Catal Surv Asia (2011) 15:2536 DOI 10.

1007/s10563-010-9105-5

Hydrogen Production by Catalytic Reforming of Liquid Hydrocarbons

Dong Ju Moon

Published online: 6 November 2010 Springer Science+Business Media, LLC 2010

Abstract In this review, we are reporting the catalytic reforming of liquid hydrocarbon fuels carried out in our research group, covering the catalytic reforming of isooctane and toluene as surrogate of gasoline, gasoline fuel processor system and steam reforming of n-hexadecane and decahydronaphthalene, main constituents of diesel. The commercial ICI reforming catalyst is prone to be poisoned by sulfur contained in iso-octane. We investigated various supported transition metal formulations and developed Ni/ Fe/MgO/Al2O3 (KIST-5) catalyst with prolonged catalytic stability ([760 h), higher activity and sulfur tolerance ability over commercial ICI and HT catalysts for ATR reaction of iso-octane. We found that the concentration of CO can be reduced to \1,800 ppm by the gasoline fuel processor system charged with KIST-5 reforming catalyst, commercial HTS catalyst and KIST PtNi/CeO2 LTS catalyst. The addition of Rh metal to spc-Ni/MgAl catalyst as promoter was found to be very effective in inhibiting the deactivation of spc-Ni/MgAl catalyst by sintering of reduced Ni metal at high temperature during steam reforming of n-hexadecane. A 0.3 wt% Rh loading on spcNi/MgAl catalyst was optimized to have the best performance for steam reforming of n-hexadecane among the prepared catalysts. The addition of Rh to spc-Ni/MgAl catalyst also restricted the deactivation of the catalyst due to carbon formation at high reaction temperature. In view point of prolonged stability and higher activity, these developed reforming catalysts have a good scope in the

reforming process of gasoline and diesel for hydrogen station and fuel processor system applications. Keywords Catalytic reforming Hydrogen production Fuel processor system Hydrogen station Steam reforming Gasoline Iso-octane Toluene N-hexadecane

1 Introduction Hydrogen has the potential to offer cleaner, more-efcient alternatives to the combustion of gasoline and other fossil fuels. Though transition from a petroleum-based to a hydrogen-based economy is expensive, in the long run it is affordable. A total conversion to a hydrogen economy society is possible in the near future. Limited petroleumbased fuels resources, rising natural gas prices, dependency on other countries for fuel, green house gas emissions are the driving forces to shift towards hydrogen economy society. Hydrogen economy will revolutionize the world in energy crises. It is eco-friendly and produces no air pollutants, green house gases when used in the fuel cells. It can be produced using diverse domestic resources including fossil fuels such as natural gas, liquid hydrocarbons and coal, nuclear, biomass and other renewable energy technologies, such as solar, wind and hydro-electric power [1]. Most of the hydrogen is now produced as an industrial scale by the process of steam reforming of natural gas or as a byproduct of petroleum rening and chemicals production. Generally, it is produced by the following processes such as steam reforming (SR), partial oxidation (POX) and autothermal reforming (ATR) of hydrocarbons. Steam reforming uses thermal energy to separate hydrogen from the carbon components of hydrocarbons,

D. J. Moon (&) Clean Energy Center, Korea Institute of Science and Technology (KIST), 39-1, Hawolgok-dong, Sungbuk-ku, Seoul, Republic of Korea e-mail: djmoon@kist.re.kr

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and involves the reaction of these fuels with steam on catalytic surfaces. The rst step of the reaction is the decomposition of the fuel into hydrogen and carbon monoxide, followed by water gas shift reaction (WGS) of the carbon monoxide and water to carbon dioxide and hydrogen [24]. Steam reforming is an endothermic process, hence some of the fuel must be burned and the heat transferred to the reformer via heat exchangers. Partial oxidation involves [5] the reaction of oxygen with fuel to produce H2 and CO when the oxygen-to-fuel ratio is less than that required for total combustion. Partial oxidation can be conducted with a catalyst (catalytic partial oxidation) or without a catalyst (non-catalytic partial oxidation). The reaction rates are much higher for partial oxidation than for steam reforming, but the H2 yield per carbon in the fuel is lower. Autothermal reforming involves the reaction of oxygen, steam and fuel to produce H2 and CO, and can be viewed as a combination of partial oxidation and steam reforming. This reforming step generates gases which contain 812% CO besides H2, CO2, CH4 and air. This CO must be converted with the help of steam to CO2 and hydrogen via WGS reaction to enrich the hydrogen [612]. Hydrogen produced by catalytic reforming of hydrocarbons such as methane, methanol, ethanol, liquid petroleum gas (LPG), gasoline, kerosene, diesel and other oil derivatives can be used as fuel for fuel cell [1316]. Hydrogen contains less energy than gasoline or diesel on a per-volume basis, so it is difcult to store enough hydrogen onboard a vehicle to travel long distance. The lack of an infrastructure for the production and distribution of H2 has stimulated research in fuel processing, in particular, the development of fuel processors for reforming of infrastructured fuels such as natural gas, liqueed petroleum gas, gasoline and diesel at the point of applications. In our previous review [1720], the hydrogen production by catalytic reforming of gaseous hydrocarbons has been reviewed. Liquid fuels can be used as the energy carriers in many applications, especially residential power generation (RPG) systems in remote areas and the auxiliary power units (APU) based on solid oxide fuel cell (SOFC) systems. Especially, diesel is an attractive fuel for the production of hydrogen by reforming because of its high gravimetric and volumetric hydrogen density and wellestablished delivery infrastructure. Ahmed et al. [21] discussed the advantages of using liquid hydrocarbons for portable and stationery fuel processors. The main problems associated with the reforming of diesel are related to catalyst degradation during the reaction due to the harsh operating conditions such as high temperatures and high H2O/C ratios, the necessary to obtain high yield of hydrogen. Degradation may be due to poisoning of the catalysts by sulfur, thermal sintering and extensive carbon

