Applied Catalysis A: General 214 (2001) 4758

Coking and regeneration of H3PW12 O40 /SiO2 catalysts

Ivan V. Kozhevnikov , Stephen Holmes, M.R.H. Siddiqui
Department of Chemistry, Leverhulme Centre for Innovative Catalysis, University of Liverpool, Liverpool L69 3BX, UK Received 27 August 2000; received in revised form 20 December 2000; accepted 21 December 2000

Abstract The coking during propene oligomerisation over silica-supported heteropoly acid (HPA) H3 PW12 O40 (PW) and its palladium-doped form (1.62.5 wt.% Pd) and subsequent catalyst regeneration have been studied. Coke formation has been found to cause rapid deactivation of the catalysts. The coked versus fresh catalysts have been characterised by 31 P and 13 C MAS NMR, XRD, XPS and TGA/TPO to reveal that the Keggin structure of the catalysts was unaffected by coke deposition in both undoped and Pd-doped PW/SiO2 . The Pd doping has been shown to affect the nature of coke formed, inhibiting the formation of polynuclear aromatics. Addition of water, methanol or acetic acid to the propene ow causes the formation of oxygenated products at the expense of propene oligomers. These additives have been found to inhibit the coking, water being the most effective inhibitor. The removal of coke from HPA catalysts has been attempted using solvent extraction, ozone treatment and aerobic oxidation. The extraction (e.g. with CH2 Cl2 ) allows removing soft coke (with the TGA removal range of 170370 C) but is unable to remove hard coke (with the TGA removal range of 370570 C). Ozone treatment can remove both soft and hard coke at 150 C. The aerobic burning of coke on the undoped PW/SiO2 proceeds to completion in the temperature range centred at 500560 C, exceeding the temperature of PW decomposition. Doping the catalyst with Pd signicantly decreases this temperature to allow catalyst regeneration at temperatures as low as 350 C without loss of catalytic activity. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Heteropoly acid; Palladium doping; Propene oligomerisation; Coke formation; Catalyst regeneration

1. Introduction Heteropoly acids (HPAs) have been extensively studied as acid and oxidation catalysts for many reactions and found industrial application in several processes [16]. HPAs are promising solid acids to replace environmentally harmful liquid acid catalysts such as H2 SO4 [14]. The HPA-based solid acid catalysts, especially those comprising the strongest Keggintype HPA such as H3 PW12 O40 (PW) or H4 SiW12 O40 (SiW), are more active than conventional solid acids
Corresponding author. Tel.: +44-151-794-2938; fax: +44-151-794-3589. E-mail address: kozhev@liv.ac.uk (I.V. Kozhevnikov).

such as SiO2 -Al2 O3 , H3 PO4 /SiO2 and zeolites [1,4]. Their use, however, is limited because of the difculty of HPA regeneration [1]. Generally, in acid-catalysed organic conversions, solid acid catalysts are deactivated by coke formation. In the case of conventional catalysts such as SiO2 -Al2 O3 or zeolites, regeneration can be successfully achieved by a controlled burning of the deposited coke with oxygen at 450550 C [7,8]. In the case of HPA catalysts, this method is not applicable as they have insufcient thermal stability. The most commonly used HPAs, PW and SiW, decompose above 465 and 445 C, respectively [9]. Given the relatively low thermostability of HPAs, the development of a technique leading to a reduction in the temperature of coke removal would be benecial for

