Applied Catalysis A: General 225 (2002) 153165

Propane dehydrogenation over molybdenum hydrotalcite catalysts

P.C.H. Mitchell , S.A. Wass
Department of Chemistry, University of Reading, Reading RG6 6AD, UK Received 28 November 2000; received in revised form 9 January 2001; accepted 30 August 2001

Abstract The preparation of catalysts having molybdate intercalated into a hydrotalcite derived from magnesium aluminium hydroxy carbonate, [Mg6 A12 (OH)16 ]CO3 4H2 O, has been investigated. The materials produced in a variety of preparations are characterised by elemental analysis, X-ray diffraction pattern, and infrared spectrum. They have been tested as catalysts for the dehydrogenation of propane, both oxidative and non-oxidative. The material, which is most active in oxidative dehydrogenation of propane and the most selective towards propene, was prepared from a calcined commercial hydrotalcite and ammonium dimolybdate with prior impregnation with terephthalic acid and nitric acid. This catalyst had a high molybdenum content (27.3%) and interlayer spacing (10.75 ). The IR of this catalyst, and the yellow colour, are consistent with a well dispersed magnesium polymolybdate which is an efcient and selective propane dehydrogenation catalyst. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Hydrotalcite; Layered double hydroxide; Molybdenum; Molybdate; Catalyst; Propane; Oxidative; Dehydrogenation; Propene

1. Introduction Efcient catalytic dehydrogenation of propane to propene is much sought as a means of converting propane to a reactive chemical feedstock, propene [13]. The dehydrogenation may be non-oxidative (sometimes called static), i.e. without dioxygen in the reaction mixture, or oxidative, with a reaction mixture that includes dioxygen. Supported vanadates [38] and molybdates (especially, magnesium molybdate) [915] have been much studied as catalysts for propane dehydrogenation. In this paper, we report a study of propane dehydrogenation over molybdate/hydrotalcite catalysts. Our aim has been to determine how the activities and selectivities of the
Corresponding author. E-mail address: p.c.h.mitchell@reading.ac.uk (P.C.H. Mitchell).

catalysts depend on the method of preparation and composition. We describe the preparations and characteristic properties of the catalysts in some detail. Our molybdate/hydrotalcites may well undergo changes of morphology during the catalysis, e.g. collapse of the layer structure. Our materials are best described as catalyst precursors. Since our aim was to relate the catalysis to the preparation and characteristics of the molybdate/hydrotalcite catalyst precursors we have not undertaken a detailed study of the post-catalysis materials. Hydrotalcite (HTC), [Mg6 A12 (OH)16 ]CO3 4H2 O, is the parent compound of the layered, double hydroxide (LDH) group of minerals, also called anionic clays, having the general formula [M(1x) 2+ Mx 3+ (OH)2 ](CO3 )0.5x nH2 O. Cations are located in coplanar [M(OH)6 ] octahedra sharing vertices and forming M(OH)2 layers with the brucite