formation due to the low H/C ratio and the high molecular weight of the molecules present in diesel fuel. Recently, proton exchanged membrane (PEM) fuel cells operating with hydrogen from hydrocarbon reforming technologies are being increasingly accepted as the most appropriate power source for future generation vehicles. It has polymer electrolyte and operates at 80 C with hydrogen as reformate, prepared externally. For PEM fuel cells, the concentration of CO should be reduced as it poisons an anode catalyst. Solid oxide fuel cell is also gaining interest, though the operating temperature is high (700900 C). It has ceramic electrolyte and can use H2/CO2/CH4 reformate as fuel which can be reformed internally or externally. It is tolerant to sulfur and there is no CO poison effect as observed in PEM fuel cells. Presently, steam reforming of hydrocarbons, especially of methane is the largest and generally the most economical way to make hydrogen and has been reported by many researchers [1, 16, 17, 21]. However, little has been reported on ATR of liquid hydrocarbon fuels [22]. The lack of infrastructure for hydrogen production and distribution as well as the current cost of hydrogen from nuclear or renewable energy has led the car manufacturers and researchers to consider on-board generation from various hydrocarbons. ATR of n-octane was applied [23] recently for developing on-board reformers for automotive applications. Ni-based catalysts had moderate activity in this reaction than noble metal catalysts which also get deactivated under reaction conditions [24]. A bimetallic NiPd catalyst show high activity with good stability. Springmann et al. [25] tested Rh-based catalyst deposited on metal sheets in a monolithnic reactor for steam reforming and ATR of liquid hydrocarbons such as iso-octane, hexane and toluene. Very little experimental data is available on liquid hydrocarbon. Krumpelt et al. [26] also reported data on pilot scale reformer of iso-octane. Catalytic partial oxidation of higher hydrocarbons such as iso-octane, n-decane and diesel fuel over Rh-coated monoliths with high yield of H2 and CO (*80%) in autothermal millisecond reactors have been reported [2729]. Addition of steam to the catalytic partial oxidation of diesel and gasoline fuel and their surrogates over precious and transition metal catalysts increase H2 and CO2 and reduce CO levels at contact times typically greater than milliseconds compared to dry conditions [30], suggesting water gas shift and steam reforming occur with the addition of steam to the reactor. In this work, the catalytic reforming of liquid fuels carried out in our research group will be reviewed covering the catalytic reforming of iso-octane and toluene as a surrogate of gasoline, the steam reforming of n-hexane as a surrogate of diesel.

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Hydrogen Production From Liquid Hydrocarbons

27

2 Features of Catalysts Generally, the composition of reforming catalyst typically comprise of transition metals (Ni, Co, Fe, etc.) or noble metals (Pt, Pd, Rh, etc.) deposited or incorporated into carefully engineered supports such as thermally stabilized alumina, doped alumina with promoters to accelerate carbon vaporization [31] and mixed metal oxides [32]. 2.1 Hydrotalcites Anionic clay-based hydrotalcites-like materials have been extensively studied [3336] in last few decades for various catalytic applications such as steam reforming, base-catalyzed organic transformations, alcohol synthesis, alkylation of phenol with alcohols, selective oxidation, isomerization of allylic compounds and decomposition of nitrogen and sulfur oxides. Hydrotalcite-derived mixed oxides are used as ion exchangers, absorbers, catalysts and catalyst supports. They show interesting properties such as high surface area, phase purity, basic surface properties, structural stability and memory effect [37]. Memory effect allows the reconstruction of the original hydrotalcite structure under mild conditions when contacting the product of the thermal treatment with water solutions containing various anions [37, 38]. Upon calcinations, hydrotalcite-like compounds form a homogeneous mixture of oxides with a very small crystal size, stable to thermal treatment and upon reduction form small and thermally stable metal crystallites [39]. Usually, supported metal catalysts used in the reforming reactions of hydrocarbons are prepared by wet impregnation of different supports. But this method has drawbacks that it is not reproducible, gives inhomogeneity in metal distribution on surface and also ne metal particles tend to sinter at high temperature resulting in the catalyst deactivation [40]. So solid phase crystallization (spc) method giving stable and highly dispersed metal-supported catalyst using pervoskite [41] and hydrotalcite [42] as precursor have been reported. 2.2 Noble Metals Loaded Hydrotalcites The reforming catalysts typically comprise of transition metals (Ni, Co, Fe, etc.) or noble metals (Pt, Pd, Rh, etc.) deposited or incorporated into carefully on the supports [43]. Takehira et al. [44] reported that Pt or Ru doped Nibased catalyst prepared from MgAl hydrotalcite-like anionic clay with citrate method showed high and stable activity for steam reforming of propane. Dreyer et al. [45] studied autotherrmal steam reforming of higher hydrocarbons such as n-decane, n-hexadecane and JP-8 over

