Production of Renewable Hydrogen by Aqueous-Phase Reforming of Glycerol Over
Production of Renewable Hydrogen by Aqueous-Phase Reforming of Glycerol Over
Production of Renewable Hydrogen by Aqueous-Phase Reforming of Glycerol Over
Renewable Energy
journal homepage: www.elsevier.com/locate/renene
a r t i c l e i n f o a b s t r a c t
Article history: NieCu catalysts derived from hydrotalcite-like compounds were prepared and evaluated in aqueous-
Received 15 January 2012 phase reforming of glycerol. The catalysts were characterized by chemical composition, textural anal-
Accepted 9 July 2012 ysis, crystalline structure and reducibility. The reaction was carried out in a batch reactor with solution of
Available online 3 August 2012
10 wt.% glycerol, at 250 and 270 C. A maximum glycerol conversion of 60% was achieved at 270 C. In the
gas phase, the H2 selectivity was always higher than 80% and formation of CO was very low (<3%) at
Keywords:
250 C. The addition of Cu decreased the formation of methane. H2 is consumed during the reaction at
Hydrogen
270 C, mainly for Cu-containing catalysts, with simultaneous formation of propylene glycol in the liquid
Glycerol
Aqueous-phase reforming
phase. Acetol, lactic acid and acetaldehyde were also formed in the liquid phase, at both temperatures.
NieCu catalysts Ó 2012 Elsevier Ltd. All rights reserved.
Hydrotalcites
0960-1481/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.renene.2012.07.006
P.V. Tuza et al. / Renewable Energy 50 (2013) 408e414 409
with alternating positively charged mixed metal hydroxide sheets 2.3. Catalytic tests
and negatively charged interlayer anions along with water mole-
cules [12]. Thermal treatments of HTLCs give a stable, high surface The reactions of APR of glycerol were carried out in an autoclave
area, homogeneous mixture of oxides with very small crystal size, batch reactor of 600 mL with 450 rpm of agitation, using 400 mg of
which by reduction results in high metallic dispersion. NieMgeAl catalyst in 250 mL of 10 wt.% glycerol solution. Before the reaction,
mixed oxides prepared from hydrotalcite precursors have been the reactor was purged with He to remove the air inside. The
successfully used as catalysts for various reactions, including catalytic tests were performed at 250 and 270 C, resulting in
reforming and oxidation of methane [13e15] and ethanol reform- autogeneous pressures of 38 and 52 atm, respectively.
ing [9,16]. On the other hand, hydrotalcite-derived CueMgeAl The catalysts were reduced ex situ under 75 mL min1 of 20%H2/
catalysts exhibit high activity for water-gas shift reaction [17]. To N2 up to 1000 C, using a heating rate of 10 C min1.
our knowledge, NieCueMgeAl catalysts derived from hydrotalcites Gas products were analyzed online by gas chromatography (GC-
have not been investigated in APR of glycerol yet. 1000), equipped with a Hayesep D column and TCD. The products
In this context, the objective of this work is to study NieCu detected in the gas phase were H2, CH4, CO2 and CO. The selectivity
catalysts prepared from hydrotalcite precursors in aqueous-phase to these products was calculated based on total moles produced in
reforming of glycerol for hydrogen production. The effect of the the gas phase, without considering water.
Cu loading (0e20 wt%) on the catalytic activity for reforming In the liquid phase glycerol and by-products were quantified by
reaction and hydrogen selectivity was investigated, correlating a Shimadzu HPLC with Aminex HPX 87H column, using 0.005 M
with structural and morphological properties of the catalysts. By- H2SO4 as eluent at 0.6 mL min1, and both UV and refractive index
products formed in liquid phase were identified and the main detectors. Conversion was calculated based on the moles of glycerol
reaction routes were proposed. in the feed. Some liquid by-products were identified by gas
chromatography-mass spectrometry (GCeMS) using a Shimadzu
QP2010 instrument with DB5 column.
2. Experimental
Table 2 above 800 C. The lines of MgO are broader in the sample of lower
Chemical composition, textural characteristics of the calcined catalysts and Ni Mg content, indicating a decrease in the size of the MgO crystal or
particle sizes of the reduced catalysts.
an increase of the Al3þ incorporation in MgO since the ionic radius
Sample NiOa (wt%) CuOa (wt%) MgO SBET VPORE Ni particle Dc of Al3þ (0.54 Å) is smaller than those of Mg2þ (0.65 Å) and Ni2þ
(wt%) (m2/g) (cm3/g) size (nm)b (%) (0.72 Å) [23]. Moreover, the reflections of MgO-solid solution are
Ni 16.7 (20) e 57.8 260.0 0.308 28.8 3.5 shifted towards wider 2q angles than in pure MgO, which also
Ni5Cu 19.1 (20) 5.3 (5) 48.0 211.3 0.480 9.4 10.7
indicates the presence of foreign ions in the oxide lattice [24].
