Applied Catalysis A: General 272 (2004) 229240

Hydrotalcites as precursors for Mg,Al-mixed oxides used as catalysts on the aldol condensation of citral with acetone
C. Noda Prez a,1 , C.A. Prez a , C.A. Henriques b , J.L.F. Monteiro a,
a

Ncleo de Catlise (NUCAT), COPPE/UFRJ, Caixa Postal 68502, CEP 21945-970, Rio de Janeiro, RJ, Brazil b Instituto de Qumica, UERJ, Rua So Francisco Xavier, 524, CEP 20559-900, Rio de Janeiro, RJ, Brazil Received 9 March 2004; received in revised form 25 May 2004; accepted 29 May 2004 Available online 24 July 2004

Abstract The use of Mg,Al-mixed oxides derived from hydrotalcites as basic catalysts for the citral/acetone aldol condensation was studied. Three series of hydrotalcite samples with different Al/(Al + Mg) molar ratios (0.2, 0.25, and 0.33), aged at different pH (10 or 13) and temperatures (333 and 473 K), were prepared as precursors. The corresponding Mg,Al-oxides were obtained by calcining the hydrotalcites at 723 K. They were characterized by N2 physisorption, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Their relative basicity was evaluated by using diacetone alcohol (DAA) retroaldolization as a model reaction. The Mg,Al-mixed oxides were efcient catalysts for the aldol condensation of citral with acetone in heterogeneous media. The best catalytic activities and pseudoionone yields were obtained from the samples with Al/(Al + Mg) molar ratio equal to 0.2 derived from hydrotalcites aged at 333 K. On the other hand, neither the aluminum content nor the pH of the synthesis gel inuenced signicantly the reaction selectivity. For mixed oxides derived from hydrotalcites aged at pH = 10 citral conversion decreased with increasing aluminum content, whereas for those obtained from precursors aged at pH = 13 citral conversion passed through a minimum for the sample with Al/(Al + Mg) = 0.25. Both trends reect the mesoporous characteristics of the samples and their relative basicity as measured by retroaldolization of DAA. Since the inuence of aluminum content on basic properties could not be clearly established, the textural characteristics best explained the observed trends. Catalysts derived from hydrotalcites aged at 473 K presented low catalytic activities, which was attributed to their lower mesoporosity. 2004 Elsevier B.V. All rights reserved.
Keywords: Citral; Pseudoionones; Basic catalysts; Hydrotalcite; Mg,Al-mixed oxides; Aldol condensation

1. Introduction Hydrotalcite-like compounds (HTLCs) or layered double hydroxides (LDHs) are anionic clays with general formula:
2+ 3+ (M1x Mx (OH)2 )x+ (Ax/m )m nH2 O

where the divalent ion can be Mg2+ , Ca2+ , Zn2+ , Cu2+ , Co2+ or Ni2+ , the trivalent ion Al3+ , Fe3+ or Cr3+ , and the compensation anion OH , Cl , NO3 , CO3 2 or SO4 2 . These materials have a structure similar to that of brucite (Mg(OH)2 ), where each Mg2+ ion is octahedrally surCorresponding author. Fax: +55 21 25626300. E-mail address: monteiro@peq.coppe.ufrj.br (J.L.F. Monteiro). 1 Present address: Universidade Estadual de Goi s, An polis, GO, a a Brazil. 0926-860X/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2004.05.045

rounded by six OH ions and the different octahedra share edges to form innite sheets. The sheets are stacked one on top of the other and are held together by weak interactions through hydrogen bonds. When M2+ cations are replaced isomorphously by M3+ cations with similar radius, the brucite-like layers become positively charged and the electrical neutrality is attained by compensating anions located in the interlayers along with water molecules [15]. The formation of a pure HTLC phase is favored by a Mg/Al molar ratio in the synthesis gel ranging between 4 and 2 (0.2 x 0.33, where x = Al/(Al + Mg)), although several authors claim that HTLCs with 0.1 x 0.5 can be prepared [1,2]. For higher x values, the increase in the number of neighboring Al-containing octahedra leads to the formation of Al(OH)3 , whereas low values of x leads to the segregation of Mg(OH)2 due to the high density of Mg-containing octahedra in the brucite-like sheets [6].