Rh-coated monolith. Noble metals, especially Rh catalysts are active in the reforming of hydrocarbons to synthesis gas and also they tolerate sulfur and prevent coke formation unlike conventional nickel catalysts which are necessary properties for any reforming catalyst used for commercial application [46]. Commercial fuels contain sulfur as aromatic rings which cannot be removed completely [47]. Hence noble metals, especially Rh is preferred even though it is costly. Moon et al. [17] reported the steam reforming of nhexadecane, a main constituent of diesel, over noble metal (Rh) modied Ni-based hydrotalcite catalyst. The catalysts were prepared by a co-precipitation and dipping methods. The noble metal modied Ni-based hydrotalcite catalyst displayed higher resistance for the sintering of active metal than Ni-based hydrotalcite catalysts prepared by conventional method. Rh modied Ni-based catalysts showed high resistance to the formation of carbon compared to the Ni-based catalysts. 2.3 Mixed Oxides and/or Noble Metal Loading In the industrial production of H2 by steam-methane reforming, Ni supported on modied alumina or mixed metal oxides are most widely used [48]. Although other Group VIII metals such as Co, Ru, Rh, Pd, Ir and Pt are active for steam reforming. Among these Ni catalysts are preferred because of their lower cost. The Ni catalysts are prone to deactivation due to sulphur poisoning and coke formation. Hence, the interest in using Rh-based reforming catalysts for steam reforming is increasing, in spite of their initial higher cost as they tend to inhibit coke formation [49]. The role of oxide supports have been investigated on the performance of Rh catalysts for the autothermal reforming of gasoline and gasoline surrogates to hydrogen [13, 50]. As a part of the development of a gasoline reformer, the reforming of iso-octane, a model compound for gasoline, over a Pt catalyst supported on a CeO2ZrO2 mixed oxide support was investigated by Villegas et al. [51]. They selected this support as its redox properties can promote noble metals activity, whereas its basic character limits carbon deposition in reforming reactions. They found that the ceria-zirconia support plays an active role in the transformation of the carbonaceous species, originating from iso-octane decomposition into gaseous products and hence, Pt/CeO2ZrO2 catalyst apparently does not get poisoned by carbon deposition. Kaila [52] used two bimetallic RhPt catalysts, with total metal loading of not more than 0.5 wt%, prepared by coimpregnation from Rh(NO3)3 and Pt(NH4)4(NO3)2 precursors. The Rh to Pt molar ratios of the bimetallic catalysts were 1.2 and 2.4 mol/mol. The performance of these bimetallic catalysts in ATR of the n-dodecanetoluene

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D. J. Moon
800

Heat of Reaction (Kcal/mol iso-octane)

mixture was compared with the performance of Rh, Pd, and Pt catalysts and the ZrO2 support. They found that thermal stability of Rh catalyst was improved when Rh was combined with Pt in the bimetallic RhPt catalysts.

600

400

H 2O/C = 1 H 2O/C = 3

3 Catalytic Reforming of Liquid Hydrocarbons Many researchers have reported Rh catalysts for partial oxidation of CH4 and C2H6, steam reforming of CH4, ethanol and propanol and dry reforming of CH4 [53], however, little has reported on ATR of hydrocarbon fuels [22]. Steam reforming of liquid hydrocarbons such as gasoline, kerosene, diesel and other oil derivatives have been reported [5456]. Liquid fuels can be used as the energy carriers in many applications especially residential power generation (RPG) systems in remote areas and the auxiliary power units (APU) based on SOFC systems. Especially, gasoline and diesel are attractive fuels for the production of hydrogen by reforming because of their high gravimetric and volumetric hydrogen density and well established infrastructure. 3.1 Catalytic Reforming of Gasoline The overall POX reforming reaction (autothermal reforming, ATR) of iso-octane, as a main component of gasoline (Eq. 1) is given by, C8 H18 xO2 3:76 N2 16 2xH2 O ! 8CO2 25 2xH2 3:76 x N2 1

200

-200

-400 -0.5

0.0

0.5

1.0

1.5

2.0

2.5

Oxygen / Carbon Ratio

Fig. 1 The effect of O/C ratio on the heat of reaction in POX reforming reaction of iso-octane at 700 C and feed molar ratios H2O/ C = 3 and 1
1e+2 1e+1 1e+0 1e-1
iso-octane H2O/C=1 O/C=1 Toluene H2O/C=1 O/C=1 iso-octane O/C=1 iso-octane H2O/C=1 iso-octane H2O/C=0.5 O/C=0.5

Carbon(mmol/hr)

1e-2 1e-3 1e-4 1e-5 1e-6 1e-7 1e-8 1e-9 1e-10 1e-11 400 600 800 1000

where x is a ratio of oxygen/fuel. During POX reforming of iso-octane and toluene, the heat of reaction and the amount of carbon formed were calculated by the Gibbs free energy minimization method [57] were reported. Figure 1 shows the effect of O/C ratio on the heat of reaction in POX reforming reaction of isooctane at 700 C and feed molar ratios H2O/C = 3 and 1. The heat of reaction for the gross-reaction is dependent on the molar ratio of oxygen/fuel, the molar ratio of H2O/fuel and the reaction temperature. There is gradual change from endothermic at sufciently low O/C molar ratio to exothermic at high O/C molar ratio, 0.6. By advantage of being able to tune the reaction heat by properly varying O/C molar ratio makes POX reforming superior to steam reforming. Hence for low energy requirement, an O/C molar ratio of C0.6 is favorable for POX reforming of isooctane. The amount of carbon formed as a function of temperature for ve reforming reactions of iso-octane and toluene are presented in Fig. 2. If the feed consists of iso-octane (1 gmol/h) and air at O/C = 1, more than 1 9 10-9 mmol h-1 of coke would form in the partial oxidation of