0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 8 6 2 - 6

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structure. Partial substitution of divalent cations by trivalent cations renders the layer positive. The positive charge is balanced by anions located between the hydroxylated layers where water molecules are also present. The HTC structure, therefore, consists of positively charged double hydroxide layers with the interlayer space lled by anions and water molecules. The interlayer species are referred to as intercalated [1621]. The hydrotalcites are porous catalyst supports [2225]. They may be ne tuned by varying the nature, concentration, and dispersion of the catalytic species, and the dimensions of the reaction space within the interlayer region. Intercalation of large polyoxometalate anions creates shape-selective catalysts [2628] and efcient catalysts for propane oxidative dehydrogenation [29]. Polyoxometalate-intercalated hydrotalcites have been prepared by, inter alia: direct synthesis (e.g. contacting a NiAl hydroxycarbonate with an aqueous vanadate solution [30,31]), anion exchange into the interlayer space expanded by prior intercalation of a large organic anion, e.g. heptamolybdate from water or aqueous ethanol into hydrotalcite intercalated with adipate, O2 C(CH2 )4 CO2 [3234], reconstruction of calcined hydrotalcite in the presence of a polyoxometalate, i.e. addition of the calcined hydrotalcite to a solution of the anion [3539]. A number of well established features of the oxidative dehydrogenation of propane to propene over V-Mg-O and Mo-Mg-O catalysts are pertinent to the work reported in this paper. The oxidative dehydrogenation proceeds according to the Marsvan Krevelen mechanism, i.e. the source of oxygen for the oxidation is lattice oxygen from the catalyst. The lattice defect is removed by a reaction with dissociatively adsorbed dioxygen [40,41]. There is no direct reaction between propane and dioxygen. The rate-determining step is irreversible dissociative chemisorption of propane, the -CH bond dissociating to give an isopropyl radical and H. The isopropyl intermediate is rapidly converted to propene by loss of a second H atom [42]. The catalysis requires both redox and acidbase functionality of the catalyst [29,4345]. The catalysts are, therefore, typically redox-active early transition metal oxides (e.g. V and Mo oxides) associated with divalent cations.

Catalytic properties depend strongly on the composition, structure and method of preparation of the catalysts. For example, among V-hydrotalcite catalysts those derived from decavanadate are more active than those from pyrovanadate [29]. Magnesium molybdate catalysts are of particular interest and provide a reference point for our work [9,4446]. The efcient catalysts contain a certain excess of MoO3 over MgMoO4 . They are characterised by a temperature-programmed reduction peak at 650 C (not found for MgMoO4 ) [46]. There is a correlation between Mo(VI) reducibility and activity [9]. The presence of a Mo(V) species, probably having a distorted pyramid structure, MoO5 5 , is shown by ESR [47,48].

2. Experimental 2.1. Materials Aluminium nitrate, Al(NO3 )3 9H2 O; ammonium heptamolybdate, (NH4 )6 Mo7 O24 4H2 O; citric acid, HO2 CCH2 C(OH)(CO2 H)CH2 CO2 H; glycerol, HOCH2 CH(OH)CH2 OH; magnesium nitrate, Mg(NO3 )2 6H2 O; sodium molybdate, Na2 MoO4 2H2 O; and terephthalic acid, C6 H4 -1,4-(CO2 H)2 , 98%, were ACS reagent grade chemicals from Aldrich. Ammonium dimolybdate, (NH4 )2 Mo2 O7 was a Climax Molybdenum Company product [49]. A commercial hydrotalcite hydrated aluminium magnesium hydroxy carbonate (Mg6 Al2 (OH)16 CO3 4H2 O) was obtained from Reheis Ireland. Laboratory prepared hydrotalcite was supplied by T.J. Pinnavaia. 2.2. Catalyst preparation Our aim was to develop a simple, effective procedure to intercalate molybdate in a hydrotalcite. Variables were the pre-treatment of the hydrotalcite (none, or calcined), the particular molybdate salt, prior intercalation by a swelling agent (glycerol, terephthalic acid), reaction temperature, exclusion of air (to minimise formation of carbonate in the hydrotalcite), nal pH (addition of nitric acid). Progress of each preparation was monitored by change of pH with time: when there was no further change reaction was complete (ca. 23 days). We rst describe our general procedures.

