Beruflich Dokumente
Kultur Dokumente
Received 23 March 1997; received in revised form 15 June 1997; accepted 17 June 1997
Abstract
New mixed (Al-Cu)-pillared clays are prepared from a crude bentonite sample (H) (Tunisia deposit) by two discrete
procedures: (a) a classical ‘D’ method by which Al or (Al, Cu) nitrate solutions, hydrolyzed with NaOH, are added to a 2%
clay suspension and (b) a ‘P’ method where the clay powder is directly dispersed in the pillaring solution. Intercalation
reactions are performed at 40°C with an OH/(Al, Cu) molar ratio equal to 1.5 or 2 and an initial atomic percentage of copper
(100 Cu/Al + Cu) of 0, 5 or 10%. Chemical analyses, XRD spectra and surface properties show that clays are intercalated
after calcination at 300°C from both preparation procedures. There is increase of the Al content, dcai and of the BET surface
area, the copper content remains quite low whatever the conditions of preparation. Nevertheless, it seems that the copper
content resulting from the ‘P’ method is higher. During phenol oxidation with hydrogen peroxide (CWPO reaction), the
copper content and the procedure of preparation significantly influence the catalytic activity. Moreover, the very low copper
solubilization proves that copper is certainly associated with alumina at the surface of the catalyst in mixed species
intercalated or/and dispersed on the clay surface. 0 1998 Elsevier Science B.V.
Keywords: Clay; Pillared clay; Mixed (Al-Cu)-pillared clay; Hydrogen peroxide; Phenol oxidation; CWPO reaction
the CWAO is generally performed between 100” and stirrer and a pH electrode. A 100 ml phenol solution
300°C and at a pressure in the l-10 MPa range, and containing 5 x 10e5 M of phenol was placed over a
also that differences in the experimental conditions 0.5 g solid catalyst in the presence of an excess of
could influence the catalyst lifetime. hydrogen peroxide (5 ml/O.5 N or 0.1 N) at atmos-
The WPO process, first adapted from the classical pheric pressure and at 293 K. All the experiments were
Fenton’s reagent allows to obtain efficient oxidation in carried out at the same pH in the 4-5 range.
rather mild conditions (0.1-0.5 Mpa, T < 100°C) with Samples of the reaction medium were analyzed in
a homogeneous Fe’+ catalyst and hydrogen peroxide order to obtain the phenol and the hydrogen peroxide
[7]. More recently, the WPO reactions were studied in conversions. Total organic carbon (TOC) was mea-
different places. Various materials have been proposed sured with a DC 80 Dohrmann equipment. Phenol and
as catalysts for the oxidation of substituted phenols at products of phenol conversion were analyzed with a
atmospheric pressure and T 5 50°C (copper/iron sup- Waters HPLC equipped with a Cis column. The main
ported over alumina or silica [8], iron + ZSM5 zeolite detected products were: catechol, hydroquinone, qui-
[9], supported metallo-porphyrins or metal phtalocya- nones, muconic acid, maleic acid, oxalic acid and
nins [lo]), but few of them could be used due to a lack acetic acid. The H202 concentration was obtained
of stability or a low activity. . . Nevertheless, should by a calorimetric method [ 181 with a UV/Visible
these problems be resolved, the CWPO would find DMS 90 Varian spectrophotometer. The content of
numerous applications. metal ions in the solution was determined from atomic
The aim of the present work was to study a hetero- absorption analysis (Perkin-Elmer 2380).