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 4 6 9 - 0

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the regeneration of deactivated solid HPA catalysts. Several known methods, such as solvent extraction, including supercritical extraction with CO2 or SO2 , and oxidation with ozone [8,10], could be useful for removing coke at lower temperatures. Modication of solid acid catalysts by platinum group metals, e.g. Pt or Pd, to enhance their regeneration is well known [7,8]. This allows a signicant reduction in the temperature of coke gasication with oxygen. Only few studies have dealt with the deactivation and regeneration of solid HPA catalysts so far [1116]. Recently, we have communicated that the Pd doping can greatly facilitate the regeneration of HPA catalysts by the aerobic burning of coke [17]. This paper presents a detailed account of our studies into the coking and regeneration of silica-supported PW catalysts in the gas-phase conversion of hydrocarbons. The oligomerisation of propene, previously studied with HPA catalysts [11,12], was chosen as a model reaction. The coked versus fresh catalysts were characterised by 31 P and 13 C MAS NMR, XRD, XPS and TGA/TPO. Various methods of coke removal such as solvent extraction, ozone treatment and aerobic oxidation were explored. The effect of palladium doping on the coke formation and burning was studied. 2. Experimental 2.1. Materials Tungstophosphoric acid, H3 PW12 O40 nH2 O, from Aldrich, palladium acetate from Johnson Matthey and silica Aerosil 300 from Degussa were used as purchased. All solvents were analytical grade and distilled before use. 2.2. Techniques Magic-angle spinning (MAS) solid-state NMR studies were carried out on a Bruker Avance DSX400 NMR spectrometer under ambient conditions. The 31 P NMR spectra were recorded at 161.99 MHz using a 7 mm rotor probe with 85% phosphoric acid as an external standard. The spinning rate was 4 kHz. The 1 H13 C cross-polarisation MAS NMR spectra were recorded at a frequency of 100.6 MHz. The peaks were referenced to tetramethylsilane (TMS) as an

external standard. The spinning rate was 34 kHz. Catalyst samples after treatment were kept in a desiccator over P2 O5 until the NMR measurements. Thermogravimetric analysis (TGA) was performed using a Perkin-Elmer TGA7 analyser. The carrier gas was air and the samples were heated from 40 to 700 C at a rate of 20 C min1 . Performed in air, TGA (TGA/TPO, temperature-programmed oxidation), allows quantitative measurement of the amount of deposited coke and the temperature of its aerobic gasication [7,8,11,12]. The TGA/TPO analysis of soft and hard coke was carried out as described elsewhere [11,17], the cokes with the TGA/TPO removal range of 170370 and 370570 C referred to as soft and hard coke, respectively. XPS studies were carried out on an AMICUS XPS spectrometer using Mg anode. The survey (wide) scans were taken using a 1.0 eV step size and 272 ms dwell time. The narrow scans were measured using a 0.1 eV step size and a dwell time of 1293 ms. XRD studies were performed on a Phillips PW1390 diffractometer under ambient conditions. Untreated catalyst samples were stored in a desiccator over P2 O5 prior to XRD measurements. The catalysts treated under a particular atmosphere were measured immediately after the treatment. 2.3. Catalyst preparation PW/SiO2 catalysts containing 20 or 40 wt.% PW were prepared by impregnating Aerosil 300 silica with an excess of a methanolic solution of H3 PW12 O40 as described elsewhere [18]. The catalysts were dried overnight at 120 C and then powdered. The BET surface areas were 285 and 140 m2 g1 for 20 and 40% PW/SiO2 , respectively. Palladium-doped 20 wt.% PW/SiO2 catalysts, containing 1.62.5 wt.% Pd, were prepared by two techniques as described elsewhere [17]: (1) by impregnating the PW/SiO2 catalyst with a toluene solution of Pd(OAc)2 followed by evaporation of toluene during which Pd(II) reduced to Pd(0) and (2) by impregnating Pd/SiO2 , prepared by loading Aerosil 300 silica with Pd(OAc)2 followed by reduction of Pd(II) to Pd(0) with H2 , with a methanolic solution of H3 PW12 O40 . The Pd-modied catalysts were nally dried overnight at 120 C. Both preparations were found to yield similar catalysts with respect to their coking and regeneration [17]. In this

