i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 4 1 e7 4 5 3

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Ni/MgOeAl2O3 and NieMgeO catalyzed SiC foam absorbers for high temperature solar reforming of methane
Nobuyuki Gokon a,*, Yuhei Yamawaki b, Daisuke Nakazawa b, Tatsuya Kodama b
a

Center for Transdisciplinary Research & Department of Chemistry and Chemical Engineering, Niigata University, 8050 Ikarashi 2-nocho, Nishi-ku, Niigata 950-2181, Japan b Graduate School of Science and Technology, Niigata University, 8050 Ikarashi 2-nocho, Nishi-ku, Niigata 950-2181, Japan

article info
Article history: Received 15 February 2010 Received in revised form 5 April 2010 Accepted 8 April 2010 Available online 3 June 2010 Keywords: Solar heat Hydrogen production Reforming Thermochemical process Ni catalyst Reticulated ceramic foam

abstract
Ni catalyst supported on MgOeAl2O3 (Ni/MgOeAl2O3) prepared from hydrotalcite, and NieMgeO catalyst are studied in regard to their activity in the CO2 reforming of methane at high temperatures in order to develop a catalytically activated foam receivereabsorber for use in solar reforming. First, the activity of their powder catalysts is examined. Ni/MgOeAl2O3 powder catalyst exhibits a remarkable degree of high activity and thermal stability as compared with NieMgeO powder catalyst. Secondly, a new type of catalytically activated ceramic foam absorber e Ni/MgOeAl2O3/SiC e and NieMgeO catalyzed SiC foam absorber are prepared and their activity is evaluated using a laboratory-scale receiverereactor with a transparent quartz window and a sun-simulator. The present Ni-based catalytic absorbers are more cost effective than conventional Rh/g-Al2O3 catalyzed alumina and SiC foam absorbers and the alternative Ru/g-Al2O3 catalyzed SiC foam absorbers. Ni/MgOeAl2O3 catalyzed SiC foam absorber, in particular, exhibits superior reforming performance that provides results comparable to that of Rh/g-Al2O3 catalyzed alumina foam absorber under a high ux condition or at high temperatures above 1000  C. Ni/MgOeAl2O3 catalyzed SiC foam absorber will be desirable for use in solar receiverereactor systems to convert concentrated high solar uxes to chemical fuels via endothermic natural-gas reforming at high temperatures. 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Currently, the countries that have abundant natural gas reservoirs close to solar sites favorably set in a sun-belt region that receives more than 1500 kWh/m2 a year enjoy a great potential to generate hydrogen using renewable energy sources. This can provide a convenient alternative to natural gas power plants, whose main advantage is signicantly reduced CO2 emissions. The thermochemical conversion of concentrated solar heat to chemical fuels has the advantage of producing energy carriers for the storage and

transportation of solar energy from the sun-belt to remote population centers [1e4]. The direct thermochemical conversion of solar radiation energy is characterized by an ideal high efciency; its thermodynamic limit for enthalpy storage is close to 100%. From the perspective of the chemical pathway for this process, the solar reforming of natural gas has been investigated as one of the most promising solar thermochemical processes [5e23]. The following endothermic reformings of natural gas are the basis for upgrading the caloric value of the hydrocarbons which produce syngas:

* Corresponding author. Tel./fax: 81 25 262 6820. E-mail address: ngokon@eng.niigata-u.ac.jp (N. Gokon). 0360-3199/$ e see front matter 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2010.04.040

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CH4 H2O(g) CO 3H2

DH298 K 206 kJ mol1,

(1)

CH4 CO2 2CO 2H2

DH298 K 247 kJ mol1.

