DOI: 10.1002/cctc.

201600793 Full Papers

Sorption-Enhanced Steam Reforming of Glycerol over Ni–

hydrotalcite: Effect of Promotion with Pt
Karan D. Dewoolkar and Prakash D. Vaidya*[a]

Sorption-enhanced steam reforming of glycerol (SESRG) is results were achieved when Pt-NiCuHTlc was employed at
a promising method for the sustainable production of hydro- T = 823 K: a H2 concentration of 98.7 mol % and adsorption ca-
gen (H2). In this work, composites of Ni and cationic-modified pacity of 1.34 mol CO2/kg sorbent was achieved. When the
hydrotalcite (HTlc) were promoted with Pt, thus resulting in multi-cycle performance was tested for 20 cycles, it was found
two novel hybrid materials Pt-NiMgHTlc and Pt-NiCuHTlc. Ac- that NiMgHTlc, NiCuHTlc, Pt-NiMgHTlc, and Pt-NiCuHTlc were
tivity trials for SESRG were performed in a fixed-bed reactor in stable for 5, 8, 13, and 18 cycles. Finally, a likely reaction path-
the range 673–873 K and it was found that the promotion way for SESRG over the investigated multifunctional materials
with Pt improved H2 purity and multi-cycle durability. The best was proposed.

Introduction

Hydrogen (H2)—a clean energy carrier—can be used in fuel they offer process simplicity, improved performance, and no
cells for efficient electricity production. Its carbon-neutral pro- diffusion limitations.
duction from steam reforming of renewable resources such as As seen in our previous works on SESR of methane[26] and
glycerol has been extensively studied.[1, 2] In particular, catalysts ethanol,[27] bifunctional Ni catalysts derived from hydrotalcite-
based on transition metals and noble metals are widely report- like materials are stable and active and improve H2 production.
ed.[3–8] However, the steam reforming process is energy-con- The high reforming activity of Ni, low cost, and ease of availa-
suming and makes many unwanted byproducts. H2 productivi- bility are renowned.[28] Hydrotalcite-like (HTlc) basic materials,
ty can be improved by sorption-enhanced steam reforming also known as layered double hydroxides, are good candidates
(SESR), which combines the reforming process with the ad- for CO2 sorption. Their general structure is given by [M(1x)2 +
sorptive separation of byproduct CO2 in a single step. Mx3 + (OH)2]x + (An)x/n·m H2O, where M2 + = Mg2 + , Mn2 + , Fe2 + ,
In SESR, pure H2 is produced at low temperature by using Cu2 + , Zn2 + , or Ca2 + , M3 + = Al3 + , Fe3 + , or Ga3 + and An =
mixtures of catalyst and chemisorbent. Thus, less energy is [CO3]2 or Cl .[29] They can be easily regenerated[30] and appro-
consumed and catalyst sintering is lowered. Also, reactors priately modified by the substitution of cations and anions. For
made of expensive materials are avoided. The chemisorbent example, the presence of Cu in the HTlc structure is beneficial
captures byproduct CO2 so that the water–gas shift (WGS) is fa- because it promotes WGS and reduces carbon deposition,[31, 32]
vored, H2 selectivity is enhanced, and subsequent processing and it is not uncommon to employ such cationic-modified
for CO2 separation is precluded. The adsorbent is periodically hybrid materials for the SESR process.[27, 33–35]
regenerated and reused. The process is cheap, simple, efficient, In this work, we applied basic composites of Ni and cationic-
and widely applicable. modified (Mg and Cu) hydrotalcite (HTlc), that is, NiMgHTlc (or
Notably, SESR can be applied for H2 production from glycer- HM1) and NiCuHTlc (or HM2) for SESRG. In addition, we pro-
ol.[9–11] So far, many aspects of sorption-enhanced steam re- moted such composites with Pt to yield two new materials, Pt-
forming of glycerol (SESRG) such as thermodynamics,[12–14] NiMgHTlc (or Pt-HM1) and Pt-NiCuHTlc (or Pt-HM2). For the
sorption kinetics,[15] and reactors[16] have been analyzed. In ad- first time, we employed these novel Pt-based materials for
dition, several experimental investigations using catalyst–sorb- SESRG. Pt is a popular steam reforming catalyst.[1, 4, 28, 36] Its high
ent mixtures[17–23] (e.g., Ni or Co–Ni catalysts mixed with Ca- or activity for CC cleavage is well-known.[1, 34] Here, the influence
Li-containing sorbents) and bifunctional catalytic materials[24, 25] of Pt promotion on the H2 purity, adsorption capacity, and
have also been reported. Bifunctional materials, which merge multi-cycle durability of the investigated composites was inves-
the catalytic and sorption features, are advantageous because tigated in a fixed-bed reactor over a wide range of process
conditions. So far, there is only scarce information on HTlc-
based hybrid materials promoted with noble metals.[28, 37–39]
[a] K. D. Dewoolkar, Dr. P. D. Vaidya
Department of Chemical Engineering
Institute of Chemical Technology
Nathalal Parekh Marg
Matunga, Mumbai 400019 (India)
E-mail: [email protected]

