Applied Clay Science 45 (2009) 213–219

Contents lists available at ScienceDirect

Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Modification of vermiculite by polymerization and carbonization of glycerol to

produce highly efficient materials for oil removal
Miguel de Araújo Medeiros, Maria T.C. Sansiviero, Maria Helena Araújo, Rochel Montero Lago ⁎
Departamento de Química, ICEx, UFMG, Campus-Pampulha, 31270-901 Belo Horizonte, MG, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Impregnation and reaction of glycerol (Gly) on the surface of expanded vermiculite (EV) was used to produce
Received 18 February 2009 a highly efficient absorbent to remove water spilled oils. The vermiculite was impregnated by glycerol
Received in revised form 18 May 2009 containing 1, 2 and 4 mol% of H2SO4 at EV/Gly ratios, i.e. 1/1, 1/2 and 1/3, and heated to 380, 580 and 750 °C.
Accepted 8 June 2009
SEM, TG, BET specific surface area, and Raman analyses indicated that glycerol at 380 °C forms a polymer
Available online 13 June 2009
layer. At higher temperatures, the polymer decomposed to form porous carbon covering the EV surface.
These materials were investigated for the removal of three different oils, i.e. diesel, soybean and engine oil
Keywords:
Vermiculite
spilled on water. The obtained results showed a remarkable increase on oil removal of 600% compared to the
Glycerol non-modified EV.
Polymerization © 2009 Published by Elsevier B.V.
Carbonization

1. Introduction
Vermiculite can be expanded or exfoliated to produce a material with
a highly porous structure (Santos, 1975; Santos and Navajas, 1976; De la
Calle and Suquet, 1988; Bergaya et al., 2006). This vermiculite (EV) floats
on the water surface (Santos, 1975) and shows great potential to remove
spilled oil due to the strong capillary action of the slit shaped pores
(Martins, 1990; Leão et al., 1996; Machado, 2000). Nevertheless, the
hydrophilic nature of the EV surface leads a low oil removal. Several
methods to produce more hydrophobic EV with higher oil adsorption are
based on polymer coating (Folke and Karlsson, 1995; Hluchan, 2002;
Machado et al., 2006a,b), carnauba wax coating (Mysore et al., 2004) and
surface modification (Martins, 1990; Martins, 2005; Bergaya et al., 2006;
Machado et al., 2006a,b).
In this study, glycerol polymerization and carbonization was used
to modify the EV surface. Glycerol is a co-product of the biodiesel
process with an estimated production of 100 ML in 2015, only in Brazil
(Klepacova et al., 2003; Dasari et al., 2005; Karinen and Krause, 2006;
Behr et al., 2008; ANP, 2009). Due to economical and environmental
issues related to this large amount of glycerol produced, novel
applications are strategically important for the biodiesel program all
over the world.
Glycerol can be condensed in the presence of acidic and basic
catalysts to produce ether type oligomers with two up to five units
⁎ Corresponding author. Departamento de Química, Universidade Federal de Minas
Gerais, Belo Horizonte, MG, 31270-901, Brazil. Tel.: +55 31 34095719; fax: +55 31
34095700.
E-mail address: rochel@ufmg.bra (R.M. Lago).
(Seiden and Martin, 1976; Jakobson et al., 1988; Eshuis et al., 1994;
Roberts et al.,1995; Jeromin et al.1998; Barrault et al., 2001; Clacens et al.,
2002; Lemke, 2003; Kraft, 2003; Barrault et al., 2004, 2005; Behr et al.
2008; Medeiros et al., in press). Recent work in our laboratories showed
that glycerol can be further polymerized to a hydrophobic, crosslinked,
highly resistant thermofix resin (Medeiros et al., 2008). This polyglycerol
resin can be pyrolyzed to produce porous carbon.
We describe the behavior of EV covered with polyglycerol (PG) and
EV covered with a porous carbon layer (Fig. 1).
2. Experimental
Glycerol P.A. (272–816 mmol), H2SO4 (2.72–10.88 mmol) and 5 g
of exfoliated vermiculite (EV) were mixed in a glass reactor of 200 mL
equipped with a cold trap to collect the volatiles. The system was
heated in an oven at 30 °C min− 1 up to 380, 580 or 750 °C.
The vermiculite was obtained from Catalão (Brazil). The granulo-
metric fraction used was 0.3–0.6 cm. The approximate composition
obtained by SEM/EDS microprobe was: (Al0.30Ti0.04Fe0.63Mg2.00)
(Si3.21Al0.79)(O10(OH)2Mg0.13Na0.02K0.10(H2O)n). The exfoliation was
carried out by introducing the vermiculite in a quartz tube at 800 °C
for 60 s.
The modified vermiculites were prepared with EV/glycerol (gly)
ratio of 1/1 and were prepared using glycerol containing 1, 2 and
4 mol% H2SO4. These EV/gly samples were heated to 580 °C for 1 h
under N2 and named hereon as G1S1-580, G1S2-580 and G1S4-580
(where G1 = glycerol/EV mass ratio 1/1, S1 sulfuric acid 1 mol%
heated to 580 °C). All the obtained samples were black in color
suggesting the formation of carbonaceous materials.

