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Applied Catalysis A: General 227 (2002) 181190

Selective etherication of glycerol to polyglycerols over impregnated basic MCM-41 type mesoporous catalysts
J.-M. Clacens , Y. Pouilloux, J. Barrault
Laboratoire de Catalyse en Chimie Organique, UMR 6503, CNRS ESIP, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex, France Received 12 June 2001; received in revised form 19 October 2001; accepted 22 October 2001

Abstract In the general context of the development of the use of agricultural products for non-food applications, and particularly in the eld of the glycerol valorisation (co-product of the triglycerides hydrolysis or methanolysis process), the selective etherication of glycerol was studied. The objective of this work is the direct and selective synthesis, from glycerol and without solvent, of polyglycerols having a low polymerisation degree (di- and/or triglycerol), in the presence of solid mesoporous catalysts. The main part of this study consists in the synthesis and the impregnation of mesoporous solids with different basic elements in order to make them active, selective and stable for the target reaction. The catalytic results obtained show that this impregnation method gives important activity, which must be correlated to an important active species incorporation. Concerning the selectivity of the modied mesoporous catalysts, the best value to (di- + tri-) glycerol are obtained over solids prepared by caesium impregnation. The re-use of these caesium impregnated catalysts does not affect the selectivity to the (di- + tri-) glycerol fraction. In the presence of lanthanum or magnesium containing catalysts, the glycerol dehydration to acrolein is very signicant whereas this unwanted product is not formed when caesium is used as impregnation promoter. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Glycerol etherication; Mesoporous catalysts; Base catalysis; Polyglycerols

1. Introduction Glycerol is mainly a natural product issued from the methanolysis of vegetable oils. In Europe, due to the increasing use of methyl esters as fuel additives, one can expect an increase of glycerol production, which could become a cheaper raw material from chemistry [1]. For example, polyglycerols and specially polyglycerols-esters (PGEs) are gaining prominence
Corresponding author. Present address: Institut de Recherches sur la Catalyse, CNRS, UPR 5401, 2 Av. A. Einstein, 69626 Villeurbanne Cedex, France. E-mail address: clacens@catalyse.univ-lyon1.fr (J.-M. Clacens).

in new products for surfactants, lubricants, cosmetics, foods additives, etc. Indeed PGEs exhibit multifunctional properties and a wide range of formulating options, if it is possible to control; (i) the length of the polyglycerols chain; (ii) the degree of esterication and (iii) the fatty acid molecular weight. These reactions are quite interesting goals for shape-selective catalytic processes. Previous works showed that the selectivity of the rst step is not really controlled and that a mixture of di- to hexaglycerol (linear or cyclic) is obtained. Then it is rather difcult to get a well-dened product and to predict the hydrophiliclipophilic balance (HLB) after esterication. In our laboratory, it was

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 9 2 0 - 6

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Fig. 1. Schematic representation of the etherication of glycerol to polyglycerols.

evidenced that the esterication of glycerol could be selective to -monoglycerides over cationic resins [2]. Nevertheless, polyglycerols and polyglycerols esters as well as acrolein were obtained as main by-products. Moreover, we observed that the modication of the pseudo-pore size of these materials improved the selectivity to PG but acrolein is always obtained over these acid catalysts. In order to obtain a selective formation of di-, tri-, tetra- or polyglycerols, we investigated rst the selective etherication of glycerol (Fig. 1) over solid bases and compared the results to those obtained with Na2 CO3 catalysts. The main objective of this work is to prepare selectively diglycerol or a mixture of (di- + tri-) glycerol by direct etherication of glycerol without use of solvent and without formation of acrolein (Fig. 2) which is mainly obtained by double dehydration of glycerol over acidic sites. In order to achieve this goal, we have prepared and modied new mesoporous basic solids by impregnation of different elements in the MCM-41 type mesoporous materials as shown by Kloetstra et al. [3]. Previous study of this reaction using alkaline exchanged zeolites [4] also showed that caesium

exchanged X zeolite was giving higher selectivity to diglycerol than Na2 CO3 whereas mesoporous catalysts containing various elements (Mg, La, Al, Mn) in the framework did not show better selectivity.