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Results and Discussion Table 1. Crystallite sizes and phases of hybrid materials.

Hybrid material Phase 2q position Crystallite size (d)

Characterization of hybrid materials [8] [nm]
All the characterization details for HM1 and HM2 are reported Pt-HM1 NiO 43.4 10.4
in our previous work.[27] X-ray diffraction (XRD) profiles of the 62.8 8.9
Pt2O 75.3 6.6
Pt-promoted hybrid materials (Pt-HM1 and Pt-HM2) before re-
HTlc 37.3 13.52
duction are shown in Figure 1. The presence of NiO in both Pt-HM2 NiO 37.5 32.4
the hybrid materials is evident from the characteristic peaks at 43.5 30.8
2q = 43.48 and 62.88 for Pt-HM1 and 2q = 37.58 and 43.58 for Pt2O 75.4 15.7
Al2O3 30.5 30.6
Pt-HM2. A typical peak representing the presence of HTlc is
35.9 32.4
seen at 2q = 37.38 for Pt-HM1. The presence of CuAl2O4 as 68.4 25.2
a spinel phase was detected at 2q = 58.68 and 638. CuO was CuO 39.1 28.3
detected at 2q = 39.18 and 49.38. Apart from these peaks, Pt- 49.3 24.6
CuAl2O4 58.6 20.9
HM2 also showed the presence of Al2O3, thus certifying that Al
63 22
remains in its mixed oxide phase. Both these hybrid materials
showed diffraction lines associated with platinum oxide at
2q = 75.38 and 75.48, thereby suggesting the effective disper-
sion of Pt on the surface of the materials. The diffraction pat- which influences activity and sorption capacity, are presented
terns observed for Pt-HM1 and Pt-HM2 were similar to those in Table 2. Both Pt-HM1 and Pt-HM2 displayed higher surface
for HM1 and HM2 obtained in our previous work.[27] These re- areas than HM1 and HM2. Also, the surface area of Pt-HM2
sults are also in good agreement with other works.[40, 41] The was much higher than that reported in a previous work.[40] The
crystallite sizes of the several phases detected from the diffrac- pore volume and pore diameter of the unused and used
tion data were calculated from the Debye–Scherrer equation. hybrid materials are also shown in Table 2.
The phases and crystallite sizes of the various peaks are pre- Scanning electron microscope (SEM) images of fresh Pt-HM1
sented in Table 1. The surface areas of the hybrid materials, and Pt-HM2 are shown in Figure 2 a, b. A highly porous and

Figure 1. XRD patterns for the hybrid materials. Top pattern: Pt-HM2, bottom pattern: Pt-HM1.

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Table 2. Surface area, pore volume, and pore diameter of the fresh and
used (after 20 cycles) hybrid materials.

Hybrid material Surface area Pore volume Pore diameter

[m2 g1] [cm3 g1] [nm]
Fresh Used Fresh Used Fresh Used
HM1 75.4 43.8 0.2 0.17 13.6 14
Pt-HM1 96.5 79.5 0.32 0.29 15.9 16.8
HM2 102 70.3 0.4 0.37 18.4 19.2
Pt-HM2 134.3 114.4 0.57 0.55 19.7 21.2

Figure 3. Glycerol conversion versus temperature plots for HM1 and HM2.
Reaction conditions: P = 0.1 MPa, GHSV = 3600 mL g1 h1, time on
stream = 3 h.