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HTLCs can be synthesized by different methods [13], the most common one being their coprecipitation from Mg2+ and Al3+ diluted solutions by mixing the latter with solutions containing carbonate and hydroxide ions. The synthesis can be carried out at constant or variable pH, in the former case under conditions of low or high supersaturation. The control of experimental parameters such as rate of addition of the reactants, pH and temperature of aging, and reactants concentration may be required since they inuence the purity, crystallinity, homogeneity, and the particle size of the solids produced. The thermal decomposition of Mg,Al-hydrotalcites at about 723 K gives rise to mixed oxides whose X-ray diffraction patterns indicate a diffuse MgO-type structure with no segregate crystalline phases [4,5,7]. Their thermal behavior in the range 300800 K is characterized by two endothermic transitions. The rst one, below 473 K, is attributed to the loss of interlayer water and the second, between 500 and 750 K, to dehydroxylation and loss of the charge compensating anions [35,7]. These structural modications are accompanied by an increase in specic surface area. When the temperature of calcination exceeds 1100 K the parent hydrotalcite is decomposed into MgO and MgAl2 O4 (spinel) phases [5,7]. The acidbase properties and, as a consequence, the catalytic activity and selectivity of these Mg,Al-mixed oxides depend on chemical composition and on the conditions of the thermal treatment used to decompose the hydrotalcite precursor, 723800 K being the range that produce the most active mixed oxides. With respect to the chemical composition, the optimum Mg/Al ratio will depend on the basic site density and strength required to activate the particular reactant. Intermediate Al/(Al + Mg) ratios lead to optimum catalytic properties in several reactions, such as isopropanol dehydrogenation (Al/(Al + Mg) = 0.25) [8], condensation of 2-hydroxiacetophenone and benzaldehyde (0.25 < Al/(Al + Mg) < 0.33) [9] and alkylation of phenol with methanol (Al/(Al + Mg) = 0.20) [10]. On the other hand, the rate of self-condensation of acetone to , -unsaturated ketones reached a maximum for Al-rich samples (Al/(Al + Mg) < 0.50) [11] whereas in the double bond isomerization of 1-pentene the Mg,Al-mixed oxides with low Al content (0.06 < Al/(Al + Mg) < 0.17) presented strong basicity and were more active than pure MgO [12]. The use of Mg,Al-mixed oxides as potential substitutes for common bases such as alkaline hydroxides, ammonia, ammonium salts or amines in new environmentally friendly processes can be advantageous since they are inexpensive, non-toxic and their basic properties can be tailored to the process under study aiming at increasing their activity and/or selectivity. They can also be easily separated and recycled and pollutant salts and by-products are not formed in the processes. Their catalytic applications include polymerization of -propiolactone [13] and alkene oxides [14], aldol, Knoevenagel, and ClaisenSchmidt condensations [5,9,1521], olen isomerization [12,22], alkylation of ketones [23] and

phenols [10], epoxidation of activated olens with hydrogen peroxide [24], glycerolysis of fats for the manufacture of monoglycerides [25], selective reduction of unsaturated ketones/aldehydes by hydrogen transfer from alcohols [26], Michael additions [27] and Wittig reaction [28]. The base-catalyzed aldol condensation of citral (3,7dimethyl-2,6-octadienal) with acetone (propanone) producing pseudoionone (6,10-dimethyl-3,5,9-undeca-trien-2-one) (PSI) and its subsequent cyclization over acid catalysts forming and -ionones are examples of processes involving products obtained from essential oils which are extensively used in the perfumery and soap industries. -Ionone is also important as a precursor in the synthesis of vitamin A. The commercial process for producing PSI involves the use of aqueous solutions of NaOH or KOH as catalysts and comprises unit operations such as neutralization, washing, phase separation, and vacuum distillation [29]. Citral conversion and pseudoionone selectivity are usually close to 60 and 80%, respectively. Besides the occurrence of undesired reactions (self-condensation of citral and PSI secondary reactions), the waste stream is an important problem. A heterogeneous process (using solid catalysts) substituting for the conventional one would reduce the amount of toxic waste and the number of steps involved. For example, the neutralization and washing steps can be eliminated and ltration can be used instead. In addition, the possibility of selecting the most active and/or the most selective catalyst can increase the total yield of desired products and can also reduce byproduct formation, thereby simplifying the distillation step. In a previous work [30] we were the rst to report on the excellent performance of a Mg,Al-mixed oxide derived from hydrotalcite as catalyst for the aldol condensation of citral and acetone. The observed conversions and selectivities were larger than those reported for the homogeneous process. Other authors [3133] have recently conrmed the activity of Mg,Al-mixed oxides and specially of the rehydrated Mg,Al-mixed oxides derived from hydrotalcites as catalysts in the same reaction, although using experimental conditions quite different from those typical of an industrial process (very low citral concentrations [31,32] or large amounts of catalyst [33]). The best performance of the rehydrated hydrotalcites (mixed hydroxides) was ascribed to the higher activity and selectivity to pseudoionones of the OH basic Brnsted sites (active sites of the rehydrated solids) as compared to those of the Lewis basic sites (oxygen anions of low coordination) present in calcined hydrotalcites (Mg,Al-mixed oxides). This work reports on the production of pseudoionones by aldol condensation of citral with acetone, using Mg,Almixed oxides with different compositions obtained from hydrotalcites synthesized under various experimental conditions (T or pH of aging of the gel) as basic catalysts. The inuence of the physico-chemical properties of the catalysts on their activity and on pseudoionone yields was studied, aiming at evaluating the heterogeneous process as a substitute for the classical homogeneous one.