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49

work, the Pd-modied catalysts prepared by the rst technique were mainly used. 2.4. Exposure of PW/SiO2 to solvent vapour An amount of 40 wt.% PW/SiO2 was treated with solvents at ambient temperature or at 150 C. At ambient temperature, the catalyst (0.5 g) was placed in a Pyrex boat and brought into contact with air saturated with the vapour of a solvent in a closed glass vessel for 18 h. The treatment at 150 C was carried out in a tubular furnace. The catalyst (0.5 g) placed in a Pyrex boat was exposed to a ow of air (80 ml min1 ) containing 7 vol.% of solvent vapour for 4 h. A gas bubbler placed in a water bath at a suitable temperature was used for saturating air with solvents. After solvent treatment, the catalyst was analysed by XRD. 2.5. Coking Coking was performed in a xed-bed ow reactor under propene at atmospheric pressure. Prior to coking, the catalyst (3.0 g) was pre-treated at 200 C under a 20 ml min1 ow of dry nitrogen for a period of 2 h. Then the sample was treated with propene at 20 ml min1 and 200 C for a certain period of time, typically 1 h for soft coke and 2 h or more for hard coke. (Hereafter soft and hard coke are referred to those with the TGA removal range of 170370 and 370570 C, respectively [7,11].) After that the volatile hydrocarbons were removed from the catalyst by purging with dry nitrogen at 20 ml min1 and 200 C for 15 min. 2.6. Propene oligomerisation and catalyst regeneration The propene oligomerisation was carried out using a stainless steel tubular xed-bed ow reactor housed in a three zone SSL tubular furnace tted with Eurotherm temperature controllers, with on-line GC analysis (a Varian 3800 Gas Chromatograph equipped with TCD and FID detectors and a 30 m VH1 megabore column). A gas mixture of propene and nitrogen was passed through the catalyst bed using mass ow controllers. A typical experiment was carried out as follows. The catalyst (1 g) was activated by heating under a nitrogen ow (30 ml min1 ) for 2 h at 200 C

in the xed-bed reactor. Then a mixture of propene and nitrogen, 1 and 49 ml min1 , respectively, was fed to the catalyst bed at 200 C. Over time, a strong deactivation of the catalyst by coke deposition was observed. In the case of 2.5% Pd-doped 20 wt.% PW/SiO2 , the deactivated catalyst was regenerated by aerobic burning of the coke as follows. The reaction was continued for a period of about 3 h then stopped, and the catalyst was cooled down in a nitrogen ow (49 ml min1 ). After that the catalyst was regenerated at 350 C in air (50 ml min1 ) for a period of 2 h. Better results were obtained when the air treatment as above followed by the reduction of the catalyst under a ow of 25% H2 in N2 at 225 C (50 ml min1 ) for 2 h. 2.7. Solvent extraction of coke A coked catalyst was placed in a 50 ml roundbottomed ask tted with a magnetic bar, and an organic solvent (20 ml) was added. The mixture was heated to reux with stirring and held at reux for 3 h. Then the mixture was allowed to cool, and the solid was isolated by ltration. Excess solvent was removed from the solid at 150 C under vacuum (102 mmHg) over a period of 3 h. 2.8. Oxidation of coke with ozone Coked catalysts (1.0 g) were treated with a gas ow containing 6% ozone in oxygen in a glass tubular xed-bed ow reactor at 150 C and a ow rate of 80 or 320 ml min1 . During the oxidation, decolouration of the catalysts occurred. The amount of coke was measured by TGA. 3. Results and discussion 3.1. Coking PW/SiO2 catalysts Passing a dry propene ow through the PW/SiO2 catalyst containing 2040 wt.% PW at 150200 C resulted in coke deposition on the catalyst surface, the amount of coke and its nature dependent on the temperature and time-on-stream, as demonstrated by TGA/TPO. Fig. 1 shows typical TGA/TPO data for the 20 wt.% PW/SiO2 catalyst coked for 1 or 3 h at

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Fig. 1. TGA/TPO for 20% PW/SiO2 coked with propene at 200 C for (a) 1 h and (b) 3 h.