(2)

In order to produce more hydrogen, solar-processed syngas (CO and H2) is shifted via a water-shift reaction, in which water catalytically reacts with CO in the following reaction:

CO H2O(g) CO2 H2 DH298

41 kJ mol1

(3)

The carbon dioxide product can then be separated, for example, via a membrane, and sequestrated. In comparison to the conventional reforming of natural gas, the solar reforming of natural gas offers distinct advantages: (1) the utilization of solar energy as a replacement for fossil fuels to obtain the necessary process heat reduces fossil fuel consumption, (2) concentrated solar radiation input theoretically upgrades the reactants energy content by 22e28%, and (3) environmentally hazardous pollutants and CO2 emissions are eliminated or reduced. A project was proposed to develop a solar methanol production system in the sun-belt [4]. In this project, the plan is for methanol or DME to be produced from natural gas (methane) and coal via methane reforming and coal gasication using solar heat as the process heat. The liquid fuel that is produced can then be transported overseas to Japan by a modied oil tanker [4]. Concentrated solar radiation has the specic properties of high density, heterogeneous distribution of thermal ux, and frequent thermal transients due to the uctuating insolation. A solar-specic reactor for reforming was proposed on the basis of a direct absorption concept in which the receiver and reformer comprise the same unit. This concept was realized in a number of solar reforming systems such as the directly irradiated volumetric reactors developed by the German Aerospace Research Center (DLR) in Germany, Sandia National Laboratories in the United States, and the Weizmann Institute of Science (WIS) in Israel [7,9e11,13,16,17]. In this concept, the concentrated solar radiation passes through a transparent window and is absorbed by an absorber of catalytically active, reticulated ceramic foam which is mounted behind the window. In these volumetric reactors, reticulated ceramic foam made of alumina and SiC, which combines high gas permeability and turbulence of ow with a geometry suitable for the effective and uniform absorption of solar radiation, is considered preferable to conventional honeycomb structures. The solar reforming of methane with CO2 using the volumetric reactor system was rst demonstrated in DLR and Sandia National Laboratories in 1990 [7]. A 200e300 kW volumetric reactor was also demonstrated at the WIS for the solar CO2 reforming of methane [17]. A prototype was realized and tested as part of the SOLASYS (Solar Upgrading of Fossil Fuels) project. The receiver has 400 kW of thermal power absorbed by the gas and an operation pressure of 10 bar. The project demonstrated the ability of the volumetric reactor receiver to generate process heat that could run the chemical reaction at a temperature of about 900  C. The syngas that was produced was used in a small gas turbine for

power generation. Further work in the ongoing SOLREF (Solar Steam Reforming of Methane Rich Gas for Synthesis Gas Production) aims to achieve a temperature higher than 900  C in order to improve the efciency of the process and to make it possible to couple the reactor with gas treatment for the production of pure hydrogen. The Commonwealth Science and Industrial Research Organisation (CSIRO) in Australia operated a solar reforming program that used a solar dish concentrator from 1997 to 2002 [19]. Two reformer designs were tested: a multistraight tube reformer consisting of six straight tubes connected in parallel, and a single coiled reformer tube [19]. This successful operation demonstrated the production of proton exchange membrane (PEM) fuel cell-quality H2. In 2004, CSIRO began a new program to commercialize this technology by building a single, small tower module of 500 kW solar capacity that would demonstrate larger scale reforming [20,21]. A smaller reformer has also been in operation for steam reforming under solar irradiation [20,21]. Highly active catalysts based on metal Rh are frequently used for the solar CO2 reforming of methane [5,8]. Rh/g-Al2O3loaded alumina and SiC foam absorbers were extensively tested for the solar reforming of methane by using solar concentrating systems capable of utilizing up to 100e300 kWth of solar power [7,9e11,13,17]. Ru catalysts have also been proposed and demonstrated as highly active alternatives to Rh catalysts for use in methane reforming. g-Al2O3-supported Ru catalyst was examined for the CO2 reforming of methane at a temperature of 550  C [24]. Berman and Epstein examined the RueCe catalyst to improve the activity and thermal stability of Ru/g-Al2O3 catalysts for the solar CO2 reforming of methane [18]. Ru/(a-Al2O3MnOx) catalysts were studied for use in solar reforming at temperatures of 500e900  C and a total pressure of 1e7 atm [25]. The present study introduces a new type of ceramic foam absorber that is coated with cost effective and high-temperature stable Ni/MgOeAl2O3 and NieMgeO catalysts. These new products were prepared and their activity was tested using a laboratory-scale receiverereactor with a transparent quartz window and a sun-simulator.