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2. Experimental 2.1. Reagents The citral used was a mixture containing 93 wt.% of the two isomers (geranial and neral) obtained from fractional distillation under vacuum of Cuban lemongrass (Cymbopogon citratus) essential oil. Acetone (99.5 wt.%, technical grade) was dried and distilled to reduce the water content to <0.07 wt.%. Diacetone alcohol (98 wt.%, mesityl oxide content <2 wt.%) and all the reagents used in hydrotalcite synthesis were technical grade ones. 2.2. Hydrotalcite and mixed oxides synthesis Hydrotalcite samples were prepared by coprecipitation from an aqueous solution of magnesium and aluminum cations (solution A) and a highly basic carbonate solution (solution B). Solution A, containing Mg(NO3 )2 6H2 O and Al(NO3 )3 9H2 O dissolved in distilled water, was 1.5 M in (Al + Mg) with an Al/(Al + Mg) molar ratio equal to 0.20, 0.25 or 0.33. Solution B was prepared by dissolving appropriate amounts of Na2 CO3 and NaOH in distilled water in order to obtain [CO3 2 ] equal to 1.0 M and a pH equal to 10 or 13 during the aging of the gel. In the synthesis procedure, solution B was placed in a 150 ml PTFE reactor and solution A was slowly dropped into it at a 60 ml/h rate under vigorous stirring at room temperature. The gel was stirred for more 140 min at room temperature and then aged under constant pH (10 or 13) for 18 h at 333 or 473 K. The solid obtained was ltered and washed with hot distilled water (353363 K) until pH 7 and dried at 353 K overnight. The synthesized samples were named HTXX/Y(Z), where XX is 100 Al/(Al + Mg) nominal molar ratio, Y is the aging temperature ( C) and Z the pH of the gel during the aging step. Three series of hydrotalcites were prepared, two aged at 333 K at different pH (10 or 13), HTXX/60(10) and HTXX/60(13), and one aged at 473 K at pH 10, HTXX/200(10). In order to obtain the Mg,Al-mixed oxides the samples were calcined under air from room temperature up to 723 K at a 1 K/min heating rate, and kept at this temperature for 10 h immediately before each run. The mixed oxides so obtained were named MOXX/Y(Z), where XX, Y and Z are the same of the parent hydrotalcite.

2.3. Hydrotalcite characterization The chemical composition of the hydrotalcite samples was determined by atomic absorption spectrometry (AAS) using a Perkin-Elmer AAS 1100B spectrometer. X-ray powder diffractograms were recorded in a Rigaku Miniex X-ray diffractometer equipped with a graphite monochromator using Cu K radiation, 40 KV and 40 mA. The software Materials Data Jude, Version 5.0, was employed for structural renement aiming at calculating the cell parameters and crystallite sizes. Thermal decomposition of the hydrotalcites was evaluated by thermogravimetric analysis (TGA) and derivative thermal analysis (DTA) carried out in a Rigaku Thermobalance TAS 100 operating under a ow of air at a 10 K/min heating rate up to 1273 K. 2.4. Mg,Al-mixed oxides characterization Mg,Al-mixed oxides were obtained from the synthesized hydrotalcites by thermal treatment under the conditions described in Section 2.2. Their textural characteristics, such as BET specic surface area, external area (t-plot method) and pore volume (BJH method), were determined by N2 adsorptiondesorption at 77 K in a Micromeritics ASAP 2000. Prior to the analyses the samples were outgassed for 3 h at 723 K. The surface composition of the Mg,Al-mixed oxides was measured by X-ray photoelectron spectroscopy (XPS) in Perkin-Elmer spectrometer, Model 1257, operating with Al K radiation, 13 kV and 20 mA. The integrated areas corresponding to the O 1s, Al 2p and Mg 2s lines were calculated taking into account the sensitivity factors for these elements. The binding energies for O 1s and Al 2p were also calculated. Before the analysis, the samples were pretreated in situ under N2 at 10 K/min up to 723 K, staying at this temperature for 30 min, and then cooled down to room temperature and transferred, under vacuum, to the analysis chamber. The morphology and the size of the particles were analyzed by scanning electron microscopy (SEM) in a JEOLJSM 5800 microscope operating at an accelerating voltage of 20 kV. Before the analysis, the samples were mounted on a stub and were sputter-coated with a ne layer of gold. The relative basicity of the catalysts was evaluated by means of the diacetone alcohol (DAA) retroaldolization as

Fig. 1. Reaction scheme of diacetone alcohol retroaldolization.

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model reaction (Fig. 1). The use of the retroaldolization of diacetone alcohol on gas phase at 313 K as a model reaction for characterization of relative basicity of solid catalysts was rst proposed by Veloso and Monteiro [34]. The reaction is easy to perform and its results are readily interpreted since acetone is the only product formed via basic catalysis. In the present work, it was used for evaluating the relative basicity of the Mg,Al-mixed oxides. The reaction was studied in a xed-bed microreactor at 1 atm, 313 K and WHSV (gram of DAA per hour per gram of catalyst) equal to 19.3 h1 . The reactant was fed to the reactor by bubbling nitrogen (170 ml/min) through a saturator containing DAA held at 303 K. Before the reaction, the original hydrotalcite was calcined in situ under the conditions presented before (Section 2.2). Then, the system was cooled down to 313 K and the reaction started. The exit stream was regularly analyzed by on-line gas chromatography (50 m CP-Sil 5CB column on a Chrompack 9000 gas chromatograph). 2.5. Catalytic tests The reaction was carried out in liquid phase employing a 50 ml stainless steel batch reactor magnetically stirred and heated with an oil bath. The active form of the catalyst was obtained by calcination ex situ under the conditions mentioned in Section 2.2. After activation, it was rapidly transferred to the reactor containing the mixture of acetone and citral. The tests aiming at comparing the performance of the different catalysts were carried out at 398 K, for 4 h, under autogenous pressure, using a acetone/citral molar ratio of 1 and 5 wt.% of catalyst with respect to the weight of reactional mixture. The products were analyzed by gas chromatography using a 50 m Carbowax 20 M capillary column in a Chrompack 9001 chromatograph (FID detector). The samples were dissolved in n-hexane (technical grade) before the analysis. The identication of the reaction products was done by gas chromatography-mass spectrometry in a Shimatzu GC/MSQP 2000A.