200 C. As seen, the longer the time of coking, the harder, i.e. more difcult to burn, the coke forms. Sample (a) coked for 1 h shows a small peak at 230 C (0.9% weight loss), which can be attributed to low molecular weight propene oligomers, referred to as soft coke, and a large peak at 505 C (4.0% weight loss), representing higher aliphatic oligomers and polyaromatics referred to as hard coke [11,17]. Sample (b) coked for 3 h contains a harder coke, burning at a higher temperature; it shows a major peak at 560 C (4.6% weight loss), apparently representing mainly polyaromatics [17]. In this temperature range, the fresh 20 wt.% PW/SiO2 catalyst shows only one peak at 450 C (0.2% weight loss) due to the decomposition of HPA, releasing 1.5H2 O per Keggin unit [17], which is negligible compared to the weight loss for the coked catalysts. Fig. 2 shows the time course of coke formation on 20 wt.% PW/SiO2 at 200 C. As seen, the coke builds up quickly, reaching the amount of ca. 5 wt.% in about 1 h, followed by a slower deposition. This indicates that the catalyst is rapidly deactivated by coking. It is also seen that the nature of coke changes with the time-on-stream: the amount of harder coke, with the TGA/TPO removal range of 370570 C, increases at the expense of softer coke with the TGA/TPO removal range of 170370 C. The reduction in the fraction of the softer coke with time suggests that the harder coke

is formed over time on the surface of the solid, probably from the rearrangement of the coke precursors initially formed. Addition of nucleophilic compounds such as water, methanol, etc. to the propene ow caused the formation of oxygenated products at the expense of propene oligomers, as expected. Quite unexpectedly, it was found that the additives strongly inhibited coke formation (Table 1). Thus, without additives, the 40 wt.% PW/SiO2 catalyst made 3.6% coke in 3 h at 150 C.

Fig. 2. Plot of the amount of coke (total, soft and hard) vs. time for 20% PW/SiO2 coked with propene at 200 C.

I.V. Kozhevnikov et al. / Applied Catalysis A: General 214 (2001) 4758 Table 1 Effect of additives (7 vol.%) to propene ow on coke formation on 40 wt.% PW/SiO2 at 150 C Additive None H2 O Methanol Acetic acid Time-on-stream (h) 3.0 3.0 3.0 3.0 Amount of coke (%) 3.6 0.5 1.7 2.6

51

Addition of water to the propene ow greatly reduced the amount of coke to 0.5%, isopropanol found together with propene oligomers among the products. Addition of methanol brought the amount of coke down to a half of that formed by pure propene, methyl isopropyl ether being formed along with propene oligomers. Acetic acid caused the least effect, although isopropyl acetate was found among the products. The additives are likely to change the catalyst activity as well. At this stage, however, it is untimely to discuss the effect of additives on coking versus catalyst activity as no activity measurement was done in this work. To explain the above results we have studied the effect of these additives on the catalyst in the absence of propene using XRD to monitor the state of HPA in the catalyst. It was found that exposure of 40 wt.% PW/SiO2 to an atmosphere of air saturated with water, acetic acid, methanol or methyl acetate at ambient temperature overnight completely destroyed the crystallinity of HPA (Fig. 3). As all these solvents easily dissolve PW, the loss of HPA crystallinity indicates that after such treatment the HPA exists as a solution intercalated in the pores of silica. In contrast, exposure of this catalyst at 150 C to an air ow containing 7 vol.% of water, methanol or acetic acid for 4 h, which is similar to the coking conditions, had practically no effect on the HPA, the Keggin structure and the crystallinity remaining unchanged (Fig. 4). Apparently at 150 C, the amount of the solvents absorbed in the catalyst is too small to affect the crystal structure of HPA.

As the additives did not affect the structure of HPA in the catalyst, their effect on the coke formation could be explained as a result of their inuence on (i) the desorption of reaction products from the catalyst surface, (ii) the acid strength of HPA proton sites or (iii) the mechanism of propene conversion. The co-feeding of water is commonly used to enhance the desorption of reaction products from the catalyst. This often leads to an increase in reaction selectivity, sometimes at the expense of activity. In our case, the additives of water and other polar solvents could facilitate the desorption of coke precursors from the catalyst, decreasing the coke laydown. On the other hand, the additives will affect the acidity of HPA catalyst and, therefore, its activity. This effect will depend on the basicity of the additives. The PW acid strength must be weaker in the presence of water or methanol than in the presence of acetic acid because the rst two are much more basic. Hence, the catalytic activity of HPA towards the coke formation, is expected to be lower with water or methanol than with acetic acid, in agreement with the experiment (Table 1). The same should apply to the propene oligomerisation as well, for the catalyst activity is likely to change parallel for oligomerisation and coke formation. The mechanism of acid-catalysed propene oligomerisation can be adequately described as a carbeniumion one, including the formation of an isopropyl carbocation type intermediate (probably as an ion pair) by proton transfer from the catalyst to propene [19,20]. Subsequent chain growth yields eventually a range of propene oligomers together with coke as a by-product. In the presence of an acid catalyst, the nucleophilic additives due to their high afnity towards carbocations will interact with the isopropyl carbocation to give oxygenated products at the expense of oligomers and coke. This is indeed the case, water being the most active scavenger of the isopropyl carbocation. The overall mechanism can be schematically represented as follows:

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Fig. 3. XRD patterns for (a) 40% PW/SiO2 as-made and after treatment at ambient temperature overnight with solvent vapour: (b) acetic acid; (c) methyl acetate; (d) water; (e) methanol.

3.2. Characterisation of coked versus fresh catalysts The 31 P NMR spectra of the as-made PW/SiO2 samples showed a well-known single peak around 15 ppm (Fig. 5a) which is associated with the Keggin-type PW [18]. The Pd-doped catalysts exhibited the same spectrum (Fig. 5b), indicating that the doping does not affect the HPA structure. This is also supported by XRD data: the XRD patterns were the same for the undoped and 2.5% Pd-doped PW/SiO2 catalysts as well as for the bulk PW (Fig. 6). Note that

the crystallinity of supported HPA catalysts can vary depending on the preparation conditions, especially on drying (cf. Fig. 6b and c). Coking of PW/SiO2 catalysts, both undoped and Pd-doped, for 1 or 3 h did not change the 31 P NMR chemical shift, although some line broadening was observed compared to the fresh catalysts (Fig. 5c and d). The latter can be explained by the interaction of HPA with coke. The signicant line broadening of the 31 P NMR spectrum for PW supported on active carbon has been reported [21]. These data indicate that the

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Fig. 4. XRD patterns for 40% PW/SiO2 after treatment (150 C, 4 h) with an air ow containing 7 vol.% of solvent vapour: (a) water; (b) acetic acid; (c) methanol.

Keggin structure in the unmodied and Pd-modied HPA catalysts is not destroyed by the formation of coke. The oxidation state of tungsten in the coked as compared to fresh catalysts was examined by ex situ XPS. The binding energies of W 4p7/2 and 4f5/2 peaks were found to be 37.9 0.1 and 39.6 0.1 eV, respectively, typical of W(VI) [22] (Fig. 7). These were practically the same for the fresh and coked undoped and Pd-doped catalysts, indicating that the presence of coke or Pd did not change the oxidation state of tungsten in the catalysts. It should be noted, however, that, as the XPS measurements were performed ex situ,

re-oxidation of tungsten in the coked catalysts could not be excluded. The ex situ XPS of the 2.5% Pd-doped catalyst, both fresh and coked, showed a doublet in the palladium region which can be assigned to Pd 3d5/2 and 3d3/2 [23], the binding energies being 338.0 and 343.2 eV for the fresh catalyst and 337.8 and 342.9 eV for the coked, respectively, indicating the similar state of palladium in both catalysts. Preliminary analysis of these spectra points to the presence of both Pd(0) and Pd(II) in the catalysts, apparently the latter being formed by aerobic oxidation of Pd(0) while exposed to air. The intensity of the peaks,

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Fig. 5.

31 P

MAS NMR spectra for 20% PW/SiO2 : (a) as-made; (b) 2.5% Pd-doped; (c) coked for 1 h at 200 C; (d) coked for 3 h at 200 C.