the conversions reported in our work were higher than those

reported earlier.[33, 34]
The influence of temperature on the gas-phase product dis-
tribution was studied and the results at a steady state in the
673–873 K range are shown in Figure 4. Similar to the results
of previous works at T > 673 K,[7, 23, 42, 43] four major products
were formed in the gas phase: H2, CH4, CO2, and CO. With the
rise in temperature, the H2 concentration increased whereas
the CH4 and CO2 content in the product decreased (see Fig-
ure 4 a, b). This is possibly due to the predominance of CH4 re-
forming[44] and reverse water–gas shift (RWGS)[20] at higher
temperatures. Interestingly, both Pt-promoted hybrid materials
displayed improved H2 production compared with the un-pro-
moted materials (see Figure 4 c, d), owing to the high reform-
ing and WGS activity of Pt. The merger of Pt, Ni, and Cu in
a single hybrid material (Pt-HM2) favored the WGS and steam
methane reforming, thereby resulting in the maximum concen-
Figure 2. SEM images of hybrid materials: a) Pt-HM1, b) Pt-HM2.
tration of H2 (93.3 mole %).
At T = 873 K, H2 was formed in lower amounts, whereas the
granular structure was observed. The large size of the particles CO formation increased. Such behavior can be ascribed to the
and their aggregation is evident. These results are in line with dominance of the RWGS reaction at high temperature.[20] No
previous work.[34] carbon deposition was observed under the tested conditions,
The chemical composition of the respective cations and owing to the high steam/carbon (S/C) ratios used. Also, the
anions in the hybrid materials was found by using energy dis- presence of Cu and Mg induces an electronic effect on the
persive X-ray spectroscopy (EDX) analysis. The ratio of Mg active phase of Ni, thereby avoiding carbon formation through
(63.5 mass %) to Al (23.8 mass %) in Pt-HM1 and Cu the Boudouard reaction.[31, 34] In addition, the operating condi-
(65.3 mass %) to Al (22.4 mass %) in Pt-HM2 was about 3. The tions used in this work belong to the coke-free regime, accord-
Ni content in all the samples was approximately 10 mass %. ing to Da Silva and Muller.[14] Higher amounts of methane were
detected in the case of HM1 and HM2, thus suggesting CO
methanation. However, CH4 formation is not desired and a cata-
Catalytic activity of the hybrid materials
lyst with high WGS activity is preferential to reduce the CO
The catalytic activity of HM1 and HM2 for glycerol conversion content of the product. In the liquid product, small amounts of
was investigated in the range 673–873 K. The results are pre- acetaldehyde and acetic acid were detected for the cases of
sented in Figure 3. Both materials facilitated glycerol reforming. HM1 and HM2. This suggests that glycerol undergoes dehydra-
As expected, the increase in temperature resulted in increased tion and subsequent dehydrogenation to form acetaldehyde,
glycerol conversion. At T = 873 K, conversion was maximized which is further converted to acetic acid.[45] At T > 673 K, acetic
(85.4 and 93.3 % for HM1 and HM2). The higher efficacy of acid may decompose over HM1 and HM2 to form CH4 and
HM2 was attributed to the additional presence of Cu. Notably, CO2. In the case of the Pt-promoted hybrid materials, no liquid

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Figure 4. Product gas distribution (mol %) on a dry basis as a function of reaction temperature under steady-state conditions for the hybrid materials a) HM1,
b) HM2, c) Pt-HM1, d) Pt-HM2. Reaction conditions: P = 0.1 MPa, GHSV = 3600 mL g1 h1.