3. Results and discussion 3.1. Characterization 3.1.1. Hydrotalcite samples 3.1.1.1. Chemical composition. The results of chemical analysis of the hydrotalcite samples, expressed by their Al/(Al + Mg) molar ratio, are shown in Table 1. As can be observed, for the samples with the largest aluminum content, the incorporation of this element from the gel was slightly smaller than that of magnesium, since the Al/(Al + Mg) molar ratios were lower than those expected. This effect was more signicant for the sample aged at 473 K and was also observed by other authors [35,36]. 3.1.1.2. XRD analysis. The X-ray diffractograms of the as-synthesized samples of series HTXX/60(10), HTXX/60(13) and HTXX/200(10) are shown in Figs. 24, respectively. Except for samples HT20/60(10) and HT20/ 200(10), they show the characteristic pattern of pure hydrotalcite in carbonate form, whose main planes are indicated in the gures. For sample HT20/60(10), besides the hydrotalcite peaks, diffraction lines corresponding to a hydromagnesite (magnesium hydroxy-carbonate tetrahydrate, 4MgCO3 Mg(OH)2 4H2 O) phase were observed, whereas for sample HT20/200(10), the indigenous phase present was identied as magnesite (magnesium carbonate, MgCO3 ). In both cases the formation of these additional phases (marked with * in the gures) can be associated to the methodology used that combines high concentration of CO2 and 3 variation of pH from 14 to 10 during the addition of the metal cations to the basic solution, favoring the formation of magnesium hydroxycarbonate/carbonate phases in the case of Al/(Al + Mg)gel molar ratios close to 0.20 [37]. The lattice parameters, a and c, typical of hydrotalcite structures with rhombohedral 3R symmetry were calculated for all samples from the peaks associated to planes (0 0 3), (0 0 6), (1 1 0) and (1 1 3) and are shown in Table 1. The values of a were in the range 0.3080.304 nm and for both series aged at 333 K they show a trend to decrease with the increase in the Al/(Al + Mg) molar ratio, as expected. This trend did

Table 1 Chemical composition and cell parameters of the hydrotalcite samples Sample HT20/60(10) HT25/60(10) HT33/60(10) HT20/60(13) HT25/60(13) HT33/60(13) HT20/200(10) HT25/200(10) HT33/200(10) Al/(Al + Mg)gel 0.20 0.25 0.33 0.20 0.25 0.33 0.20 0.25 0.33 Al/(Al + Mg)solid 0.20 0.25 0.30 0.20 0.25 0.31 0.20 0.24 0.27 a (nm) 0.3063 0.3060 0.3046 0.3078 0.3061 0.3047 0.3052 0.3056 0.3052 0.00004 0.00023 0.00023 0.00005 0.00006 0.0006 0.00005 0.0003 0.00006 c (nm) 2.349 2.332 2.291 2.389 2.338 2.288 2.310 2.319 2.304 0.0021 0.0102 0.0064 0.0022 0.0010 0.0005 0.0014 0.0008 0.0016 Crystallite size (nm) 7.3 9.7 12.7 12.9 23.2 13.0 16.0 19.8 20.4 0.2 0.3 0.2 0.3 0.3 0.3 0.2 0.3 0.3

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Fig. 2. X-ray diffractograms for samples (a) HT20/60(10), (b) HT25/60(10) and (c) HT33/60(10). Peaks marked with (*) correspond to hydromagnesite.

Fig. 4. X-ray diffractograms for samples: (a) HT20/200(10), (b) HT25/200(10) and (c) HT33/200(10). Peaks marked with (*) correspond to magnesite.

not hold for series HTXX/200(10), where a maximum in parameter a was observed for sample HT25/200(10). This can be associated to the presence of a signicant amount of magnesite as impurity in sample HT20/200(10). So, the real Al/(Al + Mg) ratio of the hydrotalcite phase in this sample was >0.20 (the bulk value from chemical analysis) and a

value of a lower than that of sample HT25/200(10) is not inconsistent. This same reasoning can be used to explain why the value of a for samples HT20/60(10) and HT25/60(10) are roughly the same. The crystallite sizes obtained from the full width at halfmaximum of the diffraction peak corresponding to plane (0 0 3) are also presented in Table 1. The results show that for samples aged at pH 10 the crystallite size increased with the increase in both aluminum content and temperature of aging. On the other hand, for series HTXX/60(13) the sample with an intermediate (0.25) value of the Al/(Al + Mg) ratio presented the largest crystallite size. 3.1.1.3. Thermogravimetric analysis. The TGA/DTA results for the as-synthesized samples are reported in Table 2.
Table 2 Thermogravimetric analysis of hydrotalcite samples Sample HT20/60(10) HT25/60(10) HT33/60(10) HT20/60(13) HT25/60(13) HT33/60(13) HT20/200(10) HT25/200(10) HT33/200(10) Loss of interlayer water wt.% Tmax a (K) 18.15 18.81 19.18 17.69 17.84 18.68 11.11 12.75 13.61 477 476 488 490 492 494 495 494 503 Dehydration/decarbonation wt.% Tmax a (K) 26.62 24.56 27.22 29.23 27.85 24.47 15.02 30.43 29.08 670 671 675 650 662 676 680 683 697

Fig. 3. X-ray diffractograms for samples (a) HT20/60(13), (b) HT25/ 60(13) and (c) HT33/60(13).

a T max is the maximum temperature of the corresponding peak in the DTA prole.