Ni10Cu 19.2 (20) 11.3 (10) 44.8 203.4 0.416 9.8 10.3
Ni20Cu 19.4 (20) 22.5 (20) 33.7 118.4 0.325 14.3 7.0 XRD analysis of the catalysts was also carried out after reduction
a
at 1000 C (Fig. 1 C). The reduction caused the formation of Ni0, with
The values in parentheses are nominal values.
b
Calculated by the Scherrer equation using (200) plane of Ni.
reflections at 44.5 , 51.9 and 76.4 (JCPDS 4e850), showing that ex
c
Dispersion of Ni metal particles. situ activation was successful in reducing the active nickel phase.
Metallic nickel is formed by the reduction of NiO and MgeNieO
solid solution [9]. It can also be observed the formation of spinel
associated with a decrease in the interlayer distance, as suggested phases (MAl2O4 with M ¼ Mg, Ni or Cu) and a small contribution of
by Chmielarz et al. [21]. Cu0 at 43.3 for the sample with higher Cu loading (Ni20Cu).
After calcination at 500 C, the characteristic peaks of HT The Ni particle sizes were calculated by the Scherrer equation,
structure disappear and XRD patterns (Fig. 1 B) show the presence using the peak at 2q ¼ 51.9 , which corresponds to the (200) plane
of poorly crystallized MgO periclase phase at 42.9 and 62.3 (JCPDS of Ni fcc. The results are shown in Table 2, together with the cor-
45e946). The presence of NiO is only evidenced by the very small responding Ni dispersion, estimated according to Anderson [25].
peak at 37.2 , since the other peaks of this phase are overlapped The use of HTLC precursors results in high dispersion of metal
with MgO at 43.3 and 62.9 (JCPDS 47e1049). On the other hand, particles, as already observed by other authors [9,23,26]. The
whatever the Cu content, no crystalline Cu-containing phase addition of copper greatly improved the Ni dispersion, which can
evolved and no well-defined spinel phase was noted. These results be related to the increased reducibility of nickel in presence of
indicate that most of Ni, and Cu and Al oxides are well dispersed in copper, as will be shown by TPR.
MgO matrix, forming a solid solution, in accordance with the Textural characteristics of the as-synthesized samples (Table 1)
literature [18,20]. Kovanda et al. [22] reported that CuAl2O4 spinel showed that samples with higher amount of copper have larger BET
was formed from CueMgeAl hydrotalcites only after calcination surface areas, which is coherent with previous results [17].
Fig. 1. XRD patterns of the as-synthesized HTLCs (A), and catalysts after calcination (B) and reduction (C). Phases: D MgO, þ NiO, Ni, A spinel phases, O Cu0.
P.V. Tuza et al. / Renewable Energy 50 (2013) 408e414 411
Fig. 3. Glycerol conversion as a function of time on stream for aqueous-phase reforming of 10 wt.% glycerol solution at 250 (A) and 270 C (B).
CO þ H2O / CO2 þ H2 (2) López et al. [34]. Acetol is produced by dehydration of glycerol
(Eq. (6)), as already observed by many authors
CO þ 3H2 / CH4 þ H2O (3) [31,35e37]. Acetaldehyde can be formed from dehydration of
ethylene glycol (Eq. (8)), which is produced by decarbonylation/
CO2 þ 4H2 / CH4 þ 2H2O (4) dehydrogenation of glycerol (Eq. (7)) [35]. Lactic acid was
produced at higher concentrations (11e13 g L1) than acetol
The main products detected in liquid phase for APR of glycerol (2e4 g L1) or acetaldehyde (4e5 g L1). The high
at 250 C were lactic acid, acetol (hydroxyacetone) and concentration of these by-products shows that formation of H2
acetaldehyde. The formation of lactic acid is related to dehy- by these side reactions is significant, justifying the high H2
drogenation of glycerol (Eq. (5)), as proposed by Ramirez- selectivities (Fig. 4).
Fig. 4. H2, CH4, CO2 and CO selectivities as a function of time on stream for aqueous-phase reforming of 10 wt.% glycerol solution at 250 C with (a) Ni, (b) Ni5Cu, (c) Ni10Cu and
(d) Ni20Cu catalysts.
P.V. Tuza et al. / Renewable Energy 50 (2013) 408e414 413
Fig. 5. H2, CH4, CO2 and CO selectivities as a function of time on stream for aqueous-phase reforming of 10 wt.% glycerol solution at 270 C with (a) Ni, (b) Ni5Cu, (c) Ni10Cu and
(d) Ni20Cu catalysts.