2. Experimental 2.1. Reaction Glycerol etherication is carried out at 533 K in a batch reactor at atmospheric pressure under N2 in the presence of 2 wt.% of catalyst, water being eliminated and collected using a Dean-Stark system. Reagents and products are analysed with a GPC after silylation [5]. Analysis conditions: GPC equipped with an on-column injector, a FID and a polar column (HT5) supplied by SGE (L = 25 m, i.d. = 0.22 mm, thickness of the lm = 0.10 m). Some of the numerous isomers of diglycerol and triglycerol (Fig. 3) are separated (cyclic and linear); among the linear isomers, it is possible to estimate the ,-diglycerol content. Batch processes are generally used in lipochemistry, especially for the esterication and transesterication reactions (except for the preparation of methyl esters).

Fig. 2. Acrolein formation by double dehydration of glycerol.

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Fig. 3. Typical polyglycerols analysis by GC.

Acrolein formation was evaluated from the excess of water produced during the reaction. Different porous solids were used in these studies differing in their surface area, porosity as well as acidobasic properties. 2.2. Preparation and characterisation of the catalysts Impregnated mesoporous materials are prepared as follows: a certain amount (see notation) of alkali, alkaline earth and/or rare earth salt is added to 5 g of pure silica or aluminosilica mesoporous material, prepared (with cetyltrimethylammonium bromide) as previously described [4] and 50 g of methanol. The mixture is agitated at ambient temperature during 2 h, the solvent is then rapidly evaporated under vacuum

and the solid is calcined under air at 723 K overnight at a heating rate of 1 K/min. Notation: element (amount of element impregnated104 mol/g) Al(Si/Al ratio), example: Cs25 Al(20) Nature of the salts: Cs (acetate), Mg (nitrate), La (nitrate), Li (nitrate) and Na (nitrate). The other catalysts used have been described previously [4]. The samples containing different elements in their framework (named incorporated mesoporous materials, notation: Me(n), where n = Si/Me ratio) were prepared according to a procedure developed in our laboratory: we add dropwise 0.2 mol of a solution of sodium silicate (27% SiO2 ) to a solution containing 0.022 mol of NaOH, 23.31 mol of H2 O, an amount of the metal nitrate salt and 0.043 mol of template (cetyltrimethylammonium bromide). The pH is

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adjusted at 10.5 with diluted HCl; then the formed gel is placed in an autoclave at 373 K for 24 h. The resulting solid is ltered, washed with water, dried at 373 K overnight and calcined under air at 823 K overnight at a heating rate of 1 K/min. Some of the solids have been recovered after reaction by ltration using hot water and/or ethanol to dissolve the polyglycerols formed, and re-used without reactivation. Characterisation of the solids was performed using X-ray diffraction, N2 adsorption, transmission electronic microscopy and chemical analysis.

3.2. Mesoporous catalysts: incorporation of elements in their framework Different solids were obtained in changing the element incorporated in the framework of a silico-alumina mesoporous material [4]. These results (Table 2) show that the nature of the element incorporated (Al, Mg, La) in the framework of mesoporous materials modied the activity. On the other hand, we have not observed signicant changes of selectivity between these catalysts and homogeneous catalysts used in the industry. In a second step concerning these direct synthesised materials, we decided to introduce some other elements in the framework of mesoporous materials, such as lithium and caesium. Table 2 also shows that the incorporation of lithium or caesium did not change the activity and the selectivity of the mesoporous materials. 3.3. Impregnation of basic elements in the framework of the mesoporous materials To increase the activity and/or the selectivity, we have impregnated different elements; Li, Cs, La, Na and Mg over mesoporous materials. 3.3.1. Comparison between incorporated and impregnated materials As shown in Table 3, the impregnated material is more active and more selective to (di- + triglycerol) than the incorporated material. 3.3.2. Inuence of the nature of the impregnated element We demonstrated here that other impregnated elements than caesium could be useful in the synthesis

3. Results and discussion In this section we will present results and interpretations obtained with catalysts prepared according to different procedures going from less selective and unstable materials to selective and stable catalysts. 3.1. Homogeneous or modied zeolite catalysts As a resume of the previous study [4], the results reported in the Table 1 shows that Na2 CO3 is a more active and the less selective catalyst; the distribution of polyglycerols being rather large. Cs exchanged zeolites are quite selective to diglycerol and triglycerol while exchanged ZSM-5 are less active and selective. This is the result of the different size of the channels of ZSM-5 solids whatever their Si/Al ratio. In that particular case, the reaction could proceed on the surface of zeolite particles rather than inside the channels. All these experiments also demonstrated that the primary hydroxymethyl groups were the most reactive giving linear and cyclic polyglycerols.
Table 1 Activity and selectivity of homogeneous and modied zeolite catalysts Catalyst (preparation) (Si/Me ratio) Na2 CO3 K/Al2 O3 (5% K) CsX (exchanged) CsX (impregnated) CsZSM-5(28) CsZSM-5(1000) Glycerol conversion (%) after 8 h or (24 h) 94 42 51 36 12 13 () (62) (79) (65) (17) (42)