2. Concept for development of new SiC foam absorber activated by Ni-based catalyst
Ni-based catalysts are generally considered economically suitable for solar reforming processes that produce a synthetic gas and hydrogen. However, Ni-based catalysts often cause carbon deposition on the surface of the catalyst during the processes, resulting in a deactivation of the catalyst. Many recent reports in the literature have indicated that the activity and stability of Ni-based catalysts are greatly improved by the use of rare-earth-based promoters or alkaline-earth metal ions [26e37]. An Ni catalyst containing MgOeCaO showed excellent activity and stability for the CO2 reforming of methane [28]. A NickeleMagnesia solid solution, Ni0.03Mg0.97O, provided ultrastable activity without carbon deposition that sustained its desirable activity in the CO2 reforming of methane for the long time of 100 days [34]. Stable and cost effective NieMgeO was proposed as a catalyst for

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solar reforming and a solar receivereabsorber that used alumina ceramic foam was prepared. The activity of the absorber was studied for solar CO2 reforming in a laboratoryscale volumetric receiverereactor under direct irradiation by a sun-simulator [36]. The SiC foam, which was reported to be more resistant to thermal shock at high temperatures in the large-scale solar test of the Rh/g-Al2O3/SiC absorber [17], was used instead of alumina foam as a matrix for the preparation of a catalytically activated Ru/NieMgeO absorber. The reforming performance of the Ru/NieMgeO/SiC absorber was investigated using a laboratory-scale volumetric receiverereactor and a sun-simulator [37]. However, as described above, other active and thermally stable Ni-based absorbers that do not use noble metals such as Pt, Rh and Ru will be desirable for solar reforming at high temperatures. Mixed oxides resulting from the thermal treatment of hydrotalcites present several interesting properties [38]. Hydrotalcite-like compounds are layered double hydroxides. The general formula of these compounds can be represented (III) x [Ax/nn]mH2O where M(II) and M(III) are as [M(II) 1 xMx (OH)2] divalent and trivalent cations and A is the compensation anion. This structure can accommodate a wide variety of the different M(II) and M(III) metals, which in turn lend it different properties. The thermal decomposition of these materials by calcination results in the formation of homogeneous mixed oxides with a high thermal stability and a larger surface area. In addition, well-dispersed metallic particles are usually obtained after a reduction treatment [38]. The preparation of heterogeneous catalysts derived from MgeAl hydrotalcite-like compounds containing Ni at the Mg sites as precursors, and their utilization for the steam and dry reforming has been reported [39e46]. Shishido et al. [40] tested Ni/MgeAl oxide catalysts derived from MgeAl hydrotalcite precursor for the CO2 reforming of methane under CH4/CO2 1:1 in a conventional ow reactor with a xed bed quartz tubular reactor at temperatures of 800  C at atmospheric pressure and a Gas 1 1 Hourly Space Velocity (GHSV) 51 Ndm3 g cat h . It was found that the Ni/MgeAl oxide catalysts exhibit higher activity than those prepared by the conventional impregnation method, such as Ni/a-Al2O3 and Ni/MgO. Tsyganok et al. [45] focused on the deposition of coke onto the Ni catalyst surface, the spatial distribution of supported Ni after the CO2 reforming of methane, and the thermal stability of Ni catalyst supported on MgeAl mixed oxide. Roh et al. [44] examined the combined

steam and CO2 reforming of methane using (H2O CO2)/CH4 of 1.2 at 800  C under atmospheric pressure at 1 1 a GHSV 265 Ndm3 g cat h . Ni/MgOeAl2O3 prepared from hydrotalcite material revealed a high degree of activity and stability in comparison to Ni/MgO, Ni/ZrO2, Ni/CeO2 and Ni/aAl2O3. Koo et al. [46] studied Ni catalyst supported MgOeAl2O3 prepared from hydrotalcite material for the combined steam and dry reforming of methane. Ni/MgOeAl2O3 prepared from hydrotalcite material exhibited remarkable coke resistance, but commercial Ni/MgeAl2O4 catalyst showed considerable coke deposition during the combined reforming. In the present work, Ni/MgOeAl2O3 catalyst derived from hydrotalcite (Mg6Al2(OH)16CO34H2O) and NieMgeO catalyst, which are much cheaper than Rh and Ru noble metal catalysts, are rst investigated in terms of their activity and the thermal stability of the CO2 reforming of methane. Second, a new type of catalytically activated ceramic foam absorbers e Ni/MgOeAl2O3 and NieMgeO catalyzed SiC foam absorbers e were prepared and evaluated in terms of their activity and thermal stability using a laboratory-scale receiverereactor with a transparent quartz window under direct light irradiation by a sun-simulator.