1200

Temperature( oC)

Fig. 2 Reaction temperature required to prevent the formation of carbon during the reforming process of iso-octane and toluene, assuming thermodynamic equilibrium

iso-octane at temperatures up to 950 C. If the feed consists of iso-octane (1 gmol/h) and H2O at H2O/C = 1, more than 1 9 10-9 mmol h-1 of coke would occur in the steam reforming of iso-octane at temperatures up to 800 C. If water is added with molar ratio of H2O/C = 1 while maintaining the O/C ratio = 1, the reactor temperature in the POX reforming of iso-octane can be lowered to 560 C before carbon formation occurs. It was found that the carbon formation temperature was increased until 600 C when the ATR reaction of toluene was carried out under the same reaction conditions of iso-octane. Various transition metal formulations, M(active)/MgO/ Al2O3, M(active)/MgO/SiO2Al2O3, Ni(major)/M(minor)/MgO/ Al2O3, Mo(major)/M(minor)/MgO/Al2O3 and Ni/Ce/ZrO2 used for ATR of toluene and iso-octane and their

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Hydrogen Production From Liquid Hydrocarbons Table 1 Characteristics of the prepared and the commercial catalysts used for ATR of iso-octane and toluene Catalyst code KIST-1 KIST-2 KIST-3 KIST-4 KIST-5 KIST-6 KIST-7 ICI
a

29

Catalyst composition Ni/MgO/Al2O3 Fe/MgO/Al2O3 Co/MgO/Al2O3 Mo/MgO/Al2O3 Ni/Fe/MgO/Al2O3 Ni/Co/MgO/Al2O3 Ni/Mo/MgO/Al2O3 Ni/CaO/Al2O3

BET surface areaa (m2/g) 29 88 66 88 74 62 72 35

Total pore volumea (cc/g) 0.207 0.228 0.305 0.294 0.212 0.172 0.259 0.085

) Ave. pore diametera (A 286.0 103.7 185.6 134.1 115.1 111.8 124.4 96.26

Derived from N2 physisorption using Quantachrome Co

characterization are summarized in Table 1. Where M is a component selected from Ni, Co, Fe and Mo. 3.1.1 Autothermal Reforming of Toluene The autothermal reforming of n-dodecane, toluene and their mixtures has been studied by Reeta K. Kaila et al. [52] over monometallic (Rh, Pd, Pt) and bimetallic (Rh/Pt) noble metal zirconia catalysts at 700900 C. The Rhcontaining catalysts were more active toward ATR reactions than the other noble metal catalysts (Pt and Pd) on zirconia. It has been reported [58] that the addition of ZrO2 to ceria leads to improvements in redox property, thermal resistance and catalytic activity for ATR at lower temperatures. Figure 3 shows the comparison of the product composition and coke deposition temperature for the ATR of isooctane and toluene. Equilibrium conversion and carbon formation temperature for ATR reaction of iso-octane and toluene were estimated by POR II simulation program, assuming thermodynamic equilibrium at 700 C, feed

molar ratios of H2O/C = 3 and O/C = 1. The carbon formation in the ATR reaction of iso-octane occurred at less than 620 C, however, it was also found that it occurred at less than 640 C in the ATR reaction of toluene. The results suggest that the selection of reasonable reforming temperature is important for the reforming of mixed hydrocarbons such as gasoline because of higher reforming temperature of toluene than that of iso-octane. It was found that Ni/Fe/MgO/Al2O3 catalyst showed better activity and sulfur tolerance over the commercial Haldor Topsoe (HT) catalyst and can be applied as ATR catalyst of gasoline fuel processor application. 3.1.2 Autothermal Reforming of Iso-Octane Catalytic partial oxidation of hydrocarbons for generating hydrogen has gained much attraction in recent years owing to its direct application in proton exchange membrane fuel cells for generating clean electrical energy. It has been widely accepted as the most promising process to meet the efciency, volume and cost goals of the transportation applications [59]. For vehicle applications, the advantage of catalytic POX reforming over SR is a low energy requirement, sulfur tolerance of a catalyst and more rapid and controlled response to the transient power requirements [5, 60]. The use of commercial SR catalyst for POX reforming of aliphatic and aromatic hydrocarbon liquids has been done by some researchers [19, 61]. However, number of problems was identied including the tendency of deactivation of the catalyst due to formation of nickel aluminate spinnels, excessive coking and susceptibility to sulfur poisoning which limit their use for vehicle applications. The problem of catalyst deactivation by carbon deposition and sulfur poisoning in the POX reforming reaction of iso-octane over commercial reforming catalyst was reported previously [19, 62]. Based on the experience of our previous research [1720], we found the ideal

H2

Product Distribution (%)

80

CO CO 2 CH 4 Carbon formation temp.