Selectivity (%) after 8 h or (24 h) Diglycerol 27 83 83 88 94 100 () (65) (62) (73) (92) (80) Triglycerol 31 17 17 12 6 0 () (31) (33) (25) (8) (20) Tetraglycerol 21 0 0 0 0 0 () (3) (4) (1) (0) (0) Others 21 0 0 0 0 0 () (1) (1) (0) (0) (0)

J.-M. Clacens et al. / Applied Catalysis A: General 227 (2002) 181190 Table 2 Etherication of glycerol with different modied mesoporous materials (incorporation method) Element incorporated (Si/element ratio) Al(20) Al(); purely siliceous Mg(20) La(20) Li(20) Cs(20) Conversion (%), 8 h (24 h) 9 12 15 33 15 10 (21) (31) (65) (94) (39) (27) Selectivity (%) 8 h (24 h) Di 74 81 90 82 80 83 (91) (86) (63) (26) (78) (78) Tri 26 19 10 18 10 5 (9) (14) (27) (23) (13) (11) Tetra 0 0 0 2

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Others 0 (24)

(9) (27) (4) (9)

Table 3 Etherication of glycerol in the presence of mesoporous catalysts impregnated and incorporated with Cs Catalysts Conversion (%) 8 h (24 h) Selectivity (%) 8 h (24 h) Di Incorporated Cs(20)Al() Impregnated Cs6 Al(20) 10 (27) 16 (43) 83 (78) 94 (83) Tri 5 (11) 4 (14) Tetra 2 (9) 2 (3) Others 0 (2) 0 (8)

of polyglycerols. The results presented (Figs. 4 and 5) show that a lanthanum impregnated catalyst is the most active but the less selective material. Magnesium impregnated material is not very active but more selective. Nevertheless, these catalysts were not studied further because they favoured glycerol dehydration and the formation of acrolein, an undesirable by-product. Finally, as the caesium impregnated material had both quite good activity and the most important selectivity for the (di- + tri-) glycerol synthesis, it was nally selected.

3.3.3. Inuence of the amount of impregnated element We observe that the catalytic behaviour depends on the amount of Cs impregnated (Figs. 6 and 7). The activity increases with the amount of Cs but the selectivity decreases. Some explanations of these results: the BET surface area of the catalysts were measured and Table 4 shows that the introduction of Cs decreases the BET surface area. This is the result of a structure collapse due to acidobasic interactions between the caesium oxide, formed during the calcination, and the silanol groups

Fig. 4. Activity of mesoporous solids impregnated with different elements.

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Fig. 5. Selectivity of mesoporous solids impregnated with different elements.

Fig. 6. Activity of mesoporous solids impregnated with a different amount of Cs.

Table 4 Chemical and physico-chemical properties of mesoporous solids impregnated with a different amount of Cs Catalysts Specic surface area (BET) (m2 /g) Before impregnation Cs6 Al(20) Cs25 Al(20) Cs50 Al(20) Cs100 Al(20)
a

Chemical analysis of Cs (104 mol/g) Before test 6.4 18.6 28.2 40.7 After test 0.1 3.2 8.9 12.0

X ray diffraction da () Before impregnation 35.7 37.3 36.2 36.2 After impregnation 33.8 No peak No peak No peak

After impregnation 620 66 12 5

838 908 410 410

d = 1.155a0 .

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Fig. 7. Selectivity of mesoporous solids impregnated with different amount of Cs.

and/or Lewis aluminium centres at the mesoporous material surface. This collapsing of the structure could explain the decrease of the selectivity of the reaction but also the more important activity. During this collapsing, the caesium oxides are dissolved in the homogeneous phase where an homogeneous and not selective process took place. Nevertheless, there is one more problem left with that type of catalysts because of the caesium leaching during the reaction. This instability of the caesium is observed whatever the amount of caesium impregnated. One solution could be the synthesis of a more stable coating (CsLaO2 ) as proposed in the literature [3], but the presence of La induces acrolein formation; what we have to avoid. As the structure of the mesoporous catalyst seems to be destroyed after impregnation of the caesium, the selectivity of these catalysts should be lowered. Such a change of the selectivity was not observed in increasing the amount of caesium. At that moment one of the most important point was to know if the structure of the porous material was really destroyed or not. In order to give an answer, some characterisations of the catalysts by transmission electronic microscopy (TEM) coupled with elemental analysis (EDX) were done. Fig. 8 shows that the solid has a mesoporous structure before impregnation. Indeed, we observe on this picture the hexagonal array of the mesoporous