products were detected thus suggesting the complete decom- are readily available for adsorption. CO2 formed during the
position of glycerol through CC bond cleavage to form steam reforming and WGS reactions is effectively adsorbed on
syngas. Thus, the addition of Pt as promoter to the hybrid ma- the surface sites, thereby resulting in enhanced H2 production.
terials improves H2 production and avoids the formation of in- The highest concentrations of H2 are seen in this region owing
termediates. The various reactions that occur in the system to the shift in the equilibrium. As time progresses, a gradual
are: transition into the breakthrough stage occurs. In this region,
the number of sites available for adsorption decreases, thus re-
Glycerol decomposition : C3 H8 O3 ! 3 COþ4 H2 ð1Þ sulting in the increase in CO2 levels. The breakthrough time of
Methanation reaction : CO þ 3 H2 ! 3 CH4 þH2 O ð2Þ the adsorbent (tb) is reached when CO2 is detected in the
outlet stream for the first time. As evident from Figure 5 c, d,
Water  gas shift : CO þ H2 O ! H2 þ CO2 ð3Þ both the Pt-promoted hybrid materials displayed longer break-
Steam methane reforming : CH4 þ H2 O ! CO þ 3 H2 ð4Þ through times (60 min and 75 min). This performance was su-
perior to that reported in previous works.[27, 34] Finally, as the
Overall SESRG : C3 H8 O3 þ 3 H2 O ! 3 CO2 þ7 H2 ð5Þ sorbent gets completely saturated, no further adsorption takes
place. In this post-breakthrough stage, the products reach
their equilibrium values and the system exhibits a catalyst-only
type behavior.
SESRG studies
The efficacy of the hybrid materials can be evaluated in
Breakthrough studies were performed to gain insights into the terms of the adsorption capacity, which was in the order
SESRG process. The dependency of concentrations of H2 and Pt-HM2 > Pt-HM1 > HM2 > HM1 (see Table 3). The results ob-
CO2 on time at T = 773 K and S/C = 9 mol mol1 was studied. tained clearly suggest that Cu-based hybrid materials exhibit
The results are represented in Figure 5. superior adsorption characteristics and produce high amounts
Figure 5 a–d shows the breakthrough curves for the hybrid of H2. In particular, Pt-HM2 gave the highest adsorption capaci-
materials. Sorbent behavior is represented by breakthrough ty of 1.1 mol CO2/kg sorbent in comparison to Pt-HM1
time (tb) and adsorption capacity (Qads). The surface area and (0.84 mol CO2/kg sorbent). These adsorption capacities are
the presence of specific cations in the hybrid material influ- higher than those reported in our previous work.[27] Hybrid ma-
ence the adsorption capacities. Three separate regions are evi- terials retain their sorption capacity until the breakthrough
dent, that is, pre-breakthrough, breakthrough, and post-break- time (see Table 3). After that, this capacity is reduced. The CO2
through. In the pre-breakthrough stage, the adsorbent sites productivity of Pt-HM1 and Pt-HM2 was 0.016 and

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Figure 5. Breakthrough curves for hybrid materials a) HM1, b) HM2, c) Pt-HM1, d) Pt-HM2. Reaction conditions: P = 0.1 MPa, T = 773 K, steam/carbon ratio = 9
mol mol1, GHSV = 3600 mL g1 h1, time on stream = 3 h.

Effect of temperature on SESRG

Table 3. Adsorption capacities of hybrid materials.[a]

Hybrid material Breakthrough time (tb) Qads The effect of temperature on the performance of Pt-HM1 and
[min] [mol CO2 kg1sorbent] Pt-HM2 was investigated in the range 673–873 K. The other re-
HM1 15 0.36
action variables were chosen to be: P = 0.1 MPa and
HM2 30 0.52 S/C = 9 mol mol1. At first, the H2 concentration in the product
Pt-HM1 60 0.84 stream increased with a rise in temperature, owing to the ef-
Pt-HM2 75 1.1 fective separation of CO2 from the product (see Figure 6). The
[a] P = 0.1 MPa, T = 773 K, S/C ratio = 9 mol mol1, GHSV = 3600 mL g1 h1, maximum value was reached at T = 773 K (89.6 mol %) for Pt-
time on stream = 3 h. HM1 and T = 823 K (96 mol %) for Pt-HM2. After that, the H2
concentration decreased with a further increase in tempera-
ture, which was possibly due to the inhibition of carbonation
0.011 mol g1 h1, respectively. The H2 productivity of Pt-HM1 reactions.[27, 46] Thus, the preferred operating temperatures for
and Pt-HM2 was higher (0.13 and 0.16 mol g1 h1) than that of optimum H2 production are 773 and 823 K for Pt-HM1 and Pt-
HM1 and HM2 (0.07 and 0.09 mol g1 h1). The enhancement in HM2, respectively.
H2 production and adsorption capacity can be attributed to
the high surface area, which in turn leads to a higher number
Effect of S/C ratio on SESRG
of adsorption sites for Pt-HM2. Also, the synergistic effect of
the active metals (Pt, Ni, and Cu) along with the smaller crystal The S/C ratio is a crucial parameter that influences the eco-
sizes resulted in higher activity and enhanced H2 production. nomics of SESRG. The role of a high S/C ratio in diminishing
Both HM1 and HM2 showed lower adsorption capacities (0.36 carbon formation is renowned; however, the excess use of
and 0.52 mol CO2/kg sorbent). This suggests that Pt addition to steam results in increased operating costs. Thus, developing
the hybrid materials results in improved H2 production. Despite hybrid materials that resist coking even at low values of S/C
its low surface area, Pt-HM1 adsorbs more CO2 than HM2, appears preferential. The influence of this parameter was inves-
which is possibly due to its improved stability in the presence tigated in the range 3–7.5 mol mol1 at T = 773 K (for Pt-HM1)
of Pt. Next, the influence of reaction variables on the per- and T = 823 K (for Pt-HM2). The other parameter values were:
formance of the Pt-promoted hybrid materials was studied. P = 0.1 MPa and GHSV = 3600 mL g1 h1. The increase in S/C