3.
3.1.

Experimental procedure
Materials

The chemicals of hydrotalcite (Mg6Al2(OH)16CO34H2O) and Ni (NO3)2$6H2O (purity 99.9%) were purchased from Wako Pure Chemical Industries Ltd. MgO powder (Grade 500A, purchased from Ube Material Industries Ltd.) was also used for preparation of the catalyst. SiC ceramic foam disks purchased from Krosaki Harima Co. were used as a matrix for the preparation of foam absorbers. The disks had diameters of 20 and 30 mm, a thickness of 10 mm, and cell size of 13 cpi (cells per linear inch). Table 1 shows the foam absorbers prepared for the present study.

3.2. Preparation of Ni/MgOeAl2O3 and NieMgeO powder catalyst

For the preparation of Ni/MgOeAl2O3 catalyst, hydrotalcite (Mg6Al2(OH)16CO3$4H2O) was used as a precursor. MgOeAl2O3

Table 1 e Catalytically activated foam absorbers used in this study. Catalyst Foam matrix Porosity (cpi) Dimensions (mm)a MgO
Ni/MgO NieMgeO Ni/MgOeAl2O3 SiC SiC SiC 13 13 13 20 30 20 30 20 30 10 10 10 10 10 10 2e 4 4
b

Loading (wt%) Ni
c

NieMgeOb

Ni/MgOeAl2O3b

11 11 2e 4 4 1e4 4

a Diameter and thickness. b With respect to the mass of the foam matrix. c With respect to the mass of the support.

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support derived from hydrotalcite was prepared by pre-calcination at various temperatures in the range of 800e1200  C for 6 h in air at a ow rate of 0.3 dm3 min1 in a normal state. The calcined powder was suspended in a nickel nitrate solution and was then left to evaporate until it was dry. The loading amount of Ni on the support was xed at 12 wt% [46]. Next, the dried powder was calcined at 600e1000  C for 6 h in air at a ow rate of 0.3 Ndm3 min1 and then reduced by a mixed gas of 50% Ar and 50% H2 at a ow rate of 0.1 Ndm3 min1 at 800  C for 1 h. NieMgeO catalyst was prepared as follows. The powder of the MgO support was suspended in a nickel nitrate solution that was then left to evaporate until it was dry. The dried powder was then ground in a mortar and then calcined at 750e1300  C for 6 h in air (at a ow rate of 0.3 Ndm3 min1). The loading amount of Ni on the MgO support was xed at 11% by weight [37]. The calcined powder was reduced at 800  C for 1 h in a mixed gas of 50% Ar and 50% H2 at a ow rate of 0.1 Ndm3 min1. The BET surface areas of the catalysts used were measured by nitrogen adsorption (Shimadzu, Micromeritics Flow Sorb II 2300) at 77 K. The catalyst powders were analyzed using XRD with CuKa radiation (MAC Science, MX-Labo) for identication of the formed phases.

until the MgO coating reached the desired degree of MgO loading on the foam. The MgO loadings were calculated from the masses of coated and uncoated foams. After the MgO coating process, an Ni2 was applied at 11 wt% Ni with respect to the mass of the magnesia support. An Ni(NO3)2 ethanol solution was added dropwise to the MgO-coated ceramic foam disk, then allowed to dry at room temperature overnight, and then calcined at 1000  C in air for 3 h. Hereinafter, the SiC foam absorber activated with Ni/MgO is referred to in this paper as Ni/MgO/SiC foam absorber. The absorbers of the Ni/MgOeAl2O3e, NieMgeOe, and Ni/ MgO-catalyzed SiC foam that were prepared are listed in Table 1.