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C. Noda P rez et al. / Applied Catalysis A: General 272 (2004) 229240 e Table 3 Chemical formula of hydrotalcites Samples HT20/60(10) HT25/60(10) HT33/60(10) HT20/60(13) HT25/60(13) HT33/60(13) HT20/200(10) HT25/200(10) HT33/200(10) Chemical formula Mg6.4 Al1.6 (CO3 )0.8 (OH)16 6.4H2 O Mg6 Al2 (CO3 )(OH)16 6.8H2 O Mg5.6 Al2.4 (CO3 )1.2 (OH)16 7.2H2 O Mg6.4 Al1.6 (CO3 )0.8 (OH)16 6.2H2 O Mg6 Al2 (CO3 )(OH)16 6.4H2 O Mg5.5 Al2.5 (CO3 )1.25 (OH)16 7.0 H2 O HT (not determined) and 36% of MgCO3 Mg6.08 Al1.92 (CO3 )0.96 (OH)16 4.3 H2 O Mg5.84 Al2.16 (CO3 )1.08 (OH)16 4.7 H2 O

Fig. 5. DTA-TGA proles for sample HT25/60(13).

For the pure hydrotalcite samples, they are in good agreement with those from the literature [35,7], which reports that hydrotalcites in the carbonate form present two welldened weight losses. The rst, up to 500 K, corresponds to the loss of interlayer water, and the second, between 548 and 723 K, is associated to dehydroxylation and decarbonation. A typical TGA/DTA prole is shown in Fig. 5. Table 2 indicates that some trends can be observed as to the inuence of the Al/(Al + Mg) ratio since both the amount of interlayer water and the maximum temperature of the peaks in the DTA proles increase with increasing Al content in each series. On the other hand, the samples aged at 473 K present a lower content of interlayer water and a dehydroxylation/decarbonation weight loss slightly larger. Fig. 6 shows the thermogram for sample HT20/60(10), which presents three peaks in the DTA prole. The rst two peaks are those typical of hydrotalcites whereas the third peak, at 779 K, is indicative of the presence of a different phase that was identied as hydromagnesite by XRD analysis and conrmed by TGA/DTA of a sample of pure hydromagnesite. For sample HT20/200(10), the third peak was an intense one observed at 790 K in the DTA prole with a corresponding weight loss of about 19%. This peak

was associated to the magnesite phase identied by XRD analysis. The results of chemical analysis (Al/(Al + Mg) molar ratio) associated to those of TGA (weight loss associated to interlayer water) allowed the calculation of the chemical formula of the hydrotalcite samples, which are presented in Table 3. In the case of sample HT20/60(10) the presence of a small quantity of hydromagnesite was not taken into account in this calculation. The samples of series HTXX/60(10) were synthesized in triplicate and the results of AAS, XRD and TGA/DTA for these samples indicated the reproducibility of the methodology used. 3.1.2. Mg,Al-mixed oxides 3.1.2.1. XRD analysis. For all the calcined samples, XRD diffraction patterns correspond to that of a poorly crystallized MgO with a periclase-type structure. In each series, as the (Al/(Al + Mg)) molar ratio increases the unit cell parameter of the periclase-type phase decreases. Similar results were also reported [27] and are associated to the progressive isomorphic substitution of Al3+ (0.50 ) for Mg2+ (0.65 ). 3.1.2.2. Textural and morphological characterization. Inspection of the N2 adsorptiondesorption results for the mixed oxides indicated that all samples, except MO33/200(10), presented IUPAC type IV isotherms, conrming that the thermal decomposition of the hydrotalcite samples produced mesoporous Mg,Al-mixed oxides. Sample MO33/200(10) presented an isotherm that resembled that of type I, reecting the importance of microporosity for this solid. The main textural characteristics of the oxides produced from hydrotalcite samples aged at 333 K are shown in Table 4. For these mixed oxides some clear trends can be observed: (i) the BET specic surface area decreased with increasing Al content; (ii) for both series, the mesopore volume calculated by the BJH method using the adsorption branch of the isotherm presented a minimum value for the samples with Al/(Al + Mg) ratio equal to 0.25; (iii) the micropore volume was not signicant (although micropores contributed signicantly to the BET area).

Fig. 6. DTA-TGA proles for sample HT20/60(10).

C. Noda P rez et al. / Applied Catalysis A: General 272 (2004) 229240 e Table 4 Textural and morphological characteristics of the mixed oxides Precursor HT20/60(10) HT25/60(10) HT33/60(10) HT20/60(13) HT25/60(13) HT33/60(13) HT20/200(10) HT25/200(10) HT33/200(10) SBET (m2 /g) 271 242 184 294 244 179 48 108 193 SEXT (m2 /g)a 179 131 96 110 73 118 24 33 5 Vmicro (cm3 /g)a 0.041 0.048 0.060 0.089 0.077 0.027 0.011 0.036 0.085 Vmeso (cm3 /g)b 0.47 0.37 0.44 0.61 0.41 0.54 0.068 0.087 0.030 Morphology

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Aggregates of porous particles with 410 m Large particles, between 400 and 700 m, along with others with 310 m Great dispersion of particle size, between 3 and 100 m Aggregates of porous particles with 410 m Large particles, between 10 and 150 m Agglomerates, porous particles with 510 m and others with 70 m n.d. n.d. n.d.

n.d. = not determined. a t-plot. b BJH method (17600 ).