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Details of each preparation are given in Table 1. The products are conveniently designated by their laboratory notebook numbers, e.g. 4. We do not claim any particular originality in the preparations (although we supply detail that is missing from some reported preparations) since our aim is a systematic study of the relation between preparative variables, composition and catalytic properties. 2.2.1. Hydrotalcite pre-treatment In preparing the catalysts, we used hydrotalcite as received, i.e. Mg6 Al2 (OH)16 CO3 4H2 O, with intercalated carbonate, or calcined hydrotalcite. By calcining and then slurrying in CO2 -free water hydrotalcite, Mg6 Al2 (OH)16 CO3 4H2 O, is converted to a synthetic analogue of the mineral meixnerite, Mg6 Al2 (OH)16 (OH)2 4H2 O. In some preparations, the synthetic meixnerite is swollen (i.e. the layer spacing is increased) by slurrying with glycerol or terephthalic acid [36,50] to facilitate incorporation of molybdate in the interlayer region. The as-received hydrotalcite was heated in a covered platinum crucible (500 C, 3 h), then allowed to cool, and subsequently stored in vacuo over soda lime and P2 O5 . The calcined hydrotalcites were handled with the exclusion of air (in vacuo or under a nitrogen or argon atmosphere) to minimise re-carbonation by CO2 . 2.2.2. Treatment of hydrotalcite with a swelling agent We describe typical procedures with glycerol and terephthalic acid. 2.2.2.1. Glycerol. Calcined hydrotalcite (typically 6.5 g) was shaken (50 C, 72 h) with glycerol decarbonated water (150 cm3 , 2:1 v/v) in a ask ushed with nitrogen. The nal pH of the suspension was 12. Some preparations retained glycerol giving a sticky product, which was difcult to lter, and which charred when calcined (300 C in air) after incorporation of molybdate. A successful preparation required careful exclusion of CO2 and thorough washing of the initial product with hot ethanol to remove glycerol. 2.2.2.2. Terephthalic acid. Calcined Mg,Al hydrotalcite (5.62 g, 1.66 102 mol) was added to a solution of terephthalic acid (5.65 g, 1.7 102 mol) and sodium hydroxide (12.24 g, 0.306 mol) in decarbonated water (200 cm3 ). The solution under

nitrogen was shaken for 24 h at 70 C. A white solid, 16(27), was ltered off, washed with water and dried in air. Analysis: C, 6.42%; H, 3.88%. 2.2.3. Incorporation of molybdate Hydrotalcite, calcined or not, was added to an aqueous solution of molybdate blanketed with nitrogen. The mixture was stirred or shaken at constant temperature until the pH became constant, generally 23 days. Nitric acid (aqueous 50%, 25 cm3 ) was added to adjust the pH to 4.5 as required. Details are given in Table 1. The product was separated by ltration, washed with water on the lter, and dried in vacuo over P2 O5 . 2.2.4. Preparations utilising terephthalic acid 2.2.4.1. Calcined hydrotalcite, Rc, terephthalic acid, ammonium dimolybdate and nitric acid, 16(28). Calcined Mg,Al hydrotalcite, Rc, (5.62 g, 1.66 102 mol) was added to a solution of terephthalic acid (5.65 g, 1.7 102 mol) and sodium hydroxide (12.24 g, 0.306 mol) in decarbonated water (200 cm3 ). The solution under nitrogen was shaken for 24 h at 70 C. A white solid, 16(27), was ltered off, washed with water and dried in air; analysis: C, 6.42%; H, 3.88%. This solid was added to a solution of ADM (8.47 g, 0.025 mol) in water (150 cm3 ) and the mixture was stirred for 12 h at 20 C. The pH of the mixture was adjusted to 4.5 with 50% aqueous nitric acid (50 cm3 ) and the mixture was stirred for a further 12 h at 20 C. The product, was washed with water and ethanol and dried in vacuo over P2 O5 : pale yellow solid, 16(28), 5.20 g; analysis: C, 0.27%; H, 0.44%; Mo, 27.33%. Sodium molybdate was used as the molybdate source in an analogous preparation 17. 2.2.4.2. Via in situ synthesis of Mg4 Al2 (OH)12 (terephthalate(2-))xH2 O. To a solution of Mg(NO3 )2 6H2 O (41.0 g, 0.16 mol) and Al(NO3 )3 9H2 O (30.0 g, 0.08 mol) in water (128 cm3 ) was added a solution of terephthalic acid (13.2 g, 0.08 mol) and NaOH (57.5 g, 50%) in water (160 cm3 ) dropwise over 90 min with vigorous stirring. The mixture was digested at 350 C for 18 h and ltered hot until most of the water had been removed (care was taken to ensure that the lter did not suck dry) [33]. The product, a white slurry, was washed with 4 300 cm3