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Figure 7. Effect of S/C ratios on SER for hybrid materials a) Pt-HM1, b) Pt-
HM2. Reaction conditions: P = 0.1 MPa, T = 773 K (Pt-HM1) or 823 K (Pt-HM2),
GHSV = 3600 mL g1 h1, time on stream = 2.5 h.

Figure 6. Effect of temperature on SER for hybrid materials a) Pt-HM1, b) Pt-

HM2. Reaction conditions: P = 0.1 MPa, steam/carbon ratio = 9 mol mol1,
GHSV = 3600 mL g1 h1, time on stream = 3 h.

ratio resulted in increased H2 concentration in the product gas.

The highest H2 purity was 96.4 mol % H2 (S/C = 6 mol mol1) for
Pt-HM1 and 98.7 mol % H2 (S/C = 4.5 mol mol1) for Pt-HM2.
These results are represented in Figure 7 a, b. Notably, H2 pro-
duction decreased at higher S/C ratios for both materials. Such
behavior is ascribed to the reduced CO2 partial pressure at
high values of S/C, thus resulting in reduced adsorption capaci-
ty.[30] Even so, it can be concluded that the Pt-promoted hybrid
materials are efficient for H2 production at lower S/C ratios.
Figure 8. Effect of sorbent mass fraction on SESRG for hybrid materials. Re-
action conditions: P = 0.1 MPa, T = 773 K (Pt-HM1) or 823 K (Pt-HM2), steam/
carbon ratio = 6 mol mol1 (for Pt-HM1) and 4.5 mol mol1 (for Pt-HM2), time
Effect of sorbent mass fraction on SESRG on stream = 2.5 h.

Knowledge of the optimum sorbent mass fraction for SESRG is

essential. Both adsorption capacity and H2 yield are dependent
Cyclic stability tests
on the mass of hybrid material. The effect of sorbent mass
fraction on H2 yield was investigated in the range 0.09– The development of highly stable sorbents is a prerequisite for
0.27 kg h mol1 at P = 0.1 MPa. Pt-HM1 was tested at 773 K the successful applications of SESRG. Sorbents that display
(S/C = 6 mol mol1) whereas Pt-HM2 was studied at 823 K multi-cycle durability and ease of regeneration are desirable. In
(S/C = 4.5 mol mol1). As shown in Figure 8, the highest H2 pro- previous work,[26] we showed that HTlc-like hybrid materials
ductivity was obtained at 0.27 kg h mol1. This corresponds to can be more easily regenerated than Ca-based materials. Treat-
3 g of hybrid material inside the reactor. This behavior is in line ment with excess steam at the reaction temperature is
with previous works.[27, 30] a straightforward method for the regeneration of HTlc-like
hybrid materials.[27, 47] The addition of steam regenerates the
basic HTlc structure and also inhibits coke deposition.[47]
To investigate the cyclic stability of the hybrid materials, 20