When mixed oxides samples with similar Al/(Al + Mg) ratios are compared, it can be observed that they present almost the same BET areas but those aged at pH = 13 presented mesopore volumes higher than those aged at pH = 10. The mixed oxides derived from the hydrotalcite samples aged at 473 K (MOXX/200(10)) exhibited very low mesoporosity, as also shown in Table 4. As a consequence, for these samples the relative importance of micropores is larger than for the samples aged at 333 K. Contrary to what was observed in the series aged at 333 K, the increase of the Al content determined an increase in the BET area of the samples aged at 473 K. The impure sample MO20/200(10) had a BET area and a porous volume much smaller than the others. The scanning electron micrographs of the samples obtained from hydrotalcites aged at 333 K indicated that they are formed by particles with irregular surface and without a well-dened shape, as illustrated in Fig. 7 for sample MO20/60(10). From the morphological aspects summarized in Table 4, apparently the pH of synthesis had no signicant inuence on the morphology of the mixed oxides, which is, however, affected by the Al content. 3.1.2.3. X-ray photoelectron spectroscopy. The surface composition of the Mg,Al-mixed oxides was determined by XPS. The O, Mg and Al surface contents, namely Os , Als and Mgs , respectively, were calculated and compared to those corresponding to the bulk contents (Ob , Mgb , Alb ). The binding energies for O 1s and Al 2p were also determined. Table 5 shows that all the samples were rather homogeneous although a slight segregation of Al in the surface could be detected, mainly for the samples of series MOXX/60(13). Differently from what was previously reported [38], the surface oxygen content was not signicantly inuenced by the chemical composition of the samples within the range of Al/(Al + Mg) ratios studied in the present work. The observed Os /Ob ratios (between 0.99 and 1.06) are higher than those reported in the literature for both pure MgO (0.92)

and for Mg,Al-mixed oxides (0.60.8) with Al/(Al + Mg) between 0.10 and 0.75 [38]. Table 5 presents the binding energies obtained for O 1s and Al 2p. These values are lower than those reported by

Fig. 7. SEM micrographs of the Mg,Al-mixed oxide MO20/60(10). (a) 450X, photo width = 293 m and (b) 3700X, photo width = 35.7 m.

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Table 5 Atomic ratios and binding energies for the mixed oxides Precursors HT20/60(10) HT25/60(10) HT33/60(10) HT20/60(13) HT25/60(13) HT33/60(13) Mgs /Mgb 0.94 0.96 0.89 0.88 0.85 0.95 Als /Alb 1.08 1.12 1.03 1.19 1.14 1.15 Os /Ob 1.03 1.00 1.05 1.05 1.06 0.99 (Al/(Al + Mg))s 0.22 0.28 0.33 0.25 0.31 0.35 (Al/(Al + Mg))b 0.20 0.25 0.30 0.20 0.25 0.31 EAl 2p (eV) 73.5 73.5 73.7 73.5 74.5 73.1 EO 1s (eV) 530.3 530.3 530.5 529.9 531.3 529.5

Wagner et al. [39] for the Al 2p in MgAl2 O4 (74.7 and 76.3 eV) but are close to those reported for pure alumina (73.774.5 eV). However, this fact is not sufcient to assure that the surface of the mixed oxides studied in this work was mainly composed by alumina. The binding energies calculated for O 1s were also not signicantly affected by the chemical composition and were consistent with those reported by Di Cosimo et al. [38] (530.1531.2 eV). However, contrary to what was observed by the latter authors, no correlation could be observed between the catalytic activity of the samples and their surface composition or the binding energy calculated from XPS. 3.1.2.4. Basicity characterization. Figs. 8 and 9 show the molar fraction of acetone formed during the retroaldolization of diacetone alcohol for the oxide samples derived from HTLCs aged at 333 K. When the original synthesis was performed at a pH = 10 an inverse relationship can be observed between activity of the oxide sample (as given by the acetone molar fraction) and its Al content (Fig. 8series MOXX/60(10)). This seems to support previous observations of other authors [13] that the basic site density of mixed oxides derived from hydrotalcites decrease with increasing Al content. However, the same behavior was not observed when the original synthesis was performed at a pH = 13 (samples MOXX/60(13)), as shown in Fig. 9. Now, the samples with the highest and the lowest Al content exhibited

the same behavior, both being more active than the sample with the intermediate Al content (MO25/60(13)). It has been previously suggested that although the basic site density decreases with increasing Al content the relative proportion of strongly basic site increases [5,13]. This could explain the minimum observed for the catalytic activity of sample MO25/60(13). Although this possibility cannot be discarded, one would expect it to hold for demanding reactions and this is not the case of the diacetone alcohol retroaldolization reaction, which can be easily performed even at room temperature. Fig. 10 shows that a very good correlation is observed between acetone initial molar fraction and external area for all the oxide samples derived from hydrotalcites aged at 333 K. This suggests that for a facile reaction such as the present one accessibility of the reactant to the active sites on the surface of the mesopores and on the external surface of the particles (as expressed by Sext ) is the governing parameter rather than the strength of the sites or their theoretical global concentration (related to the Al content). This same relationship does not hold for the BET surface area, suggesting that the contribution of the micropores is not signicant. Fig. 11 shows the activity of the Mg,Al-mixed oxides of series MOXX/200(10). Now any correlation between activity and physico-chemical characteristics of the samples is difcult to be drawn since sample MO20/200(10) is of a distinct nature. It can be seen that the samples of this series