0169-1317/$ – see front matter © 2009 Published by Elsevier B.V.

doi:10.1016/j.clay.2009.06.008
214 M. de Araújo Medeiros et al. / Applied Clay Science 45 (2009) 213–219
Fig. 1. Modification of vermiculite by catalytic polymerization of glycerol and carbonization.
Fig. 2. Polymerization of glycerol at 280 °C in the presence of 1 mol% H2SO4 monitored
by ESI-MS (detail: glycerol consumption during the reaction).
The modified vermiculites were characterized by: (a) BET specific
surface area (22 cycles N2 adsorption/desorption in an Autosorb 1
Quantachome); (b) powder XRD (Rigaku, model Geigerflex, with Ni
filtered Cu-Kα — λ = 1.54184 Å, 4° min− 1); (c) thermogravimetric
analyses (Shimadzu TGA60 simultaneous DTA–TG), under air and N2
atmosphere with heating rate of 10 °C min− 1; (d) scanning electron
microscopy (SEM) in a Jeol-84A with Au sputtering coated samples
fixed in a carbon tape; (e) Fourier transform infrared (FT-IR) spectros-
copy, using a Perkin Elmer Spectrum GX FT-IR System and (f) Raman
spectroscopy using a Renishaw INVIA, with lens 50× and opening of
0.55. The mercury porosimetry measurements were performed in a
Quantachrome type PoreMaster 60 porosimeter.
The sorption experiments were carried simulating an oil spilling
situation using 15 mL of contaminant, i.e., diesel, soybean and engine oil,
in 100 mL water under stirring. Amounts of 0.5 g of modified vermiculite
were added to the suspension. After 3 min the modified vermiculite was
removed and the excess of the contaminant present on the modified
vermiculite surface was removed in a sieve. The sorbed oil was measured
by weighting. All the sorption tests were carried out in triplicate.
3. Results and discussion
ESI-MS (electrospray ionization mass spectrometry) showed that
at 280 °C oligomerization to di, tri and tetraglycerol and polymeriza-
tion to larger molecules took place during the first hours of reaction
(Fig. 2).
The reaction formed a highly resistant thermofix resin composed
of a crosslinked polyether (Scheme 1).
Scheme 1. Formation of carbon by thermal decomposition of polyglycerol.
At 300–400 °C small amounts of carbon were formed. At higher
temperatures polyglycerol decomposed to porous carbon (Scheme 1).
Pure EV showed flat layers with small fragments on the edges
(Fig. 3). G1S1-580 and G1S2-580 (Fig. 3b–d) had irregular deposits on
the surface with 0.5–4.0 µm long needle-like structures.
SEM images of G1S2-580 and G2S2-580 (Fig. 4b and c) were similar
to those displayed in Fig. 3. However, a porous structure completely
covered the EV layers of G3S2-580 (Fig. 4c and d).
SEM images of G1S1 showed that the needle shaped structures
present at 380 and 580 °C (Fig. 5a–c) were completely destroyed at
750 °C (Fig. 5d).
The specific surface area BET measurements, to samples EV, G1S1-
380, G1S1-580, G1S1-750, G1S2-580, G1S4-580, G2S2-580 and G3S2-
580, indicated that the carbon deposits did not affect significantly the
specific surface area (ca. 3, 2, 4, 4, 4, 5, 3 and 3 m2.g-1, respectively),
especially micro and mesopores. On the other hand, a significant
increase on the macroporosity was observed by mercury porosimetry
for G1S1-580 and G1S1-750 which increased from 1.2 cm3 g− 1 for EV
to 1.7 and 1.9 cm3 g− 1. In fact, visual inspection of the samples after
reaction with glycerol showed further expansion to almost twice the
original volume.
EV showed above 400 °C a small mass gain probably associated
with some oxide formation followed by a mass loss likely related to
the dehydroxylation and carbonate decomposition (Fig. 6).
G1S1-380 showed a mass loss of ca. 10% up to ca. 620 °C likely due
to the decomposition/oxidation of the polyglycerol and mainly to the
oxidation of carbon deposits. Carbon contents estimated from the TG
analyses for the different samples are shown in Fig. 7.
The G1S1 series showed a decrease on the carbon content from 10
to 4% between 380 and 750 °C. The higher temperature should lead to
a further decomposition of polyglycerol to volatile compounds. As
expected, the carbon content decreased from ca. 17 to 4%, when the
Gly/EV ratio decreased from 3:1 to 1:1.
In the XRD diagrams (Fig. 8) the main EV reflection at 25.8°
(d = 0.354 nm) remained present in all samples. Thus, the modifica-
tion of vermiculite did not affect significantly the vermiculite structure.
In general, reflection intensities after modification decreased. Some
small reflections disappeared likely due to the carbon layer.
The EV showed no Raman signal while all modified vermiculites
exhibited a band at ca. 1587 cm− 1 (Fig. 9). As the samples were black,
this band, termed G band related to tangential vibration modes,
suggests the formation of graphitic structures (Reich and Thomsen,
2004). A band at ca. 1386 cm− 1 is likely related to defect carbon
structures, such as amorphous carbon termed band D (Reich and
Thomsen, 2004; Tuinstra and Koenig, 1970; Wang et al., 1990). As the
temperature increased to 580 and 750 °C the intensity of both bands
increased due to enhanced formation of carbon. Although the carbon
formation mechanism is not clear, it is likely related to the thermal
decomposition of polyglycerol. Typical Raman bands of glycerol and
 M. de Araújo Medeiros et al. / Applied Clay Science 45 (2009) 213–219 215