however, was too low for quantitative analysis. Similar observation of Pd(0) and Pd(II) by XPS in the partially reduced salt Pd3 [PMo12 O40 ]2 has been reported [24]. Earlier we reported the 13 C CP MAS NMR spectra for coked PW/SiO2 catalysts [17]; these were found different for the coked undoped and Pd-doped PW/SiO2 catalysts. The undoped catalyst coked for 1 or 3 h showed a broad peak around 21 ppm referenced to TMS which was attributed to aliphatic hydrocarbons. There was also another peak there, around 129 ppm, which was assigned to polyaromatic hydrocarbons. The relative intensity of the aromatic peaks was higher in the hard coked samples. The 2.5% Pd-doped 20 wt.% PW/SiO2 catalysts coked for both 1 and 3 h showed peaks which could only be assigned to aliphatic hydrocarbons. Thus, both polyaromatic

and aliphatic coke form on the unmodied catalyst, while Pd-doping inhibits the formation of polyaromatics. The latter may be explained assuming that palladium can promote hydrogen transfer between coke precursors, thus facilitating the formation of the aliphatic coke. 3.3. TGA/TPO measurements for Pd-doped catalysts Our TGA/TPO data (Fig. 1) show that the aerobic gasication of coke from the undoped PW/SiO2 catalyst proceeds to completion in the temperature range centred at 500560 C, i.e. well above the decomposition temperature of HPA, which makes impossible regeneration of the catalyst by this method. We have found that Pd doping allows signicant reduction in the temperature of coke burning [17].

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Fig. 6. XRD patterns for (a) bulk PW, (b) 40% PW/SiO2 as-made and (c) 40% PW/SiO2 doped with 2.5% Pd.

Fig. 8 shows the TGA/TPO for the 1.62.5% Pd-doped PW/SiO2 catalysts coked for 1 h at 200 C. It can be seen that the addition of Pd gradually decreases the temperature of coke burning, down to 350 C at 2.5% Pd, that is ca. 100 C below the temperature of HPA decomposition. The effect of Pd doping appears to be two-fold. On the one hand, the Pd can catalyse the combustion of coke, on the other, it inhibits the formation of hard polyaromatic coke (see above). Similar results were obtained for Pt/Al2 O3 catalyst [7]. It was assumed that either platinum catalyses the oxidation of coke or coke deposited on the metal is different from that on the alumina [7]. 3.4. Catalyst regeneration by aerobic oxidation Oligomerisation of propene was studied as a test reaction for the deactivation/regeneration of the Pd-modied catalysts. Product analysis using gas chromatography showed the major products to be C12 to C18 oligomers. Similar results for the oligomerisation of propene using HPAs have been reported earlier [11]. The 2.5% Pd-doped 20% PW/SiO2 catalyst showed a very high initial activity, followed by a rapid deactivation (Fig. 9). The reaction was continued for a period of about 3 h, and by that time the conversion dropped to about 17%. Then the reaction was stopped, the

Fig. 7. XPS of the 20% PW/SiO2 catalyst: (a) fresh; (b) coked (200 C, 3 h).

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Fig. 8. TGA/TPO for 20% PW/SiO2 coked with propene at 200 C for 1 h: (a) undoped catalyst; (b) 1.6% Pd-doped; (c) 2.0% Pd-doped; (d) 2.5% Pd-doped.

catalyst was regenerated at 350 C in air for a period of 2 h and rerun. In the second run the performance of the catalyst was virtually the same as that in the rst run [17]. In contrast, the undoped PW/SiO2 catalyst did not regain its activity after regeneration under the above conditions. Even better results were obtained

when the Pd-doped catalyst was regenerated by air treatment as above, followed by the reduction under a ow of 25% H2 in N2 at 225 C for 2 h to convert Pd(II) formed during the aerobic oxidation to Pd(0). Fig. 9 shows the performance of the fresh and regenerated catalysts.

Fig. 9. Catalyst performance of fresh and regenerated 2.5% Pd-doped 20% PW/SiO2 for propene oligomerisation.

I.V. Kozhevnikov et al. / Applied Catalysis A: General 214 (2001) 4758 Table 2 Extraction of coke with reuxing DCM (3 h) from 20 wt.% PW/SiO2 coked with propene at 200 C for 1, 2 or 3 h Time of coking (h) Amount of coke (%) Hard 1.0 2.0 3.0
a b

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Residual coke (%) Soft 1.0 0.9 0.7 cokeb Total 4.9 5.2 5.3 Hard cokea 2.6 3.4 3.7 Soft cokeb 0.2 0.5 0.6 Total 2.8 3.9 4.3

cokea

3.9 4.3 4.6 TGA removal range: 170370 C. TGA removal range: 370570 C.