414 P.V. Tuza et al. / Renewable Energy 50 (2013) 408e414
its lower Ni dispersion. Ni5Cu catalyst presented the highest H2 [18] Rodrigues ACC, Henriques CA, Monteiro JLF. Influence of Ni content in
physico-chemical characteristics of Ni, Mg, Al-hydrotalcite like compounds.
selectivity at 250 C, with the smallest amount of CO and CH4.
Mater Res 2003;6:563e8.
However, this catalyst provided the least desirable performance at [19] Dussault L, Dupin JC, Dumitriu E, Auroux A, Guimon C. Microcalorimetry, TPR
270 C because of low conversion and almost total consumption of and XPS studies of acidebase properties of NiCuMgAl mixed oxides using
hydrogen. The consumption of H2 is related to hydrogenation of LDHs as precursors. Thermochim Acta 2005;434:93e9.
[20] Kannan S, Dubey A, Knozinger H. Synthesis and characterization of CuMgAl
acetol, formed by dehydration of glycerol, producing propylene ternary hydrotalcites as catalysts for the hydroxylation of phenol. J Catal
glycol. Lactic acid and acetaldehyde were also formed in liquid 2005;231:381e92.
phase, besides small traces of heavier by-products. [21] Chmielarz L, Kustrowski P, Rafalska-qasocha A, Majda D, Dziembaj R. Catalytic
activity of CoeMgeAl, CueMgeAl and CueCoeMgeAl mixed oxides derived
from hydrotalcites in SCR of NO with ammonia. Appl Catal B 2002;35:
Acknowledgments 195e210.
[22] Kovanda F, Jirátová K, Rymes J, Kolousek D. Characterization of activated Cu/
Mg/Al hydrotalcites and their catalytic activity in toluene combustion. Appl
The authors thank Núcleo de Catálise/COPPE/UFRJ for providing Clay Sci 2001;18:71e80.
the FRX, BET analysis and also GCeMS; Angela Rocha for helping [23] Takehira K, Shishido T, Wang P, Kosaka T, Takaki K. Autothermal reforming of
CH4 over supported Ni catalysts prepared from MgeAl hydrotalcite-like
with GCeMS; and CNPq for the financial support granted to carry anionic clay. J Catal 2004;221:43e54.
out this work. [24] Fornasari G, Gazzano M, Matteuzzi D, Trifiró F, Vaccari A. Structure and
reactivity of high-surface-area Ni/Mg/Al mixed oxides. Appl Clay Sci 1995;10:
69e82.
References [25] Anderson JR. Structure of metallic catalysts. London: Academic Press; 1975.
[26] Shishido T, Sukenobu M, Morioka H, Furukawa R, Shirahase H, Takehira K. CO2
[1] Dunn S. Hydrogen futures: toward a sustainable energy system. Int J reforming of CH4 over Ni/MgeAl oxide catalysts prepared by solid phase
Hydrogen Energy 2002;27:235e64. crystallization method from MgeAl hydrotalcite-like precursors. Catal Lett
[2] Huber GW, Iborra S, Corma A. Synthesis of transportation fuels from biomass: 2001;73:21e6.
chemistry, catalysts, and engineering. Chem Rev 2006;106:4044e98. [27] Ashok J, Subrahmanyam M, Venugopal A. Hydrotalcite structure derived
[3] Adhikari S, Fernando SD, Haryanto A. Hydrogen production from glycerol: an NieCueAl catalysts for the production of H2 by CH4 decomposition. Int J
update. Energy Convers Manage 2009;50:2600e4. Hydrogen Energy 2008;33:2704e13.
[4] Cortright RD, Davda RR, Dumesic JA. Hydrogen from catalytic reforming of [28] Chmielarz L, Kustrowski P, Rafalska-qasocha A, Dziembaj R. Influence of Cu,
biomass-derived hydrocarbons in liquid water. Nature 2002;418:964e7. Co and Ni cations incorporated in brucite-type layers on thermal behaviour of
[5] Davda RR, Shabaker JW, Huber GW, Cortright RD, Dumesic JA. A review of hydrotalcites and reducibility of the derived mixed oxide systems. Thermo-
catalytic issues and process conditions for renewable hydrogen and alkanes chim Acta 2003;395:225e36.
by aqueous-phase reforming of oxygenated hydrocarbons over supported [29] Manfro RL, Costa AF, Ribeiro NFP, Souza MMVM. Hydrogen production by
metal catalysts. Appl Catal B 2005;56:171e86. aqueous-phase reforming of glycerol over nickel catalysts supported on CeO2.
[6] Shabaker JW, Davda RR, Huber GW, Cortright RD, Dumesic JA. Aqueous-phase Fuel Process Technol 2011;92:330e5.
reforming of methanol and ethylene glycol over alumina-supported platinum [30] Huber GW, Shabaker JW, Dumesic JA. Raney NieSn catalyst for H2 production
catalysts. J Catal 2003;215:344e52. from biomass-derived hydrocarbons. Science 2003;300:2075e7.