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cycles of reaction and regeneration were performed. The reac- promoted materials. Our results were in line with previous
tions were carried out at the optimal conditions for the hybrid works.[30, 35, 48] The cyclic stability of our Pt-promoted hybrid ma-
materials. In the case of our hybrid materials, the regeneration terials was higher than those reported previously.[23]
was carried out by passing excess steam (1.5 to 2 times the re- Towards the end of 20 cycles, the hybrid materials showed
quired flow rate of steam) at the reaction temperature for a decrease in H2 concentrations. This reduction in H2 produc-
20 min. The complete regeneration of CO2 was ascertained by tion can be attributed to the sharp decline in the surface area
its presence in the exit stream from GC analysis. (see Table 2). A plausible reason for the decrease in surface
The concentrations of H2 and CO2 over 20 cycles are report- area may be metal sintering (see Table 4) and reduced porosity.
ed (see Figure 9 a–d). It is evident that both the Pt-promoted The SEM images of the hybrid materials after 20 cyclic tests are
hybrid materials exhibit superior stability of up to 13 (Pt-HM1) shown in Figure 11 a–d. It is noteworthy that our lab-made
and 18 (Pt-HM2) cycles. Contrarily, the un-promoted hybrid hybrid materials displayed encouraging performance in contin-
materials remained stable for five (HM1) and eight (HM2) uous operation cycles.
cycles, respectively. The resilience and ease of regeneration of
our materials make them suitable for real applications. The
Reaction pathway
multi-cycle durability can be attributed to a strong metal–sup-
port interaction, improved CO2 adsorption, and enhanced sta- A schematic representation depicting the plausible SESRG reac-
bility as a result of the presence of Pt. As evident from XRD tion pathway over the investigated hybrid materials is pro-
analysis (Figure 10), the HTlc structure was largely retained posed (see Figure 12).
after the cyclic tests. The marginal rise in crystallite sizes (see The un-promoted hybrid materials HM1 and HM2 are as-
Table 4) suggested that the sintering effect on the Ni and Cu sumed to follow the first pathway. In this route, the adsorbed
particles in the promoted materials was lowered. This suggests glycerol molecule undergoes subsequent dehydration and de-
the role of Pt as a textural promoter in enhancing stability. hydrogenation reactions. This leads to the formation of acetal-
Low intensity peaks for MgAl2O4 were observed for HM1 and dehyde. Then, the adsorbed acetaldehyde undergoes reactions
Pt-HM1. A phase transformation from alumina to boehmite of hydration–dehydrogenation to form acetic acid. This may be
(AlOOH) was seen for all hybrid materials after the cyclic tests. due to the fact that the hybrid material with basic features
In addition, distinct peaks for Cu and CuO along with spinel promotes fast dehydrogenation.[30] Acetic acid undergoes pos-
CuAl2O4 were detected for HM2 and Pt-HM2. Reduced Pt0 sible CC bond cleavage to form CH4, CO, CO2, and H2. The
species with increased crystallite size were obtained for both presence of Ni as an active agent effectively promotes CC

Figure 9. Cyclic stability studies for hybrid materials a) HM1, b) Pt-HM1, c) HM2, d) Pt-HM2. Reaction conditions: P = 0.1 MPa, T = 773 K (HM1 and Pt-HM1) or
823 K (HM2 and Pt-HM2), steam/carbon ratio = 6 mol mol1 (HM1 and Pt-HM1) or 4.5 mol mol1 (HM2 and Pt-HM2), GHSV = 3600 mL g1 h1.

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Figure 10. XRD patterns for the hybrid materials post cyclic tests.

Table 4. Crystallite sizes and phases of hybrid materials after cyclic tests.

Hybrid material Phase 2q position Crystallite size (d)

[8] [nm]
HM1 Ni 43.2 52.6
53.5 20.6
HTlc 37.3 48.5
AlOOH 14.4 72.9
28.1 43.8
38.2 40.4
MgAl2O4 36.1 39
44.4 32
HM2 Ni 43.3 33.7
AlOOH 28.4 65.9
37.2 45.5
Cu 52.4 27.5
75.4 26.6
CuO 35.7 54.4
48.4 33.4
CuAl2O4 63 24.4
Pt-HM1 Ni 43.5 34.7
53.7 26.3
HTc 37.5 41.3
AlOOH 61.8 27.7
75.5 18.9 Figure 11. SEM images of hybrid materials after 20 cyclic tests: a) HM1,
MgAl2O4 32.8 52.6 b) HM2, c) Pt-HM1, d) Pt-HM2.
66.5 15.1
Pt0 39 34.8
68.2 17.2
Pt-HM2 Ni 43.1 36.7 bond rupture.[36] The products CO and CH4 subsequently un-
AlOOH 37.1 41.7 dergo WGS [Eq. (3)] and steam reforming [Eq. (4)] reactions to
78.8 24.6 form CO2 and H2. In the case of HM1, there is a possibility for
Cu 56.6 27.2 methanation of CO [Eq. (2)], leading to higher amounts of CH4
74.9 25.1
CuO 35.6 24 being formed. Finally, the CO2 formed gets adsorbed and pure
36.3 45 H2 is released.
CuAl2O4 62.5 26.6 For the case of the Pt-promoted hybrid materials, the
Pt0 47.6 30.1 second pathway seems feasible. In this pathway, fast
68 25.4
decomposition involving CC bond rupture of glycerol occurs

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Figure 12. Proposed reaction pathways for SESRG.