Fig. 3. SEM images: (a) EV; (b) G1S1-580; (c) G1S2-580; (d) G1S4-580.
216 M. de Araújo Medeiros et al. / Applied Clay Science 45 (2009) 213–219

Fig. 4. SEM images: (a) EV, (b) G1S2-580; (c) G2S2-580; (d) G3S2-580.
 M. de Araújo Medeiros et al. / Applied Clay Science 45 (2009) 213–219 217

Fig. 5. SEM images: (a) EV; (b) G1S1-380; (c) G1S1-580; (d) G1S1-750.
218 M. de Araújo Medeiros et al. / Applied Clay Science 45 (2009) 213–219
Fig 6. TG curves in air for EV, G1S1-380, G1S1-580, G1S1-750, G1S2-580, G2S2-580, and
G3S2-580 (in detail DTA).
Fig. 7. Carbon contents determined from TG data.
polyglycerol, between 1000 and 1500 cm− 1, corresponding, i.e. the
bond vibration CCO (1054 and 1115 cm− 1) and vibration of OH
primary groups (1149 and 1109 cm− 1) (Mudalige and Pemberton,
2007; Mendelovici et al., 2000) were not observed. These results
suggest that most of the polyglycerol decomposed.
Fig. 8. XRD diffractograms of EV-580, G1S2-580, G2S2-580, G3S2-580 and G1S1-750.
Fig. 9. Raman spectra of pure EV and G1S1-380, G1S1-580 and G1S1-750.
The results of oil sorption experiments are shown in Fig. 10.
EV absorbed similar amounts of the different oils with approxi-
mately 0.8–1.2 goil/gEV. When EV was impregnated with glycerol (Gly/
EV = 1/1) and heated at 380 °C, the oil sorption capacity increased
almost twice to ca. 2 goil/gEV. As the temperature was increased to 580
and 750 °C oil sorption reached 4–5 goil/gEV. Soybean oil sorption can
be used to compare this efficiency with previous data published. Some
care must be taken in comparing different vermiculites and different
expansion procedures. Nevertheless, the modified EV showed higher
oil sorption compared with several EV based materials in the literature.
For example, soybean sorption has been reported as 2.2 goil/gEV
(Machado et al., 2006a,b), 3.1 goil/gEV (Martins, 1990, commercially
available) and 4.1 goil/gEV (Mysore et al., 2004).
This increase in oil removal (2–5 goil/gEV) is likely related to the
extensive carbonization of the polyglycerol at 750 °C which produced
a much more hydrophobic carbon surface.
As the H2SO4 concentration was increased from 1 to 2 and 4 mol%,
no significant difference of soybean oil sorption was observed (Fig. 11).
Apparently, the carbonization was not strongly affected by the amount
of catalyst when exceeding 1 mol%. Without H2SO4 no reaction took
place and the glycerol was completely lost by evaporation.
As larger amounts of glycerol were impregnated on EV (sample
G2S2-580 and G3S2-580) only a small increase on the oil sorption was
observed. These results clearly indicate that the sorption capacity did
Fig. 10. Effect of temperature on the sorption of soybean, diesel and engine oil.
 M. de Araújo Medeiros et al. / Applied Clay Science 45 (2009) 213–219
Fig. 11. Effect of H2SO4 concentration and Gly/EV ratio on the sorption of soybean oil.
not depend strongly on the glycerol content above the ratio 1/1.