3.5. Coke removal Finally, we attempted the removal of coke from HPA catalysts using solvent extraction and oxidation with ozone. These methods have been described in the literature for the removal of carbonaceous deposits from various catalysts [8]. 3.5.1. Solvent extraction Extraction of coked HPA catalysts was attempted with reuxing solvents at atmospheric pressure, the residual coke determined by TGA. As solvents, toluene, cyclohexane and dichloromethane (DCM) were used, none of these dissolves PW. Of these solvents, DCM showed better results. Table 2 presents the data on DCM extraction of three samples of 20 wt.% PW/SiO2 coked for different period of time (1, 2 or 3 h), with an increasing fraction of the hard coke. For the most lightly coked catalyst (1 h), DCM extraction removed 42% of the total coke content (78% of the soft coke and 34% of the hard coke). With the sample coked for 2 h, we observed removal of 25% of the total coke content (43% of the soft coke and 22% of the hard coke). For the catalyst coked for 3 h, 19% of the total coke content was removed (14% of the soft coke and 19% of the hard coke). Since the HPA is not soluble in DCM, extraction of coke using this solvent would have appeared to have some utility for very lightly coked HPA catalysts. 3.5.2. Oxidation with ozone Some success in the removal of coke from, e.g. pentasil zeolite catalysts [25] and Pt-Re/Al2 O3 [26] at relatively low temperatures (T < 180 C) has been reported when ozone was used as the oxidant. Unlike oxygen, with ozone, the coke burning was non-selective and there was no preferential burning

at the metal centres during coke removal [26]. Ozone has been used to remove the organic surfactant at 250 C in the synthesis of mesoporous MCM-41 type zeolites [27]. To test the utility of ozone for the burning of coke on the surface of silica-supported HPA catalysts, the 20 wt.% PW/SiO2 catalyst coked at 200 C for 3 h, containing 5.3% of coke, was used. The method employed involved heating the coked catalyst under a ow of 6% ozone in oxygen (80 ml min1 ) at 150 C for 6 h. This resulted in a reduction of 40% of the total coke content. As the coke was removed, the catalyst was observed to become paler in colour. Some catalyst particles however remained black. Increasing the ow rate of O3 /O2 to 320 ml min1 improved the efciency of this process, with only a 5 h period necessary to remove all coloration from the surface of the catalyst, the residual amount of coke being <0.5%. No breakdown of the HPA Keggin structure was observed (31 P NMR) after coke removal. Recoking of the regenerated catalyst gave 5.0% coke deposition which indicates nearly full recovery of catalyst activity.

4. Conclusions The development of a technique leading to a reduction in the temperature of coke removal is of importance for regeneration of deactivated solid HPA catalysts. The formation of coke during the oligomerisation of propene, although rapidly deactivating the catalyst, does not affect the Keggin structure of silica-supported PW which justies attempts to regenerate such catalyst. Palladium doping of PW/SiO2 catalysts inhibits the formation of polyaromatic coke; only aliphatic coke, that appears easier to burn, is detected. In contrast, the undoped catalysts form a

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mixture of aliphatic and aromatic coke. Solvent extraction of coke using DCM under reux proved to be relatively successful in removing both hard and soft coke from very lightly coked HPA catalysts. Ozone treatment can be used to clean up heavily coked HPA catalysts at temperatures as low as 150 C, completely removing both hard and soft coke. This method, whilst perhaps not of great practical interest, should enable us to remove surface coke without destroying the HPA, thus allowing to probe the acid sites after catalyst regeneration. Most importantly, the aerobic gasication of coke on Pd-modied PW/SiO2 occurs at signicantly lower temperatures than on the undoped PW/SiO2 , which allows regeneration of the catalyst without destroying the Keggin structure of PW, hence without loss of its catalytic activity.

Acknowledgements This work was supported by BP Amoco Chemicals Ltd. We are indebted to Dr. H. He (Liverpool University) for measuring the NMR spectra and to Dr. A. Roberts (Kratos Analytical) for measuring the XPS spectra. References
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