700

60

650

40

600

20

550

0 Iso-octane Toluene

500

Fig. 3 The comparison of the product composition and coke deposition temperature for the ATR of iso-octane and toluene, respectively. Reaction temperature = 700 C; feed molar ratios of H2O/C = 1 and O/C = 1

Carbon Formation Temperature( C)

100

750

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D. J. Moon

operating conditions for POX-reforming reactions as: temperature 700 C, feed molar ratio of H2O/C = 3 and O/C = 1. KIST-5 catalysts showed a little higher H2 selectivity than commercial ICI catalyst. Selectivity of H2 and CO progressively increased with increasing reaction temperature. Hydrogen selectivity over KIST-5 and ICI catalysts were 65 and 64% at 700 C, respectively and CO selectivity was 11.3 and 13.4%, respectively. POX reforming of iso-octane was carried [60] over various catalyst formulations (Table 1) for gasoline fuel processor applications. The effect of sulfur impurities on the stability of each catalyst was also investigated in the POX reforming reaction of iso-octane. The performance of prepared catalysts was compared with that of the commercial ICI catalyst. Generally the reforming of hydrocarbons always has potential to form coke. If the reactor is not properly designed or operated, coking is inclined to occur. So the reactor temperature required to prevent the formation of carbon during the reforming process of iso-octane was estimated by PRO-II simulation program, assuming thermodynamic equilibrium [1720]. Overall, Ni/M/MgO/Al2O3 catalysts are more active than M/MgO/Al2O3 catalysts. Especially, the catalytic formulations using Ni as a major active component with a minor active component such as Fe or Co are found to be more active than the other catalytic formulations. The KIST-5 catalysts before and after the POX reforming reaction of iso-octane have not shown any major change in XRD phase patterns. Also, no metallic carbide such as nickel carbide and ferric carbide was formed during POX reforming of iso-octane at 700 C for 24 h. Modied Ni/(Co or Fe)/MgO/Al2O3 system can be considered as an alternative option to the commercial reforming catalyst for POX reforming of iso-octane. Figure 4 shows the comparison of the KIST-5 catalyst with the commercial ICI catalyst for the product distribution in the POX reforming of iso-octane. It was identied that KIST-5 catalyst showed similar activity to commercial ICI catalyst. To elucidate the effect of sulfur impurities on the catalytic deactivation, we investigated the POX reforming reaction of iso-octane containing 100 ppm sulfur. Figure 5 represents the comparison of the KIST-5 with commercial ICI catalyst for sulfur tolerance in the POX reforming of iso-octane at 700 C space velocity = 8,776 h-1, feed molar ratios of H2O/C = 3 and O/C = 1. KIST-5 catalyst displayed better activity and sulfur tolerance than commercial ICI catalyst, even though none of the systems were found to be completely sulfur resistant. Table 2 gives characteristics of the commercial ICI catalyst and KIST-5 catalysts before and after ATR of iso-octane under tested conditions. Long term stability for the KIST-5 catalyst in the ATR reaction of iso-octane containing sulfur less than 5 ppm at

70

Product Distribution (%)

60 50 40 30 20 10 0

ICI KIST 5

H2

CO

CO 2

CH 4

Fig. 4 The comparison of the KIST-5 with the commercial ICI catalyst for the product distribution in the POX reforming of isooctane. Reaction temperature = 700 C; space velocity = 8,776 h-1; feed molar ratios of H2O/C = 3 and O/C = 1
100
ICI - H2 KIST 5 - H2 KIST 5 - CH4 KIST 5 - CO KIST 5 - CO2

Product Distribution (%)

80

ICI - CH4 ICI - CO ICI - CO2

60

40

20

0 0 5 10 15 20 25

Time (h)

Fig. 5 Sulfur tolerance for the KIST-5 (Ni/Fe/MgO/Al2O3) and commercial ICI catalysts in the POX reforming of iso-octane containing sulfur (Cs = 100 ppm). Reaction temperature = 700 C; space velocity = 8,776 h-1; feed molar ratios of H2O/C = 3 and O/C = 1

700 C, space velocity = 8,776 h-1, feed molar ratio of H2O/C = 3 and O/C = 1 is shown in Fig. 6. The KIST-5 catalyst was found to be stable more than 800 h under the tested conditions. Ferrandon and Krause found out [34] superior activity and stability of Rh/LaAl2O3 for long term tests of monoliths samples for the ATR of sulfur-free gasoline. But KIST-5 catalyst comprising of Ni/Fe/MgO/ Al2O3 proved to be the best in the ATR of iso-octane with long term stability of more than 800 h and also economical unlike the noble metal based catalyst. 3.1.3 Gasoline Fuel Processor System The successful development of a fuel cell system is dependent on the development of a fuel processor. Hydrogen is an ideal fuel for proton exchange membrane

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Hydrogen Production From Liquid Hydrocarbons Table 2 Comparison of the characteristics of KIST catalyst with commercial ICI catalyst before and after ATR reaction of iso-octane Catalyst ICI Before the reaction After the reaction of iso-octane (Cs \ 5 ppm) After the reaction of iso-octane (Cs = 100 ppm) KIST-5 Before the reaction After the reaction of iso-octane (Cs \ 5 ppm) After the reaction of iso-octane (Cs = 100 ppm)
a b c

31

BET surface areaa (m2/g) 35.3 26.7 19.9 73.6 61.9 49.4

Total pore volumea (cc/g) 0.085 0.069 0.049 0.212 0.185 0.166

Active metal S. A. (m2/g)b 0.789 0.543 0.397 1.906 1.528 1.397

Carbon contentc (wt%) 0.01 5.8 25.7 0.01 4.9 19.6

Sulfur contentc (wt%) 0.003 0.004 0.006 0.003 0.004 0.005

Derived from N2 Physisorption using Quantachrome Co Derived from CO chemisorption using Micromeritics Co Measured by Elemental Analyzer
100 H2 CO CO2 CH4