Probably, the sorption capacity depends on the formation of a carbon
layer covering the EV surface and this layer is already formed for the
Gly/EV ratio 1/1.
4. Conclusion
Glycerol in the presence of H2SO4 as catalyst was polymerized on
the expanded vermiculite surface at 380, 580 and 750 °C. This reaction
produced a polymeric layer at lower temperatures which carbonized
at higher temperature. The products showed remarkable oil sorption
capacity of ca. 500% for soybean, engine and diesel, especially after
heating to 750 °C (sample G1S1-750) due to the formation of a
hydrophobic carbon layer.
Acknowledgements
The authors are grateful to CNPq, CAPES, FAPEMIG and UFMG for
the research funds.
References
ANP, 2009. Agência Nacional do Petróleo, Gás Natural e Biocombustíveis. http://www.
anp.gov.br/doc/dados_estatisticos/Producao_de_biodiesel_m3.xls.
Barrault, J., Clacens, J.M., Pouilloux, Y., 2001. Methods for etherifying glycerol, and
catalysts for implementing said methods. WO0198243.
Barrault, J., Clacens, Y., Pouilloux, Y., 2004. Selective oligomerization of glycerol over
mesoporous catalysts. Top. Catal. 27, 137–142.
Barrault, J., Jerome, F., Pouilloux, Y., 2005. Polyglycerol and their esters as an additional
use for glycerol. Lipid Technol. 17, 131–135.
Behr, A., Eilting, J., Irawadi, K., Leschinski, J., Lindner, F., 2008. Improved utilization of
renewable resources: new important derivatives of glycerol. Green Chem. 10, 13–30.
Bergaya, F., Theng, B.K.G., Lagaly, G., 2006. Handbook of Clay Science. Vol. 1, Ed. Elsevier
Science, Amsterdam.
Clacens, J.M., Pouilloux, Y., Barrault, J., 2002. Selective etherification of glycerol to
polyglycerols over impregnated basic MCM-41 type mesoporous catalysts. Appl.
Catal. A: Gen. 227, 181–190.
219
Dasari, M.A., Kiatsimkul, P.P., Sutterlin, W.R., Suppes, G.J., 2005. Low-pressure
hydrogenolysis of glycerol to propylene glycol. Appl. Catal. A: Gen. 281, 225–231.
De la Calle, C., Suquet, H., 1988. Vermiculites. In: Bailey, S.W (Ed.), Reviews in
Mineralogy: Hydrous Phyllosilicates, vol. 19. Mineralogical Society of America,
Washington, p. 725. Chap 12.
Eshuis, J.I., Laan, J.A., Potman, R.P., 1994. Polymerization of glycerol using a zeolite
catalyst. WO9418259.
Folke, E., Karlsson, J., 1995. Method for the protective treatment of mineral material
structures, treatment composition intended for performing of the method and use
thereof. US5782961.
Hluchan, S., 2002. Vermiculita hidrofobizada encapsuladora de petróleo e seu
respectivo processo de obtenção. PI0202900-6.
Jakobson, G., Linke, H., Siemanowski, W., 1988. Process for the preparation of
polyglycerines. EP0296341.
Jeromin, L., Gutsche, B., Bunte, R., Jordan, V., 1998. Process for the production of
diglycerol. US5710350.
Karinen, R.S., Krause, A.O.I., 2006. New biocomponents from glycerol. Appl. Catal. A:
Gen. 306, 128–133.
Klepacova, K., Mravec, D., Hajekova, E., Bajus, M., 2003. Etherification of glycerol. Pet.