geneous catalytic WPO of organic compounds using
clay-based catalysts [ll]. To improve the catalytic 2.2. Methods of preparation of Al-and (Al-G)-
efficiency of the process, the idea was to combine a pillared clays, XRD characterization and N2
porous support and active sites for the adsorption of adsorption
organic compounds for the activation of H202 and to
obtain complete oxidation. Natural clays were then (a) A crude Tunisian clay (H) from the Hdidoudi
intercalated or pillared with aluminum or mixed (alu- deposit was used without any purification. This clay is
minum-copper) polyoxocations. In the latter case, an an interstratified illite/smectite bentonite, well char-
increase in both, the specific surface area and the acterized and described in a previous work [ 161. The
number of active sites was expected. Previous works illitic fraction represents ca. 13% of the interstratified
carried out in this domain were mainly concerned with material. The smectic fraction, in sodium-form, has a
the preparation of thermally stable materials which pronounced beidellitic character, quartz being the
can be used in numerous areas and replace other acid main impurity. The average elemental formula deter-
materials like zeolites [12-141. Besides their textural mined from the Na-exchanged purified fraction is:
role, the intercalating species can also act as active Nac.78 K0.15 Lsi7.27 A40.731’” FA12.78 Feo.79 Mgo.5#’
sites for different reactions (oxidation, (CO, Hz), Ozo (OH)+ The CEC of the calcined solid is ca.
functionalization. . .), especially if mixed pillared enti- 75 meq/lOO g and its nitrogen BET surface area is
ties can be prepared and intercalated [ 151. We report in 59 m’/g.
this paper the first results obtained in the oxidation of The pillaring solutions were prepared by dissolving
an aqueous solution of phenol over mixed (Al-Cu)- 0.1 M-Al and Cu nitrates in 0.2 M-NaOH solutions.
pillared bentonites. The hydrolysis molar ratio, R = OH/(Al + Cu), was
1.2 or 2. Solution volumes were adjusted to have an
atomic ratio Cu/(Al+ Cu) of 0, 5 or 10%. The
2. Experimental solutions always remain clear and the pH is around
3.8. Above this pH, the Cut+ ions hydrolyze and
2.1. Oxidation procedure precipitate as hydroxides [ 171.
Two methods were used for pillaring:
Oxidation of the phenol solution was performed in a ?? the usual ‘ex-situ’ method, called ‘D’, where the
thermostated glass reactor of 250 ml equipped with a pillaring solution is slowly added to the clay
.I. Barrault et al./Applied Catalysis B: Environmental 15 (1998) 269-274 271
Table 1
Main characteristics of (Al-Cu)H clays
Preparation method: D P
suspension (2% w/w). This method requires the confirm that Keggin ‘Alis’ species formed in
handling of large volumes of liquid; and the solution migrated into the interlamellar space
. a discrete method, called ‘P’, where the dry clay or/and that these species were formed inside the
powder (2 g) is directly dispersed in the same clay.
amount of a pillaring solution. This method pre- Chemical analyses of the aluminum and copper in
sents some advantages: (i) it decreases the amount the pillared clays show that the copper content of the
of liquid used for the preparation; and (ii) it is mixed pillared clays is generally very low (< 1%) and
easier to reduce the final pillared air-dried catalyst that the alumina content is the same (Table 1). The
to powder. final copper content which does not correspond to the
The pillaring reaction was performed with continu- value expected could indicate a partial incorporation
ously stirring at 40°C. The mixture was left to settle of copper in agreement with previous observations on
for 48 h to reduce the liquid volume, the suspension (Al-Fe)-laponites.
was then washed by five dialysis with distilled water In our previous works, based on H2 TPR, XRD and
until a Cl-free supernatant was obtained, and then 27A1 NMR, we suggested that a fraction of iron was
dried at 80°C. The dry materials were crushed and associated with pillaring species which could mean
calcined for 2 h at 300°C. that a limited isomorphic substitution of aluminum for
(b) Samples are labeled as a function of the initial iron was obtained [15,19]. A similar result could be
conditions and methods of preparation (Table 1). Only obtained with mixed copper systems. However, recent
the daai pillared sample interlamellar distances which ESR studies of Cu centers supported on Al-, Ti- and
give a significant information on the efficiency of the Zr-pillared montmorillonite clays show that cupric
pillaring method appear in Table 1. XRD spectra were ions could form links with the pillars rather than with
obtained by reflexion (Xc,) with a Siemens D500 the silicate sheet and that these materials show superior
diffractometer. catalytic performance in the hydroxylation of phenol
(c) Nitrogen adsorption experiments were per- POI.
formed at liquid nitrogen temperature using a Carlo The influence of the preparation method and the
Erba Sorptomatic 1900 instrument. The samples were copper concentration in the initial pillaring solution on
degassed overnight at 140°C before analysis. the nitrogen BET surface area, microporous volume
and total porous volume values are also listed in
Table 1. Al-pillaring leads to the expected increase
3. Results and discussion of textural parameters. The same increase can be
observed with the mixed (Al-Cu)-pillared clays.