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of deionised water and stored as slurry in 500 cm3 of water until required. A portion of the product was dried in vacuo over P2 O5 : white solid, 11(21a), 3.57 g; analysis: C, 8.64%; H, 3.54%; N, 0.77%. The molybdate, Mg12 Al6 (OH)36 (Mo7 O24 )xH2 O, was synthesised. To the slurry from above was added a solution of Na2 MoO4 2H2 O (25.4 g, 0.11 mol) in water (45 cm3 ). The mixture was stirred vigorously for 30 min. It was then acidied with nitric acid (4 M, 35 cm3 ) and stirring was continued for another 30 min. The off-white product was ltered off, washed with 5 200 cm3 portions of deionised water, and dried in vacuo over P2 O5 . The product was a pale cream solid (analysis found: C, 1.21%; H, 2.53%; Mo, 23.41%; yield = 14.23 g). 7.00 g of this material was further dried in an oven at 125 C for 24 h. The oven dried material, 11(21b), was yellow: 6.36 g; analysis: C, 1.27%; H, 2.20%; Mo, 25.07%. 2.2.5. Magnesium molybdate, Mg2 Mo3 O11 Our procedure followed Miller et al. [46] and Courty et al. [51]. To a solution of AHM (5.30 g, 4 103 mol) and magnesium nitrate (5.13 g, 0.02 mol) in water (25 cm3 ) was added citric acid (14.50 g, 0.069 mol) and the mixture was stirred until the solution was clear. The solution was evaporated to dryness. The product was a pale yellow hygroscopic solid which was stored in vacuo over P2 O5 . This material was heated in vacuo at 80 C for 24 h and in air at 600 C for 48 h giving a pale yellow solid 13: C, H, N, 0.1%; Mo, 51.91%; calc. Mg2 Mo3 O11 : Mo, 49.31%. 2.3. Catalyst characterisation 2.3.1. Elemental analyses Catalysts were submitted for microanalysis, in duplicate, to Medac Ltd. The elements C, H, N, Mo were determined. 2.3.2. BET surface areas Surface areas were determined by the Catalyst Evaluation and Optimisation Service, University of St. Andrews, Scotland. Catalysts were pre-treated in owing nitrogen for 1 h at the degassing temperatures of 95 and 200 C. Surface area measurements were made on a Gemini 2360 instrument from Micromeritics using nitrogen at 196 C. Nitrogen adsorption was

measured at ve P/P0 values between 0.05 and 0.2. The reference was kaolinite (15.4 m2 /g). 2.3.3. X-ray diffraction Powder X-ray diffraction patterns were obtained with a Siemens D5000 dual goniometer diffractometer and a graphite monochromator using Cu K radiation. 2.3.4. Infrared spectra Fourier transformed infrared (FTIR) spectra were recorded for the catalysts in pressed KBr pellets on a Perkin-Elmer 1720-X FTIR spectrometer. 2.4. Catalytic activity measurements 2.4.1. Reaction test Catalytic testing was carried out by Dr. Robert Marshall, Catalyst Evaluation and Optimisation Service, University of Glasgow, Scotland. The catalytic tests were carried out at atmospheric pressure in a continuous ow system with a stainless steel tube (i.d., 2 mm) as reactor. The procedure used was based upon that of Miller et al. in the oxidative dehydrogenation of propane over magnesium molybdates [46]. For non-oxidative dehydrogenation (straight dehydrogenation) the reactant gas mixture comprised 18 mol% C3 H8 , 82 mol% He and for oxidative dehydrogenation 18 mol% C3 H8 , 9 mo1% O2 and 73 mol% He. The total gas ow was 25100 ml/min depending on the catalyst. The test procedure was as follows. After loading the catalyst, the gas mixture for non-oxidative dehydrogenation was established and passed through the reactor. The temperature of the reactor was raised in this ow of gas to 400 C at 5 C/min. A time interval of 0.5 h was allowed before analysis of the reactor efuent online by GCMS. Thereafter, the temperature was raised from 400 to 600 C in 25 C intervals (at 5 C/min) and allowed to equilibrate for 10 min at each temperature before sampling. After the sampling at 600 C in the non-oxidative conditions, the reactor was cooled to 400 C and oxygen introduced. After the oxidative dehydrogenation conditions were established, a further 0.5 h was allowed before samples were analysed at this temperature and then the temperature of the reactor raised to 600 C (at 5 C/min) with samples taken every 25 C as before. At the end of the test, the catalyst was cooled in a ow of he-