[Eq. (1)]. This leads to the formation of syngas, which can be Conclusions
confirmed by the absence of liquid byproducts. Such absence
of liquid intermediates in the SER of glycerol is not uncom- Pt-promoted cationic-modified HTlc-based hybrid materials
mon.[21] The adsorbed CO molecule then undergoes a WGS re- were investigated for effective in situ CO2 removal and im-
action to form CO2 and H2. The role of Ni, Mg, and Cu in the proved H2 production. Both the Pt-promoted hybrid materials
promotion of dehydrogenation reactions and CC bond cleav- possessed higher adsorption capacities and cyclic stability in
age is renowned. In addition, the presence of Pt, which has comparison to the un-promoted materials. Optimization of the
high WGS activity and enhanced stability, is beneficial. As no SESRG process was done by evaluating the effect of various re-
significant intermediate byproducts are present, high concen- action variables on the performance of the Pt-promoted
trations of H2 are obtained. In the end, the CO2 thus formed hybrid materials. Amongst all the hybrid materials, Pt-HM2
gets effectively adsorbed, releasing H2 in a way similar to the showed great potential for enhanced H2 production. It gave
previous pathway. In conclusion, the hybrid material design the highest H2 concentrations (above 98 mol %) and adsorption
plays a critical role in the formation of different products in- capacities (1.34 mol CO2/kg sorbent) at its optimal conditions.
volved in the SESRG process. A reaction pathway demonstrating the role of the various
metals in the hybrid materials was suggested. Such novel
multi-functional materials are promising for improved H2
production.
General Remarks
Enhanced H2 production along with satisfactory multi-cycle
performance was achieved by using our Pt-promoted hybrid Experimental Section
materials. From the optimization studies, we can determine Materials
the maximum adsorption capacities for the hybrid materials.
Nickel nitrate, magnesium nitrate, copper nitrate, aluminium ni-
Pt-HM1 gives a maximum adsorption capacity of 1.12 mol CO2/
trate, sodium carbonate, sodium hydroxide, and chloroplatinic acid
kg sorbent at its optimal conditions, that is, T = 773 K, hexahydrate used in the synthesis of the HTlc-based hybrid materi-
P = 0.1 MPa, S/C = 6 mol mol1, tb = 70 min. The breakthrough als were procured from Sigma–Aldrich Pvt. Ltd., Mumbai. Glycerol
time and adsorption capacity for Pt-HM1 was higher than that (purity 99 %), used in all experiments, was also purchased from
reported in previous works.[27, 47] Importantly, Pt-HM2 exhibited Sigma–Aldrich Pvt. Ltd., Mumbai. Gases such as air, H2, and nitro-
the highest adsorption capacity of 1.34 mol CO2/kg sorbent at gen (N2) in cylinders (purity 99.995 %) were acquired from Industrial
its optimal conditions, that is, T = 823 K, P = 0.1 MPa, S/C = Oxygen Company Ltd., Mumbai. Standard calibration gas mixtures
4.5 mol mol1, tb = 90 min. This adsorption capacity was much containing CO, CO2, and CH4 were procured from Chemtron Labo-
ratory Pvt. Ltd, Mumbai.
higher in comparison to an earlier work.[32] The adsorption ca-
pacities of the Pt-promoted materials were much superior to
those for the un-promoted materials. HM1 and HM2 gave ad- Hybrid material synthesis
sorption capacities of 0.65 and 0.9 mol CO2/kg sorbent, respec-
A co-precipitation technique was used to synthesize the HTlc
tively. The addition of a noble metal such as Pt to the hybrid
hybrid materials (NiMgHTlc and NiCuHTlc) according to a method
materials proved successful for enhancing the adsorption ca- previously reported in the literature.[49] Nitrates of the respective
pacity. However, there is scope for improving the multi-cycle aforesaid metal components were used in appropriate amounts.
performance by modifying the anions or addition of suitable The ratio of M2 + /M3 + was selected as 3 so as to have a higher ba-
metals to the HTlc structure. sicity in the material, thereby leading to effective adsorption of