80

60

40

20

0 0 100 200 300 400 500 600 700

Reaction Time (h)

Fig. 6 Long term stability for the KIST-5 catalyst in the ATR reaction of iso-octane containing sulfur less than 5 ppm. Reaction temperature = 700 C; space velocity = 8,776 h-1; feed molar ratios of H2O/C = 3 and O/C = 1

fuel cell because it simplies system integration and hence being increasingly accepted as the most appropriate power source. Since there is no hydrogen infrastructure, the development of fuel processor and hydrogen station has been hot issue for commercialization of fuel cell system. The lower efciency of gasoline in comparison with methanol can be compensated by the much higher energy density of gasoline compared to methanol and also by the well-developed infrastructure for gasoline [61]. Due to the favorable factors required for the on board generation of H2 in the fuel cell system, POX reforming of gasoline attracts much attention primarily because of low energy requirement. It is reported [61] that the fuel cell performance was progressively degraded by CO poisoning of Pt anode catalyst. Therefore, many researchers studied [6, 63, 64] high

temperature water gas shift (HTS) and low temperature water gas shift (LTS) reactions and/or preferential partial oxidation (PROX) to reduce the CO concentration within the tolerance limit of the Pt anode catalyst. Especially, the WGS reaction is a critical step during the fuel processing since CO poisons the PEM electro-catalyst and LTS catalyst was prone to be deactivated by sulfur poisoning and thermal cycling [64]. The WGS reactors charged with currently available commercial HTS and LTS catalysts constitute about a third of the mass, volume and cost of the fuel processor system. Gasoline fuel processor system consists of six sections: feed supply section, evaporator, POX reforming reactor, HTS reactor, LTS reactor and GC analysis sections. As a part of the development of gasoline fuel processor system for integration with PEM fuel cell, we investigated [65, 66] POX reforming reaction of iso-octane with/without 100 ppm sulfur over a commercial reforming catalyst. We also investigated HTS reaction over Fe3O4Cr2O3 commercial catalyst and LTS reaction over Cu/ZnO/Al2O3 commercial catalysts to remove CO from the hydrogen rich-stream produced by POX reforming reaction. Table 3 lists the characteristics of KIST reforming catalyst, commercial HTS and KISTLTS catalysts used in gasoline fuel processor system. It was found that the commercial reforming catalyst was prone to be poisoned by sulfur contained in iso-octane, but there is no coke deposition at 700 C under the tested conditions. The product distribution data from three different reaction stages over the KIST reforming catalyst (KIST-5), commercial HTS catalyst and KIST-LTS catalyst are shown in Fig. 7. The H2 and CO2 concentrations after the gases passed through HTS and LTS reactors increased while those of CO and CH4 decreased. The concentration of CO can be reduced to \1,800 ppm when KIST-5 reforming catalyst, HTS catalyst and LTS

Product Distribution (%)

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32 Table 3 Characteristics of catalysts used in gasoline fuel processor system Catalysts Ni/Fe/MgO/Al2O3 Fe3O4Cr2O3 PtNi/CeO2
a b c d

D. J. Moon

Reaction ATR HTS LTS

BET surface areaa (m2/g) 74 57 78

Total pore volumea (cc/g) 0.212 0.073 0.049

Active metal surface areab (m2/g) 0.213 0.127 0.086

Maker KISTc ICId KISTc

Derived from N2 physisorption using Quantachrome Co Derived from CO chemisorptions using Micromeritics Co KIST-Korea Institute of Science and Technology, South Korea ICI-Imperial Chemical Industries Co

Fig. 7 The product distribution from three different reaction stages over the KIST-5 catalyst system (ATR: Ni/Fe/MgO/Al2O3; HTS: Fe3O4Cr2O3; LTS: PtNi/CeO2). The ATR over KIST catalyst was carried out at reaction temperature 700 C, space velocity = 8,776 h-1, molar ratios H2O/C = 3 and O/C = 1. HTS and LTS reactions were carried out at 450 C and 250 C, respectively

(PtNi/CeO2) catalyst are charged with the gasoline fuel processor system. In our previous work [65, 66], it was reported that the concentration of CO can be reduced to 3,000 ppm when commercial ICI, HTS and LTS catalysts were charged in gasoline fuel processor system. The partnership for a new generation of vehicles (PNGV) has a set a goal to reduce the weight of the shift reactors to 75%. For integration with PEM fuel cell, the preferential PROX reactor and the development of new high performance catalysts with sulfur and coke-resistance are needed. 3.2 Catalytic Reforming of Diesel In previous paper [65], we reported high and stable activity of Ni-loaded catalysts prepared from MgAl hydrotalcitelike anionic clay for steam reforming of LPG. The concentration of H2 after 5 h was nearly same over spc-Ni/ MgAl and ICI catalysts for SR of LPG. The concentration