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lium overnight and discharged from the reactor when cool. The performance of a catalyst is referred to conversion of propane (C), selectivity (S) and product yield (Y): C= S= Y = mol propane consumed mol propane in feed mol propene produced Y = mol propane in feed C mol propene produced mol propane consumed

molybdate 17 or the in situ preparation from magnesium and aluminium nitrates, terephthalic acid and ADM 11. The starting molybdate is unimportant: this is not surprising since at a given Mo concentration (here, ca. 0.3 mol/dm3 ) different molybdates will converge to the same solution species at a given pH, hepta- or octamolybdate at pH 4.5. 3.1.1.2. Pre-treatment of the hydrotalcite. The hydrotalcites as received (Pnc and Rnc) contained interlayer carbonate anions. When these materials are calcined carbonate and water are removed. For example, the mass loss on calcining the Pnc material in vacuo at 500 C corresponded to the loss of 1CO2 and 12H2 O per formula unit: Mg6 Al2 (OH)16 (CO3 )(H2 O)4

3. Results and discussion Preparative variables, the catalyst composition, interlayer spacing from XRD, and infrared peaks are summarised in Table 1. The inuence on the Mo concentration in the catalysts and on the interlayer spacing of the source of molybdenum (ammonium dimolybdate or heptamolybdate), of the method of preparation, and of the nal pH of the reaction solution is shown diagrammatically in Fig. 1. Pertinent XRD spacings and IR peaks are also listed. In the XRD, we report the (0 0 1) reection, which denes the interlayer spacing and is generally the strongest peak. Where appropriate (i.e. when two phases are clearly present), a weak peak is labelled as w and relative intensities are given in parentheses. The XRD patterns of the molybdate-intercalated materials were noisy and broadened compared with the XRD of the hydrotalcites indicating a loss of crystallinity due to the intercalation procedure. In some products, the presence of unreacted hydrotalcite was evident in the XRD pattern. 3.1. Catalyst preparation and composition 3.1.1. Catalyst preparation 3.1.1.1. Molybdenum concentration in the catalysts. The highest molybdenum concentrations (2530 wt.%) are for those catalysts prepared at pH 4.5 by the addition of nitric acid to the reaction solutionwhether by the impregnation of the commercial hydrotalcite with ADM (15 and 19) or with terephthalic acid followed by ADM 16 or sodium