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CO2. An aqueous solution of the metal nitrates was slowly added with a TCD. A Hayesep DB column (length 3.6 m) was used for de-
into a beaker containing an aqueous solution of sodium carbonate tecting H2, CH4, CO2, and CO. In addition, the liquid products were
under continuous stirring at room temperature and constant pH of periodically collected and analyzed by GC employing Tenax
10. The pH of the solution was maintained by using an aqueous column (length 1.9 m). Standard calibration gas and liquid mixtures
solution of sodium hydroxide (2 m). The resulting suspension was were used to determine the product composition. The steam-to-
then kept at room temperature for 24 h. The precipitate thus ob- carbon ratio was equal to 9 mol mol1 unless stated otherwise. The
tained was filtered and washed several times with de-ionized liquid feed rate was varied from 0.25 to 1.25 mL min1.
water to remove any traces of nitrates; this was further confirmed
The conversion of glycerol was defined as follows:
by the brown ring test. The resulting material was dried at 383 K
overnight and ground into a fine powder and calcined at 1073 K
½Glycerolin  ½Glycerolout
for 5 h in air. The addition of platinum (2.5 wt %) to the prepared Glycerol conversion ð%Þ ¼  100 ð6Þ
½Glycerolin
hybrid materials was carried out by the incipient wetness impreg-
nation technique. An aqueous solution of chloroplatinic acid hexa-
hydrate was impregnated over the HTlc material. The resulting ma- where [Glycerol]in and [Glycerol]out represent the inlet and outlet
terial was dried at 383 K for 2 h and calcined at 873 K for 4 h. The molar flow rate (mol h1) of glycerol. The H2 yield was defined as:
material was then crushed and sieved to fine particles with 30–
60 mesh size (0.3–0.6 mm). In all the hybrid materials, 10 wt % ½H2 out
H2 yield ð%Þ ¼  100 ð7Þ
nickel loading was maintained. The hybrid materials were designat- 7  ½Glycerolin
ed as NiMgHTlc (HM1), Pt-NiMgHTlc (Pt-HM1), NiCuHTlc (HM2), and
Pt-NiCuHTlc (Pt-HM2). where [H2]out represents the outlet molar flow rate (mol h1) of H2.
The gas hourly space velocity (GHSV) was defined as:

Characterization of hybrid materials GHSV ¼ Inlet gas flow ðmL min1 Þ=Weight of material ðgÞ ð8Þ
The synthesized hybrid materials were characterized by using sev-
The adsorption capacity of the adsorbents was calculated by using
eral physico-chemical techniques. Crystallinity and textural patterns
the relationship:
were predicted from XRD (X-ray diffraction) data, which were re-
corded by using a Rigaku–miniflex powder diffractometer with CuK
½F  C 0  tb 
(1.54 ) radiation. Nitrogen adsorption–desorption techniques (Mi- Qads ¼ ð9Þ
W
cromeritics ASAP2010) were used to find the BET (Brunauer–
Emmet–Teller) surface area, pore volume, and pore diameter by
BJH (Barrett–Joyner–Halenda) and multipoint BET method. SEM where F is the total molar flow of the feed gas (mol min1), C0 is
(scanning electron microscope) micrographs and EDX (energy dis- the initial CO2 concentration (mole %), W is the mass of the solid
persive X-ray spectroscopy) data were obtained by using a JEOL- adsorbent loaded on the column (g), and tb is the stoichiometric
JSM 6380 LA instrument. time in minutes, determined from the breakthrough curve.

Experimental setup Acknowledgments

A SS-316 tubular fixed-bed down-flow reactor (inner diameter
K.D.D. is thankful to the Department of Science and Technology,
19 mm, outer diameter 25.4 mm, and length 560 mm), purchased
from Chemito Technologies Pvt. Ltd., Mumbai, was used in all ex- Government of India, New Delhi, for providing financial assis-
periments. The setup was supplied with a control panel, tempera- tance (DST-INSPIRE [IF140201]). P.D.V. is grateful to the Technical
ture-controlled furnace, gas chromatograph (GC 8610) unit, and Education Quality Improvement Program (TEQIP) Phase II—
a data acquisition system (Proficy HMI/SCADA-ifax software). The Center of Excellence for Process Intensification (CoEPI) at ICT,
temperature was controlled by using a temperature controller Mumbai.
(West, Germany). A pressure transducer (0–100 bar) enabled the
measurement of pressure with an uncertainty of  0.1 bar.
Keywords: glycerol · hydrogen · sorption-enhanced reforming

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K. D. Dewoolkar, P. D. Vaidya*
&& – &&
Sorption-Enhanced Steam Reforming
of Glycerol over Ni–hydrotalcite:
Effect of Promotion with Pt

Sorption-enhanced steam reforming: (SESR) of glycerol. The hybrid materials

Two novel Pt-promoted cationic modi- demonstrated excellent activity and sta-
fied hydrotalcite-based hybrid materials bility with high purity hydrogen (> 95
were synthesized and tested for the mol %).
sorption-enhanced steam reforming

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