of H2 was maintained during reaction time (186 h) at 800 C, GHSV = 20,000 h-1 with H2O/C = 2. However, it decreased over commercial ICI catalyst due to the formation of carbon. Memory effect property of hydrotalcite-like support allows the reconstruction of the original hydrotalcite structure under mild conditions when contacting the product of the thermal treatment with water which minimizes the degradation of the catalyst during steam reforming reaction. Steam reforming of LPG over nickel-based and noble metals modied nickel based catalysts using (different Ni to Mg ratio) hydrotalcite-like support is reported [17, 38, 42] recently. A spc-Ni/MgAl catalyst was prepared by coprecipitation method and later also modied with noble metals (Ru, Rh) by dipping method. Among the non impregnated Ni-based catalysts, spc-Ni/MgAl catalyst shows good performance up to 186 h for steam reforming of LPG, though the activity was found to be declined at 800 C, H2O/C = 2 and GHSV = 20,000 h-1. Figure 8 shows the XRD patterns of hydrotalcite (MgAl) and 0.3 wt% Rh spc-Ni/MgAl catalysts prepared by dipping method. XRD pattern (a) is typical hydrotalcite peak pattern taken after drying at 60 C for 12 h in air. Then after calcining at 850 C for 5 h, hydrotalcite structure changed to MgNiO crystalline form (b). When Rh modied spcNi/MgAl catalyst was prepared using spc-Ni/MgAl by dipping method followed by drying at 80 C for 6 h, Mg NiO structure was found to reconstitute to hydrotalcite by memory effect (c). XRD pattern (d) shows loaded Rh forms RhxOx on the surface of Rh modied spc-Ni/MgAl catalyst prepared by dipping method. Figure 9 shows the product distribution of noble metal modied Ni-based catalysts for steam reforming reaction with time on stream up to 53 h at reaction conditions: temperature = 700 C, GHSV = 20,000 h-1 and H2O/C = 1.0. Ru modied spc-Ni/MgAl catalyst showed H2: 64*66%, CH4: 5*7%, CO: 18*21%, CO2: 6*10% product distribution by vol(%) whereas Rh modied spc-Ni/MgAl catalyst formed H2: 67%, CH4: 4.9%, CO: 19%, CO2: 8% by vol(%). It was found that Rh loaded catalyst showed stable performance

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Hydrogen Production From Liquid Hydrocarbons

100

33

80

Out gas vol. %

60

40

H2 CO CH 4 CO2

20

0 0 100 200 300 400 500 600 700 800 900 1000 1100

Fig. 8 XRD patterns of prepared catalyst: (a) spc-Ni/MgAl-hydrotalcite; (b) after calcination at 850 C for 5 h; (c) after dipping (b) in an aqueous solution of Rh(III) chloride and drying; (d) after calcination of 0.3 wt% RhNi/MgAl catalyst; lled circle, MgNi O; open square, NiAl2O4; lled square, hydrotalcite

Time (h)

Fig. 10 Out gas distribution for SR of LPG over 0.3 w%t RhNi/ MgAl catalyst for 1,100 h (S/C = 3.0, GHSV = 20,000 h-1, temperature = 800 C)

100 90 80 70

60 50 40 30 20 10 0 0 5 10 15 20 25 30 35 40 45 50 55

H2 CO CH4 CO2

Time (h)

formation. This concludes that the addition of Rh metal to spc-Ni/MgAl enhanced the reforming activity of LPG as well as constrain to the carbon deposition. Also 0.3 wt% Rh spc-Ni/MgAl catalyst was found to have prolonged stability up to 1,100 h in the steam reforming of LPG as shown in Fig. 10. These results draw a conclusion that 0.3 wt% Rh spc-Ni/MgAl catalyst is desirable LPG SR catalyst for application in hydrogen station and fuel processor systems. The spc-Ni/MgAl catalyst displayed better activity than ICI commercial CH4 SR catalyst, but was having tendency to coke formation even though carbon formed did not affect adversely in this reaction. It was found that 0.3 wt% Rh spc-Ni/MgAl catalyst showed the strong restraint of carbon formation compared to 0.3 wt% Ru spc-Ni/MgAl catalyst. The overall POX reforming of n-hexadecane as a surrogate of diesel is given in Eqs. (24) [6771]. C16 H34 32 H2 O ! 49 H2 16 CO2 DH 2336 kJ=mol C16 H34 16 O2 ! 17 H2 16 CO2 DH 5694 kJ=mol C16 H34 16 H2 O 8 O2 ! 33 H2 16CO2 DH 1739 kJ=mol 2 3 4

Fig. 9 Out gas distribution for SR of LPG over 0.3 wt% RhNi/ MgAl catalyst for 53 h (S/C = 1.0, GHSV = 20,000 h-1, temperature = 700 C)

for SR of LPG without uctuation in product distribution under severe reaction conditions: temperature = 700 C, GHSV = 20,000 h-1, H2O/C = 1.0. Moon et al. reported that the TEM images and TGA proles of 0.3 wt% Ru spc-Ni/MgAl and 0.3 wt% Rh spcNi/MgAl catalysts before and after the reaction [17]. It was found that plenty of carbon was formed on Ru spc-Ni/ MgAl catalyst, during the reaction, compared to Rh spc-Ni/ MgAl catalyst. The TGA proles also show more weight loss for Ru spc-Ni/MgAl catalyst compared to Rh spc-Ni/ MgAl catalyst which agrees well with TEM data. This infers that Ru metal is not effective for inhibition of carbon

Out gas Vol %

The main problems associated with the reforming of diesel are related to catalyst degradation during the reaction due to the harsh operating conditions (high temperature and H2O/C ratio) used to obtain high hydrogen yield. It is mainly caused due to the poisoning of catalyst by sulfur, thermal sintering and extensive carbon formation due to the low H/C ratio and high molecular weight of the molecules present in diesel fuel. Generally, reforming catalyst

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34 Table 4 Characteristics of the modied spc-Ni/Mg/Al based catalysts before and after steam reforming of n-hexadecane Catalyst BETa (m2/g) Before the reaction Dispersion (%) Before spc-Ni/MgAl RhNi/MgAlA RhNi/MgAlB RhNi/MgAlC
a b c b