structure. The comparison of Fig. 8 with that of the Fig. 9, which represents an impregnated mesoporous solid, demonstrates that the characteristics of the mesoporous arrangement are still observed (without amorphous domain). So we conclude that, even if the XRD structure is no more observed, due to a decrease of the long range order of the porous system of the solid, there is still a short range ordered solid which can explain the high selectivity obtained with these impregnated mesoporous solids.

Fig. 8. TEM picture of a mesoporous solid (Al(20)).

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Fig. 9. TEM picture of a mesoporous solid impregnated with caesium (Cs25 Al(20)).

Moreover, the EDX analysis shows that wherever the analysis is done, the same amount of caesium is observed. As caesium clusters are not observed over the impregnated solid, it is concluded that the caesium is highly dispersed all over the mesoporous support.

3.3.4. Experiments with different types of caesium catalysts In order to know the role of the leached caesium on the selectivity of the reaction, we decided to compare three different catalysts: an impregnated one, a pure

Fig. 10. Etherication of glycerol, activity of different Cs catalysts [homogeneous (CsOH), heterogeneous (Cs25 Al(20)) and mixed (Al(20) + CsOH)].

Fig. 11. Etherication of glycerol, selectivity of different Cs catalysts [homogeneous (CsOH), heterogeneous (Cs25 Al(20)) and mixed (Al(20) + CsOH)]. Di: diglycerols (, , ), tri: triglycerols ( , , ), di + tri: diglycerols and triglycerols (, , ).

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Fig. 12. Activity of the re-used catalyst.

homogeneous CsOH catalyst and a mixture of mesoporous aluminosilica and caesium hydroxide, all these catalysts containing the same amount of Cs. Figs. 10 and 11 show that the homogeneous CsOH is the most active but the less selective catalyst. What is very important for industrial application, is the (di-+ tri-) selectivity at high conversion (85%). We notice that the impregnated catalyst is very selective (87%) compared to the homogeneous CsOH (63%). This result would mean that the porous impregnated catalyst has a real inuence on the selectivity and lead to a

shape selectivity (selectivity due to the control of the porous structure, i.e. the pore size). 3.3.5. Re-use of the catalysts A catalyst giving a high selectivity to (di- + triglycerol) has been re-use (Cs25 Al(20)R) in order to know if the leaching of caesium was affecting the selectivity of the solid. Figs. 12 and 13 show that the two catalysts (Cs25 Al(20) and Cs25 Al(20)R) have the same selectivity to di- and triglycerol. The activity of the re-use catalyst is lower than that of the initial

Fig. 13. Selectivity of the re-used catalyst.

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one, what can be explain by the different caesium content of the two solids.

Acknowledgements The authors gratefully acknowledged support from the FAIR program of the European Community.

4. Conclusion In this study, we have prepared new impregnated mesoporous materials and observed that the best compromise between activity, selectivity and catalyst leaching was obtained with caesium impregnated on pure mesoporous silica materials. At a conversion of 80%, such catalysts have a very high selectivity to [di- + triglycerol] (90%) compared to that of a homogeneous industrial processes (72%). This result represents a strong improvement of both the selectivity and the yield to [di- + triglycerol] even if the glycerol conversion is quite high (8090%). References
[1] A.J. Kaufman, R.J. Ruebush, in: T.-H. Applewhite (Ed.), Proceedings of the World Conference on Oleochemicals into 21st Century, American Oil Chemist Society, 1991, p. 10. [2] S. Abro, Y. Pouilloux, J. Barrault, in: Proceedings of the 4th Symposium on Heterogeneous Catalysis and Fine Chemicals, Basel, 812 September 1996. [3] K.R. Kloetstra, M. van Laren, H. van Bekkum, J. Chem. Soc., Faraday Trans. 93 (6) (1997) 1211. [4] J.-M. Clacens, Y. Pouilloux, J. Barrault, C. Linares, M. Goldwasser, Stud. Surf. Sci. Catal. 118 (1998) 895. [5] M.R. Sahasrabudhe, JAOCS 44 (1996) 376.