= Mg6 Al2 O9 + CO2 + 12H2 O The layer structure is regenerated when the resulting oxide (Mg6 Al2 O9 ) is plunged into water. During the re-hydration, it might be supposed that species in the solution may become intercalated. We carried out a number of experiments to discover whether molybdate would substantially displace carbonate from the uncalcined materials or whether calcination prior to molybdate impregnation was to be preferred. It is quite clear (Table 1) that the molybdate uptake (or the fraction taken up) (8, 9; 12, 18, 14) is greater for the calcined materials. However, when the impregnation is carried out at pH 4.5 in the presence of nitric acid (19, 15) molybdate uptake is high (3133 wt.%) with both the uncalcined and calcined materials. Presumably, nitric acid displaces intercalated carbonate: the carbon analyses are the lowest for the nitric acid treated materials and carbonate bands are absent from the infrared spectra (19, 15). 3.1.1.3. Intercalation with glycerol or terephthalic acid. The idea is that intercalation of, e.g. glycerol or terephthalic acid will open up the interlayer space of a hydrotalcite so facilitating the subsequent incorporation of molybdate. Our experience (Table 1) was that glycerol did not enhance the molybdate uptake or greatly increase the interlayer spacing (4, 8). The materials obtained after glycerol treatment of the hydrotalcite were sticky, difcult to lter and wash. The use of glycerol conferred no advantage.

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Fig. 1. Preparation of molybdenum/hydrotalcite catalysts showing (a) Mo content of the catalysts vs. nal pH of the impregnating solution, (b) Mo uptake from solution as the ratio of the nal Mo concentration (Mof ) to the initial concentration (Moi ) vs. nal pH. Numbers on the plots are the catalyst labels as in Table 1. Sources of Mo are AHM, ammonium heptamolybdate, and ADM, ammonium dimolybdate; TA refers to prior intercalation of hydrotalcite with terephthalic acid; 4.5 refers to those catalysts prepared by the addition of nitric acid to bring the impregnating solution to pH 4.5; D is the catalyst prepared by Drezdzons method (see text).

Terephthalic acid as intercalant was used in two ways. In the Drezdon in situ preparation of Mg,Al hydrotalcite the product (11a) contains intercalated terephthalic acid (Table 1). However, after incorporation of molybdate, some terephthalic acid remained and the lattice spacing decreased (11b). In the second procedure, terephthalic acid was used along with nitric acid during the incorporation of molybdate into a calcined commercial hydrotalcite (16, 17). In terms of

the amount of incorporation of molybdate or increased lattice spacing, there was no advantage in the use of terephthalic acid (cf. 16 and 17 with 15). In the material prepared from sodium molybdate (17) terephthalic acid was retained. 3.1.1.4. Reaction temperature and time. In previous work, intercalation procedures were generally carried out at elevated temperatures, e.g. 70 C. We generally

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adopted this reaction temperature although we tried a few preparations at room temperature (20 C). In comparable preparations (9, 12), there was less molybdate incorporation at the lower temperature. Intercalation of molybdate is slow. We monitored some preparations by following the change of pH with time (assuming that reaction was complete when there was no further change of pH). Between 2 and 3 days was needed for the system to reach equilibrium. 3.1.1.5. Summary: optimum preparation. The procedure that incorporates the most intercalated molybdate is the reaction of a hydrotalcite with a molybdate solution with the addition of sufcient nitric acid to give pH 4.5 (19, 15). The mixture should be stirred or shaken for 23 days at 70 C preferably under nitrogen (to eliminate uptake of carbon dioxide from air). Comparable uptakes were obtained with the commercial hydrotalcite uncalcined and calcined. There was no advantage in using glycerol or terephthalic acid, allegedly to facilitate molybdate intercalation. The in situ method of Drezdzon, which yields molybdate-intercalated Mg,Al hydrotalcite, has the advantage of shorter reaction time (0.5 h) and no prior hydrotalcite preparation. However, the simplest procedure is to stir uncalcined commercial Mg,Al hydrotalcite with molybdate at pH 4.5. 3.1.2. Location and structure of molybdate in the catalysts Pertinent data are included in Table 1 and Fig. 2. We take as evidence for intercalation of molybdate