3.1. Characterization of clay catalysts The BET surface area increases from 59 m2/g to
ca. 170 m2/g for the mixed (Al-Cu) clays.
Whatever the preparation method (‘D’ or ‘P’) and These materials, like the (A1a5Cug)HP2 sample,
the ratio R (1.5 or 2), all the crude pillared (inter- have a very good ageing and thermal stability. The
calated samples heated at 300°C) samples with 0,5 or &,i spacing, the surface area and the microporous
10% Cu in the initial pillaring solution, exhibit X-ray volume remain practically unchanged after one-year
dool diffraction peaks ca. 1.7-1.8 nm. These results ageing and heating at 500°C (10 h).
212 J. Barrault et al./Applied Catalysis B: Environmental 15 (1998) 269-274
Time (h)
Fig. 1. Effect of copper on the catalytic properties of pillared clays Fig. 2. Phenol oxidation over (AlLCu)-pillared clays. Effect of
(‘D’ preparation, R = 1.5). Copper content: (A) 0%; (m) 0.16%; preparation procedure: (+) ‘P’ (Cu = 0.39%); (I) ‘D’
and (+) 0.26%. (CLI = 0.16%), (R = 1.5).
3.2. Phenol oxidation oxidation (Fenton-type reaction) than the solid dis-
persed in the solution [ 111.
3.2.1. ‘Blank experiments’
In the absence of a catalyst, no significant phenol 3.2.3. Effect of the preparation process
conversion was observed from ‘blank experiments’ of From Fig. 2, we can see how the procedure of the
phenol oxidation with hydrogen peroxide. preparation (over mixed (Al-Cu)-pillared clays) influ-
When the clay was pillared with pure aluminum ences the phenol conversion. As mentioned in the
oxyhydroxides species and used in phenol oxidation, experimental part, the main difference between the
the activity was very low which, owing to the absence two procedures is that the clay powder is introduced in
of active sites, is quite normal. the ‘AlCuOH’ solution (‘P’), whereas the ‘AlCuOH’
solution is added to the clay suspension (‘D’). When
3.2.2. Effect of copper the preparation is changed, there is a strong modifica-
Since the solids are prepared via the ‘D’ process, tion of the phenol conversion: the ‘P’ solid being much
after the addition of copper to the pillaring solution more active than the ‘D’ solid. In fact, the higher
there is a strong increase of the phenol conversion activity could be due to the higher copper content
(Fig. 1) even if the copper content is low. The plateau (0.39% instead of 0.16%) resulting from the change in
observed for a phenol conversion around 50% is due to the preparation procedure.
the complete hydrogen peroxide conversion. The During the first period of the reaction (8 h) over the
H202 content was checked periodically during the ‘D’ sample, there are primary transformations of
oxidation experiment. Moreover, an increase of phe- phenol into intermediate products, especially light
nol conversion was obtained when fresh hydrogen acids. This is in agreement with the reactional scheme
peroxide was added to the reaction medium. The proposed by Devlin and Harris [21]. The conversion of
analysis of the reaction medium after a 24 h reaction these light acids is generally the rate-limiting step and
indicates that, in both cases, the copper concentration could be favored by the increase of the copper content.
in the solution is under 2 ppm. This result clearly A surface characterization of these materials, now in
shows the increase of the stability of copper when it is progress, will fetch more information on the nature of
introduced via a pillaring solution and mixed hydro- the copper species.
