the support and catalysts The samples of catalyst were characterized by FT-IR to understand the interaction between vanadium and clay.

4. For the similar reason. which is very close to the band at 1026 cm− 1 of V2O5 (Fig. Conclusions In conclusion. The lower cost and less pollution of clay as support of catalyst may be positive and competitive for the reaction of hydroxylation in the future. Gao. . There are no significant changes in XRD spectra between the original clay. 1996) (Fig. 4A). 5B and C). 5A). The band about 812 cm− 1 (Fig. We envisioned the V–O–Al and V–O–Si bonds structure may be the active centre for the oxidation of benzene to phenol. vanadium in the bridge of V–O–V could be replaced by other metal of the support to form the new bridges of V–O–M (Scheme 1b). and acid-treated and calcined clay. It is suggested that the changes in peak position of the V _ O stretching mode were attributed to the interaction between vanadium and clay. XRD spectra of the clay-supported vanadium change a little from that of original clay.X. 1996). The XRD of support and catalyst. 6. showing stability of clay to heat. 5A). Fig. 4D) (Concepcion et al.5%). It is believed that the new bridges of the V–O–Al and V–O–Si were formed in the claysupported catalysts. The results of XRD of support and catalyst are shown in Fig. The bridge of V–O–Al and V–O–Si may be formed in the catalysts and be the active centre for the reaction. C the mixture of clay and V2O5. 6. 1995) (Fig. the catalyst of clay-supported vanadium oxides is effective for the direct hydroxylation of benzene to phenol and shows 14% conversion of benzene and 94% selectivity to phenol. Fig.and acidtreatments. whereas the band of Al–O bond in the bridge V–O–Al (Scheme 1c) shifts to 591 cm− 1 and becomes sharper. respectively. suggesting vanadium stayed at outside of layer. The band of the Si–O rocking vibrations appears about 472 cm− 1 (Handke and Mozgawa. 5B and C). Xu / Applied Clay Science 33 (2006) 1–6 5 Fig. D V2O5. the band of the M–O bond in the bridge V–O–M would shift and change under the influence of vanadium. 5 displays the IR spectra of the samples at low wavenumber between 400 and 900 cm− 1. 1997) whereas the band of the vibration of V–O bond disappears in the IR spectra of the clay-supported vanadium oxides (Fig... both of them weakened and broadened. 2002). Scheme 1. There are two new bands at 591 and 424 cm− 1 that appeared in the spectra of the clay-supported vanadium oxides (Fig. In addition. V _ O stretching mode. whereas the band of the Si–O bond in the bridge V–O–Si (Scheme 1d) shifts to 424 cm− 1. 5. 5C and D) is assigned to the vibration of V–O bond in the bridge of V–O–V (Scheme 1a) (Botto et al. B clay. When vanadium was supported on the clay (Fig. The band of the Al–O bond in the stretching model of AlO6 octahedra appears about 604 cm− 1 (Morterro and Magnacca. J. The vibration of the V–O bond in the bridge V–O–M is not IR active (Wachs. Owing to the interaction between the vanadium and the clay. IR spectra of sample A V/clay (2. the bands of clay at 1154 cm− 1 and of V _ O at 1024 cm− 1 shifted from 1127 to 1013 cm− 1.

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