Fig. 8. Acetone formation from retroaldolization of DAA (atmospheric pressure, 313 K, WHSV = 19.3 h1 ): ( ) MO20/60(10), ( ) MO25/60(10) and ( ) MO33/60(10).

Fig. 9. Acetone formation from retroaldolization of DAA (atmospheric pressure, 313 K, WHSV = 19.3 h1 ): ( ) MO20/60(13), ( ) MO25/60(13) and ( ) MO33/60(13).

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Fig. 10. Relation between initial activity for retroaldolization of DAA and external area: ( ) MO20/60(10), ( ) MO25/60(10), ( ) MO33/60(10), ( ) MO20/60(13), ( ) MO25/60(13) and ( ) MO33/60(13).

have activities similar to those of the samples of the other two series although having much smaller external areas than the latter. This suggests that surface concentration of sites with the necessary strength to catalyze the retroaldolization of diacetone alcohol is larger for series MOXX/200(10). 3.2. Citral/acetone aldol condensation The aldol condensation between acetone and citral catalyzed by Mg,Al-mixed oxides, whose mechanism is represented in Fig. 12, formed as main products two isomers of pseudoionone (PSIA and PSIB ). Other compounds originating from the condensation either between two molecules of citral (PCS) or between pseudoionone and one or two acetone molecules were also observed as minor products. Only traces of diacetone alcohol, derived from the selfcondensation of acetone, were found.
Fig. 12. Mechanism for acetone/citral aldol condensation on basic catalysts.

Fig. 11. Acetone formation from retroaldolization of DAA (atmospheric pressure, 313 K, WHSV = 19.3 h1 ): ( ) MO20/200(10), ( ) MO25/200(10) and ( ) MO33/200(10).

According to this mechanism, the rst step in the aldol condensation of acetone and citral is the abstraction of an -proton from acetone catalyzed by the basic sites, forming the carbanion (1). This species attacks the carbon of the carbonyl group of citral forming the carbanion (2), which is then dehydrated, restoring the basic sites and forming pseudoionone (cis and trans isomers). As can be observed in Fig. 13, for Mg,Al-mixed oxides derived from hydrotalcites aged at 333 K the highest activity was presented by the catalyst with the lower aluminum content in each series. For those obtained from the gel aged at pH 10 (MOXX/60(10) series), citral conversion decreased with the increase in Al/(Al + Mg) ratio, a behavior analogous to that observed for the retroaldolization of diacetone alcohol. Again, these results can be associated to both tex-

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Fig. 13. Citral conversion as a function of Al/(Al + Mg) molar ratio for samples MOXX/60(10) and MOXX/60(13) (398 K, autogenous pressure, acetone/citral = 1 (molar), 5 wt.% of catalyst).

Fig. 15. PSI and PCS selectivities as a function of citral conversion (398 K, autogenous pressure, acetone/citral = 1 (molar), 5 wt.% of catalyst) for samples MOXX/60(10) and MOXX/60(13).

tural characteristics (mesoporosity, as reected by external surface area) and relative basicity, which is expected to decrease with increasing Al content. On the other hand, for the mixed oxides derived from the gel aged at pH = 13 (MOXX/60(13) series), citral conversion passed through a minimum for Al/(Al + Mg) equal to 0.25, as also observed for diacetone alcohol retroaldolization. Again, mesoporosity and relative basicity can explain this observed trend. However, as shown in Fig. 14, a single correlation between external surface area and activity cannot be dened for the two series, contrary to what was shown before for diacetone alcohol retroaldolization. Such a correlation holds for each series separately. For samples with similar external areas, those of series MOXX/60(13) are much more active than those belonging to series MOXX/60(10). This suggests that for the aldol condensation reaction between citral and acetone not only the concentration of accessible basic sites but also their relative strength play an important role. Since this reaction is much

Fig. 14. Relationship between citral conversion and external area for the mixed oxides MOXX/60(10) ( ) and MOXX/60(13) ( ).