expansion of the interlayer spacing beyond ca. 8 . Spacings near to or above 10 were found for 7 and 12 (uncalcined, AHM), 16, 17 (calcined, TA, nitric acid), 19 (uncalcined, ADM, nitric acid), 15 (calcined, ADM, nitric acid) and 11 (Drezdzon). For 7 and 12, obtained by reacting the uncalcined Mg,Al hydrotalcites with AHM, the higher d-spacing component was minor (see Table 1) indicating little intercalation. In those catalysts prepared at pH > 78, the predominant molybdate species was the MoO4 2 ion (IR band at ca. 830 cm1 , see Table 1). Those catalysts prepared at pH 4.5 and with high molybdate loadings (11c, 19, 15, 17) had an infrared peak at ca. 920930 cm1 and peaks or shoulders near 890 cm1 indicative of polymolybdate. It is noteworthy that those catalysts with the highest molybdate concentrations and d-spacings (11, 19, 16, 17), all prepared at pH 4.5, were yellow (Table 1). Magnesium molybdate is also yellow, but the XRD and IR of our yellow materials did not obviously correlate with the XRD and IR of any form of magnesium molybdate (see footnote to Table 1). We recall [32] that aqueous solutions of heptamolybdate are acidic, causing hydrolysis of hydrotalcites and some dissolution of magnesium in the host layers. Previous studies of intercalation of heptamolybdate reported that heptamolybdate intercalate had a basal spacing (c/3) of 12 [33,35]. Consequently, reections at 12, 6 and 4 would be expected as (0 0 3), (0 0 6) and (0 0 9) reections, respectively. However, our AHM and ADM products showed different patterns. It is noteworthy that a broad reection at 1011 was observed for our molybdate

Fig. 2. Lattice spacing in the catalysts vs. Mo content. Catalysts labelled as in Fig. 1.

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intercalates. A similar phase has been reported in almost all previous reports on synthesis of polyoxometalate intercalates [30,31,33,35,36,38,52,53]. It has been suggested that this phase is a poorly ordered MgAl salt of polyoxometalates. Evidently, we have prepared such a material. The question also arises whether our materials contain any MoO3 , an expected product of the thermal decomposition of AHM and ADM. The IR and XRD of our materials do not show the strong peaks characteristic of MoO3 (see footnote to Table 1). Signicant amounts of MoO3 are not present.

3.2. Catalyst activity and selectivity 3.2.1. Activity and selectivity of selected catalysts as a function of temperature Propane conversion and selectivity towards propene for selected materials and the homogenous reaction are shown as a function of temperature (400600 C) in Fig. 3. Our conditions are similar to those reported by Miller et al. except that we used helium rather than nitrogen as the inert diluent. We note 1. Conversions greater than ca. 5% require temperatures of 550 C and above.

Fig. 3. Propane dehydrogenation over selected catalysts, a calcined commercial hydrotalcite (labelled Reheis) and in the absence of a catalyst (homogeneous): conversion and selectivity vs. temperature.

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Fig. 4. Dehydrogenation of propane over various catalysts: yield of propene vs. propane conversion. (a) Non-oxidative: our Mo/HTC catalyst 16, Mg molybdate + MoO3 [9,11,46], GaCr/Zr phosphate [54], Cr/Zr phosphate [55]. (b) Oxidative: VMgO and VAlPO [46], Mg molybdate + MoO3 [9,11,46], our Mo/HTC catalyst 16, NiMoO4 [8]. The line of unit slope represents conversion of propane to propene with 100% selectivity.