D. J. Moon

After the reaction Active metal particle size (nm) 6.33 8.34 7.50 7.37 Dispersionb (%) Ni 0.25 1.04c 1.54 2.75 3.13 Ni ? Rh Active metal particle size (nm) 401.73 93.23c 66.03 36.89 32.41

After 42

Ni 17.12

Ni ? Rh 12.16 13.53 13.80

198 105 107 106

Measured by N2 physisorption using Quantachrome Co Measured by CO chemisorption using Micromeritics Co After SR of n-hexadecane for 53 h at 950 C

comprise of transition metals (Ni, Co, Fe, etc.) or noble metals (Pt, Pd, Ru, Rh, etc.) deposited or incorporated on supports such as thermally stabilized alumina, doped alumina with promoters to accelerate reforming of hydrocarbon [72]. Recently, the works on steam reforming of n-hexadecane (n-C16H34) as a main constituent of diesel have been reported [17, 73, 74] over spc-Ni/MgAl and noble metal (Rh) modied Ni-based catalysts listed in Table 4. The spc-Ni/MgAl catalyst derived from hydrotalcite precursor was prepared by co-precipitation method and RhNi/MgAl catalyst was made by dipping method. The steam reforming of n-hexadecane over these catalysts carried out at 900 C, GHSV = 10,000 h-1and feed molar ratio of H2O/C = 3. Catalytic performances of these catalysts after the reaction for 5 h and 53 h are compared in Fig. 11. The H2 concentration and the product distribution for the steam reforming of n-hexadecane over 0.3 wt% Rh spc-Ni/MgAl catalyst was maintained constant during steam reforming. However, H2 concentration over spc-Ni/MgAl catalyst was decreased due to drastic shrinkage in the metal dispersion and increase in active metal particle size [39]. The addition of Rh metal to the spc-Ni/MgAl catalyst as a promoter very effectively inhibited the sintering of Ni metal under tested conditions. The SR of n-hexadecane on spc-Ni/MgAl and Rh spc-Ni/ MgAl catalysts was carried out at 900 C, feed molar ratio of H2O/C = 3 and GHSV of 10,000 h-1 for 53 h to conrm the role of Rh metal with restraint of Ni metal sintering. Figure 12 represents the product distribution with time on stream over 0.3 wt% Rh spc-Ni/MgAl catalyst for 53 h. The initial activity from start up to 5 h over spc-Ni/MgAl catalyst was found to be similar to 0.3 wt% Rh spc-Ni/MgAl catalyst. However, activity of 0.3 wt% Rh spc-Ni/MgAl was constant during the SR of n-hexadecane. On the other hand, activity of spc-Ni/MgAl catalyst decreased slowly with enhancement in degree of deactivation from 45 h after the commencement of the reaction. The SR of decahydronaphthalene as a second

100

H2 CO
80

H2 in out gas (vol %)

60

40

20

0 after 5h after 53h after 5h after 53h 20wt% Ni/MgAl 0.3wt% Rh-Ni/MgAl

Fig. 11 The comparison of concentrations of H2 and CO in the SR of n-hexadecane over spc-Ni/MgAl and 0.3 wt% RhNi/MgAl catalysts for 53 h (S/C = 3.0, GHSV = 10,000 h-1, temperature = 900 C)

constituent of diesel on spc-Ni/MgAl catalyst was carried out at 900 C, feed molar ratio of H2O/C = 3 and GHSV of 10,000 h-1 [75, 76]. Figure 13 shows the product distribution with time on stream over spc-Ni/MgAl catalyst for 53 h. The concentration of CO was slowly decreased with increasing CO2 and carbon formation. This result may be considered that the deactivation of catalyst was caused by the carbon formation by Boudart reaction (Reaction 5) under the tested conditions. 2CO ! CO2 C 4 Conclusions and Future Directions This is a review on the works carried out on the production of hydrogen by catalytic reforming of liquid hydrocarbon fuels namely a main surrogate of gasoline and diesel. 5

123

Hydrogen Production From Liquid Hydrocarbons

100

35

80

60

40

H2 CO CH4 CO2

20

0 0 5 10 15 20 25 30 35 40 45 50 55

(PtNi/CeO2) catalyst. The concentration of CO was found to be reduced to \1,800 ppm in this system. We found that commercial reforming catalyst was prone to be poisoned by sulfur contained in iso-octane. We investigated modied hydrotalcite based formulations for the reforming of diesel and compared to spc-Ni/ MgAl catalyst. The addition of Rh metal to the spc-Ni/ MgAl catalyst also acts as a promoter, inhibiting the sintering of Ni metal particles during catalytic reforming of n-hexadecane, a surrogate of diesel under tested conditions. For applications in commercial process studies on the catalytic reforming over structured catalyst by the modication of the developed catalysts in this work will be needed in near future.
Acknowledgments Author would like to thank our coworkers for their valuable research contributions in reforming of liquids hydrocarbons summarized in this review. The author would also like to acknowledge nancial support from KIST to carry out this research in Clean Energy Center, Korea Institute of Science and Technology (KIST).

Out gas vol (%)

Time (h)

Fig. 12 The product distribution with time on stream in the SR of n-hexadecane over 0.3 wt% RhNi/MgAl catalyst for 53 h (S/C = 3.0, GHSV = 10,000 h-1, temperature = 900 C)

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