xides. Indeed, when an ‘Alis’-pillared clay was simply
impregnated or exchanged with a copper salt, then 3.2.4. Effect of the hydrolysis
dried and calcined according to the usual procedure In our work, we found that the change of the
for the preparation of heterogeneous catalysts, copper (OH/Al + Cu) ratio from 1.5 to 2, when the solids
was more easily solubilized, its content in the solution were prepared via the ‘D’ process, significantly mod-
after phenol oxidation being ca. 30-40 ppm. These ified the phenol conversion (Fig. 3) even if the copper
species, therefore, are more active in the phenol content was the same. When the materials were
.I. Barrault et al/Applied Catalysis B: Environmental 15 (1998) 269-274 273
0: i----i
0 1 2 3 4 5 6 7
Time (h)
Moreover the change of copper content, even if ]51 P. Gallezot, N. Laurain, P. Isnard, Appl. Catal. B 9 (1996) Lll.
slight, with the modification of the preparation pro- I61 D. Duprez, F. Delanoe, J. Barbier Jr, P. Isnard, G. Blanchard,
Catal. Today 29 (1996) 317.
cedure is a good way for increasing the copper sub-
[71 P. Striolo, H. Debellefontaine, Proc. First Int. Conf. Adv.
stitution and the catalytic properties. Indeed, most Oxidation Technol., London, Ontario, 25-30 June 1994,
important is the large increase in the rate of phenol p. 184.
oxidation into carbon dioxide after the addition of WI A.R. Sanger, T.T.K. Lee, K.T. Chuang, in K. Smith, EC.
copper mainly due to a heterogeneous oxidation (in Sanford (Eds.), Progress in Catalysis, 1992, p. 197.
[91 C. Pulgarin, D. Peringer, P. Alberts, J. Kiwi, J. Mol. Catal. A:
the presence of the pillared clay) rather than to a
95 (1995) 61.
homogeneous Fenton-like oxidation. Work now in UOI (a) C. Labat, J.L. Seris, B. Meunier, Angew. Chem., Ind. Ed.
progress is focused on the surface characterization Engl. 29 (1990) 1471; (b) A. Sorokin, B. Meunier, J. Chem.
of these materials, especially on the characterization Sot., Chem. Commun. 1994, 1799; (c) A. Sorokin, J.L. Seris,
B. Meunier, Science 268 (1995) 1163.
of aluminum-copper interactions.
Cl11 K. Echachoui, Thesis, University of Poitiers, 1996.
WI D.E.W. Vaugham, Catal. Today 2 (1988) 187.
u31 F. Figueras, Catal. Rev. Sci. Eng. 30 (1988) 457.
Acknowledgements [I41 R. Burch, Catal. Rev. Sci. Eng. 2 (1988) 185.
Cl51 F. Bergaya, N. Hassoun, J. Banault, L. Gatineau, Clays
This work has been done within the framework of Minerals 28 (1993) 109.
[I61 N. Frini, M. Crespin, M. Trabelsi, D. Messad, H. van Damme,
the AVICENNE EEC program. The funding thereof is
F. Bergaya, Appl. Clay Sci., (1996) in press.
gratefully acknowledged. 1171 C.F. Baes, R.E. Messmer, the hydrolysis of Cations, Wiley,
New York, 1976.
U81 GM. Eisenberg, Ind. Eng. Chem., 15-5 (1943) 327.
References u91 E Bergaya, J.Barrault, in: I.V. Mitchell (Ed.), Pillared
Layered Structures, 1990, p. 167.
L-w K. Bahranowski, R. Dula, M. Labanowska, E.M. Serwicka,
[l] F. Luck, Catal. Today 27 (1996) 195.
Appl. Spectrosc. 50(11) (1996) 1439.
[2] J. Levee, A. Pintar, Catal. Today 24 (1995) 51.
WI H. Devlin, I. Harris, Ind. Eng. Chem., Fundam. 23 (1984)
[3] S. Imamura, M. Nakamura, N. Kawabata, J. Yoshida, S.
387.
Ishida, Ind. Eng. Chem. Prod. Res. Des. 25 (1986) 34.
WI J.P. Jolivet, ‘De la solution a l’oxyde’, CNRS Ed., 1994.
[4] A. Pintar. J. Levee, J. Catal. 135 (1992) 345.