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2. Both the oxidative and non-oxidative propane conversions over the catalysts are greater than the homogeneous conversion. The materials are therefore, acting as catalysts. 3. Selectivities towards propene are also higher than in the homogeneous reaction for non-oxidative hydrogenation, but in the oxidative dehydrogenation, only catalyst 16 confers appreciably more selectivity (nearly 100%) than the homogenous reaction (60%) at 550 and 600 C. 4. Comparing the catalytic behaviour of the molybdenum containing catalysts with the commercial hydrotalcite (Rc), we see that molybdenum enhances activity and selectivity in oxidative dehydrogenation and selectivity, but hardly activity, in non-oxidative dehydrogenation. Thus, molybdenum has a specic catalytic role especially in oxidative dehydrogenation. 3.2.2. Catalyst properties and catalyst behaviour We discuss the catalytic results at mostly 550 and 600 C where conversions are signicant. We see (Fig. 3) that catalyst 16 is the most effective catalyst in enhancing conversion and selectivity especially in oxidative dehydrogenation. This material was prepared from calcined commercial hydrotalcite and ADM with prior impregnation with terephthalic acid and nitric acid. Of the materials tested, 16 has the highest molybdenum and the biggest interlayer spacing and surface area. The composition of the terephthalic acid precursor corresponds approximately to the intercalation of 1/3 mol of terephthalic acid per hydrotalcite unit, i.e. Mg6 Al2 (O16 H14.67 )[C6 H4 (CO2 )2 ]0.33 (calculated (found): C, 6.04 (6.42); H, 3.05 (3.88)]. For a heptamolybdate intercalated hydrotalcite, the ideal composition of the anhydrous compound would be Mg6 Al2 (OH)16 (Mo7 O24 )0.33 ; the composition of 16 is close to this [calculated (found): H, 1.95 (0.44); Mo, 27.0 (27.3)]. There was no evidence from XRD or IR (see Table 1) of MoO3 in this catalyst. We compare our results with literature data for both oxidative and non-oxidative dehydrogenation of propane in Fig. 4 by plotting propene yield (Y, Section 2.4.1) versus conversion at 500600 C for the catalysts indicated. Our hydrotalcite supported catalyst, 16, out performs the other catalysts. It is striking that the vanadium catalysts are more active, but less selective than the molybdenum catalysts.

The slopes of the yield/conversion plots for non-oxidative dehydrogenation (0.87) and oxidative dehydrogenation (0.80) are similar. Thus, the catalysts show the same pattern of catalytic chemistrynot surprising since slow step is initial CH bond breaking [13] giving an adsorbed isopropyl radical [45]. Finally, we note that the layered structure of heptamolybdate-pillared hydrotalcite is destroyed at ca. 500600 C with the formation of MgAl2 O4 , MgMo2 O7 and MgMoO4 [16,56,57]. We regard the intercalated hydrotalcite as the precursor of the active catalyst, a well-dispersed magnesium polymolybdate.

4. Conclusions We have prepared catalysts having molybdate intercalated into a hydrotalcite derived from magnesium aluminium hydrotalcite, [Mg6 A12 (OH)16 ]CO3 4H2 O. Intercalation of molybdate is favoured by low pH (4.5). The material, which was most active in oxidative dehydrogenation of propane and the most selective towards propene, was prepared from a calcined commercial hydrotalcite and ammonium dimolybdate with prior impregnation with terephthalic acid and pH adjusted to 4.5 by addition of nitric acid. This catalyst (16) had a high molybdenum content (27.3%) and interlayer spacing (10.75 ). The IR of this catalyst, and the yellow colour, are consistent with a well-dispersed magnesium polymolybdate which is an efcient and selective propane dehydrogenation catalyst.

Acknowledgements We thank Climax Molybdenum Co. for funding this research, The Leverhulme Trust for the award of a Leverhulme Emeritus Fellowship to PCHM, C.J. Hallada and A.W. Armour of Climax for their interest and support, and T.J. Pinnavaia (Michigan State University) for supplying a hydrotalcite and for helpful comments; the X-ray Unit, Postgraduate Research Institute for Sedimentology, The University of Reading, for X-ray powder patterns; the Catalyst Evaluation and Optimisation Service, University of Glasgow and University of St. Andrews, Scotland, for catalytic and surface area measurements (Dr. Robert Marshall).

P.C.H. Mitchell, S.A. Wass / Applied Catalysis A: General 225 (2002) 153165

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