[7] Shabaker JW, Huber GW, Cortright RD, Dumesic JA. Aqueous-phase reforming [31] Wawrzetz A, Peng B, Hrabar A, Jentys A, Lemonidou AA, Lercher JA. Towards
of ethylene glycol over supported platinum catalysts. Catal Lett 2003;88:1e8. understanding the bifunctional hydrodeoxygenation and aqueous phase
[8] Soares RR, Simonetti DA, Dumesic JA. Glycerol as a source for fuels and chemicals reforming of glycerol. J Catal 2010;269:411e20.
by low-temperature catalytic processing. Angew Chem Int Ed 2006;45:3982e5. [32] Grenoble DC, Estadt MM, Ollis DF. The chemistry and catalysis of the water
[9] Cruz IO, Ribeiro NFP, Aranda DAG, Souza MMVM. Hydrogen production by gas shift reaction: 1. The kinetics over supported metal catalysts. J Catal 1981;
aqueous-phase reforming of ethanol over nickel catalysts prepared from 67:90e102.
hydrotalcite precursors. Catal Commun 2008;9:2606e11. [33] Vannice MA. The catalytic synthesis of hydrocarbons from H2/CO mixtures
[10] Behr A, Eilting J, Irawadi K, Leschinski J, Lindner F. Improved utilisation of over the group VIII metals: V. The catalytic behavior of silica-supported
renewable resources: new important derivatives of glycerol. Green Chem metals. J Catal 1977;50:228e36.
2008;10:13e30. [34] Ramírez-López CA, Ochoa-Gómez JR, Fernández-Santos M, Gómez-Jiménez-
[11] Shabaker JW, Huber GW, Dumesic JA. Aqueous-phase reforming of oxygen- Aberasturi O, Alonso-Vicario A, Torrecilla-Soria J. Synthesis of lactic acid by
ated hydrocarbons over Sn-modified Ni catalysts. J Catal 2004;222:180e91. alkaline hydrothermal conversion of glycerol at high glycerol concentration.
[12] Cavani F, Trifiró F, Vaccari A. Hydrotalcite-type anionic clays: preparation, Ind Eng Chem Res 2010;49:6270e8.
properties and applications. Catal Today 1991;11:173e301. [35] King DL, Zhang L, Xia G, Karim AM, Heldebrant DJ, Wang X, et al. Aqueous
[13] Basile F, Basini L, D’Amore M, Fornasari G, Guarinoni A, Matteuzzi D, et al. Ni/ phase reforming of glycerol for hydrogen production over PteRe supported
Mg/Al anionic clay derived catalysts for the catalytic partial oxidation of on carbon. Appl Catal B 2010;99:206e13.
methane: residence time dependence of the reactivity features. J Catal 1998; [36] Miyazawa T, Kusunoki Y, Kunimori K, Tomishige K. Glycerol conversion in the
173:247e56. aqueous solution under hydrogen over Ru/C þ an ion-exchange resin and its
[14] Tsyganok AI, Tsunoda T, Hamakawa S, Suzuki K, Takehira K, Hayakawa T. Dry reaction mechanism. J Catal 2006;240:213e21.
reforming of methane over catalysts derived from nickel-containing MgeAl [37] Pompeo F, Santori G, Nichio NN. Hydrogen and/or syngas from steam
layered double hydroxides. J Catal 2003;213:191e203. reforming of glycerol: study of platinum catalysts. Int J Hydrogen Energy
[15] Fonseca A, Assaf EM. Production of the hydrogen by methane steam reforming 2010;35:8912e20.
over nickel catalysts prepared from hydrotalcite precursors. J Power Sources [38] Dasari MA, Kiatsimkul PP, Sutterlin WR, Suppes GJ. Low-pressure
2005;142:154e9. hydrogenolysis of glycerol to propylene glycol. Appl Catal A 2005;281:
[16] Comas J, Dieuzeide ML, Baronetti G, Laborde M, Amadeo N. Methane steam 225e31.
reforming and ethanol steam reforming using a Ni(II)eAl(III) catalyst [39] Nakagawa Y, Tomishige K. Heterogeneous catalysis of the glycerol hydro-
prepared from lamellar double hydroxides. Chem Eng J 2006;118:11e5. genolysis. Catal Sci Technol 2011. http://dx.doi.org/10.1039/c0cy00054j.
[17] Ferreira KA, Ribeiro NFP, Souza MMVM, Schmal M. Structural transformation [40] Meher LC, Gopinath R, Naik SN, Dalai AK. Catalytic hydrogenolysis of glycerol
of CueMgeAl mixed oxide catalysts derived from hydrotalcites during shift to propylene glycol over mixed oxides derived from a hydrotalcite-type
reaction. Catal Lett 2009;132:58e63. precursor. Ind Eng Chem Res 2009;48:1840e6.