Coal 45, 54–57.
Kraft, A., 2003. Method for preparing polymers of glycerol with a saponite catalyst.
US6649690.
Leão, V.A., Martins, J., Machado, L.C.R., Vieira Filho, S.A., 1996. In: Ramachandran, V.,
Nesbitt, L.C. (Eds.), Second International Symposium on Extraction and Processing
for the Treatment and Minimization of Wastes, pp. 305–313.
Lemke, D.W., 2003. Processes for preparing linear polyglycerols and polyglycerol esters.
US6620904.
Machado, L.C.R., 2000. Caracterização de Vermiculitas Visando sua Esfoliação e
Hidrofobização para Adsorção de Substâncias Orgânicas. Dept. de Geologia, Univ.
Fed. de Ouro Preto, Ouro Preto, MSc Thesis.
Machado, L.C.R., Lima, F.W.J., Paniago, R., Ardisson, J.D., Sapag, K., Lago, R.M., 2006a.
Polymer coated vermiculite–iron composites: novel floatable magnetic adsorbents
for water spilled contaminants. Appl. Clay Sci. 31, 207–215.
Machado, L.C.R., Torchia, C.B., Lago, R.M., 2006b. Floating photocatalysts based on TiO2
supported on high specific surface area exfoliated vermiculite for water deconta-
mination. Catal. Commun. 7, 538–541.
Martins, J., 1990. Processo Aperfeiçoado de Hidrofobização de Vermiculita Expandida,
BR. 39004025.
Martins, J., 2005. Processo aperfeiçoado de hidrofobização de silicatos hidratados e
outros minerais hidratados. PI0502450-1.
Medeiros, M.A., Rezende, J.C., Araújo, M.H., Lago, R.M., 2008. Efeito da temperatura no
preparo de polímeros derivados do glicerol, 22° Encontro Regional da Sociedade
Brasileira de Química – MG, Belo Horizonte, AB72-AB72.
Medeiros, M.A., Araújo, M.H., Augusti, R., Oliveira, L.C.A., Lago, R.M., Acid-catalyzed
oligomerization of glycerol investigated by electrospray ionization mass spectro-
metry, J. Braz. Chem. Soc. in press.
Mendelovici, E., Frost, R.L., Kloprogge, T., 2000. Cryogenic Raman spectroscopy of
glycerol. J. Raman Spectrosc. 31, 1121–1126.
Mysore, D., Viraraghavan, T, Jin, Y.C., 2004. Removal of oil by vermiculite. Fresenius
Environ. Bull. 13, 560–567.
Mudalige, A., Pemberton, J.L., 2007. Raman spectroscopy of glycerol/D2O solutions. Vibr.
Spectrosc. 45, 27–35.
Reich, S., Thomsen, C., 2004. Raman spectroscopy of graphite. Phil. Trans. R. Soc. Lond. A
362, 2271–2288.
Roberts, G., Minihan, A.R., Laan, J.A.M., Eshuis, J.J.W., 1995. Polyglycerol production.
WO9521210.
Santos, P.S., 1975. Tecnologia de Argilas Aplicada às argilas Brasileiras. Ed. Edgard
Blucher Ltda, São Paulo.
Santos, P.S., Navajas, R., 1976. Ensaios Preliminares de Piroexpansão de Vermiculita da
Bahia em Forno Piloto Experimental. Rev. Bras. Tecnol. 7, 415–431.
Seiden, P., Martin, J.B., 1976. Process for preparing polyglycerol. US3968169.
Tuinstra, F., Koenig, J.L., 1970. Raman spectrum of graphite. J. Chem. Phys. 53, 1126–1130.
Wang, Y., Alsmeyer, D.C., McCreery, R.L., 1990. Raman spectroscopy of carbon materials:
structural basis of observed spectra. Chem. Mater. 2, 557–563.