more demanding than the retroaldolization of diacetone alcohol, the different behavior of the samples would indicate that those obtained from the gel aged at pH = 13 contain a larger concentration of sites strong enough to catalyze the abstraction of a proton from the methyl group of the acetone molecule (which is more difcult than extracting a proton from the hydroxyl group of the diacetone alcohol molecule). The Mg,Al-mixed oxides with Al/(Al + Mg) equal to 0.20 or 0.25 derived from both series present similar catalytic activities, indicating that the smaller external surface areas for series MOXX/60(13) samples were compensated by the larger number of active sites for these samples. A signicant difference was observed only for samples MO33/60(10) and MO33/60(13) and could be related to both the higher fraction of strong enough basic sites and the larger external surface area presented by the mixed oxide derived from the gel aged at pH 13. Fig. 15 presents the selectivity to pseudoionones (PSI) and to the product of self-condensation of citral (PCS) as a function of citral conversion. It can be observed that in the conditions studied neither the aluminum content nor the pH of aging have a clear inuence on reaction selectivity. In spite of the scatter of the data points, there is a slight trend for decreasing selectivity to pseudoionone with increasing citral conversion. For conversions between 25 and 60%, PSI selectivities in the range 8060% were observed while those for PCS were always smaller than 13%. These results conrm that citral conversions and PSI selectivities equivalent to those in homogeneous medium can be attained in heterogeneous medium using Mg,Al-mixed oxides as catalysts. Fig. 16 shows that for both MOXX/ 60(10) and MOXX/60(13) series the best pseudoionone yields were obtained with the samples with the lowest Al content, MO20/60(10) and MO20/60(13), the ones with the highest conversions. The catalytic activities for samples MOXX/200(10) are presented in Fig. 17 and they show the same trend as ob-

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239

Fig. 16. Pseudoionones yield (%) as a function of Al/(Al + Mg) molar ratio for samples MOXX/60(10) and MOXX/60(13) (398 K, autogenous pressure, acetone/citral = 1 (molar), 5 wt.% of catalyst).

Fig. 17. Citral conversion as a function of Al/(Al + Mg) molar ratio for samples MOXX/200(10) (398 K, autogenous pressure, acetone/citral = 1 (molar), 5 wt.% of catalyst).

served before for the retroaldolization of diacetone alcohol. However, it can be seen that these oxides had catalytic activities lower that those of the samples derived from hydrotalcites aged at 333 K, different from what was observed for the model reaction. Now, no signicant difference in the concentration of sites strong enough to catalyze the condensation reaction could be detected so as to compensate for the smaller surface areas of samples MOXX/200(10).

4. Conclusions Chemical analyses of the synthesized hydrotalcites showed that the samples with an Al/(Al + Mg) molar ratio in the synthesis gel equal to 0.33 incorporate less Al than Mg, a trend that was more signicant for the samples aged at 473 K. For samples aged at pH = 10 with Al/(Al + Mg) = 0.20, although hydrotalcite was the main phase formed, hydro-

magnesite (HT0/60(10)) and magnesite (HT20/200(10)) patterns were observed along with those from pure hydrotalcite. For the other samples only pure hydrotalcite was formed. Textural characterization of the Mg,Al-mixed oxides derived from hydrotalcite samples aged at 333 K showed that the BET area decreased with increasing aluminum content, that mesoporous volumes were minima for samples with Al/(Al + Mg) ratio equal to 0.25, that microporous volumes were not very signicant, and that the external areas reect the contribution of the mesoporous system. For the oxides originated from series HTXX/200(10), the BET specic area increased with the increase in the Al content, whereas the mesoporous volume was maximum for sample HT25/200(10). These oxides presented low mesoporosity and the relative importance of microporous volume, which increases with the increase in Al content, was greater than for samples aged at 333 K. SEM showed that the Mg,Al-mixed oxides were formed by aggregates of particles with different sizes. From XPS analyses it was observed that these aggregates were rather homogeneous with a slight segregation of Al in the surface, specially for samples synthesized at pH equal to 13. No correlation between binding energies or oxygen surface composition and the basic properties of the samples determined by retroaldolization of diacetone alcohol was observed. The catalytic evaluation of the Mg,Al-mixed oxides derived from hydrotalcites aged at 333 K showed citral conversions in the range of 2060% and pseudoionone selectivities between 60 and 80%. These values are similar to those reported for the reaction in homogeneous media and conrm the potential use of these solids as heterogeneous catalysts. The work reported here is part of a systematic study that is under way aiming at optimizing the conditions for this reaction. For both series of mixed oxides derived from hydrotalcites aged at 333 K, the highest catalytic activity and pseudoionone yield were obtained with the catalyst with the lower aluminum content. For the series aged at pH = 10, citral conversion decreased with the increase in aluminum content, whereas for the mixed oxides derived from series HTXX/60(13), citral conversion pass through a minimum for the sample with Al/(Al + Mg) = 0.25. Both trends reect the mesoporous characteristics of the samples and their relative basicity as measured by retroaldolization of DAA. Since the inuence of aluminum content on the basic properties was not clear, the textural characteristics seem to be those that best explain the observed trends. On the other hand, neither the Al content nor the pH of aging of the hydrotalcite precursors had signicant inuence on reaction selectivity. For the samples of the series HTXX/200(10), the conversions were signicantly lower than those of the corresponding samples aged at 333 K. These results can also be explained by the textural and morphological characteristics of the samples.

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Acknowledgements This work is part of the project V.5 Desarrollo de Catalizadores para Procesos de Qumica Fina that was nanced by CYTEDPrograma Iberoamericano de Ciencia y Tecnologa para el Desarrollo. The authors would like to thank CAPESCoordenao de Aperfeiomento de Pessoal de Nvel Superior, FAPERJFundao de Amparo Pesquisa do Estado do Rio de Janeiro, and UERJ (PROCIENCIA Program) for the nancial support.

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