3.4. Activity testing of Ni/MgOeAl2O3 and NieMgeO powder catalyst

The experimental setup is illustrated in Fig. 1(a). The powder catalyst (0.0725 g) was packed in the reactor of a transparent quartz tube with an inner diameter of 23 mm. The thickness of the catalyst bed was set to 1 mm. The powder catalyst was put on a occose quartz and sandwiched between SiC foam for xation of the powder catalyst inside the quartz tube while the alumina tubes were inserted for the preheating of the reactant gas mixture beneath the lower SiC foam. The quartz tube reactor was placed in an electric furnace and insulated with refractory bricks. A CH4eCO2 gas mixture (pCH4 50% and pCO2 50%) was fed into the reactor at a ow rate of 0.2 N dm3 min1 at Gas Hourly Space 1 1 at 1 atm. The powder catalyst Velocity (GHSV) 165 Ndm3 g cat h in the reactor was then heated at 900  C in order to carry out the methane reforming. The temperature of the catalyst bed was measured using a K-type thermocouple placed at the center of the catalyst bed that was in contact with it and that was packed inside the reactor. The efuent gases were analyzed by gas chromatography equipment (Shimadzu, GC-8A) with a thermal conductivity detector (TCD) to determine the gas composition. Ni/MgOeAl2O3 powder catalyst was tested at a ow rate of min1 (Gas Hourly Space Velocity 1.4 N dm3 1 1 (GHSV) 1155 Ndm3 g cat h ), which was 7 times higher than that which was used testing the NieMgeO powder catalyst. Because it displayed extremely high activity, the methane conversion reached 100% under all testing conditions at a ow rate of 0.2 Ndm3 min1.

3.3. Preparation of Ni/MgOeAl2O3 and NieMgeO catalyzed SiC foam absorber

The Ni/MgOeAl2O3 catalyzed SiC foam absorber was prepared as follows. The SiC ceramic foam disks used in the experiments were initially coated with Ni/MgOeAl2O3 particles by the wash-coat method described below. The coating of the foam disks was performed by soaking them in a well-stirred aqueous slurry of ne Ni/MgOeAl2O3 particles. The Ni/MgOeAl2O3-coated foam was dried at 100  C for 24 h then calcined at 1000  C for 2 h in an N2 stream at a ow rate of 0.4 Ndm3 min1. It was necessary to keep the density of the slurry (10e20 g dm3) sufciently low in order to prevent the pores of the foam structure from clogging. These Ni/MgOeAl2O3 coating processes were repeated until the loading reached 1e4 wt%, with the Ni/MgOeAl2O3 loadings estimated from the difference in their weight before and after the coating process. For the preparation of the NieMgeO catalyzed SiC foam absorber, the SiC foam disk was initially coated with NieMgeO particles by the wash-coat method described below. The coating of the foam disks was performed by soaking them in a well-stirred aqueous slurry of ne NieMgeO particles. The NieMgeO-coated foam was subsequently dried at 100  C for 24 h then calcined at 700  C for 2 h in an N2 stream at a ow rate of 0.4 Ndm3 min1. These NieMgeO coating processes were repeated until the loading reached 2e4 wt%, with the NieMgeO loadings estimated from their difference in weight before and after the coating process. For comparison, a SiC foam absorber activated with Ni/ MgO was also prepared using the same SiC foam disk, according to the procedure used in a previous work [37]. The SiC foam disk was rst wash-coated with MgO slurry solution, then dried at room temperature overnight, and then calcined at 1000  C for 1 h in air. This MgO coating process was repeated

3.5. Activity testing of catalytically activated SiC foam absorbers by Xe-light irradiation
A double-walled quartz reactor was used for the catalytic activity tests of the prepared absorbers. The experimental setup is illustrated in Fig. 1(b). The inner diameter of the outer quartz reactor was 39 mm, while the inner quartz tube had an inner diameter of 31 mm, and the thickness of both quartz tubes was about 2 mm. The absorber disk was attached to a porous quartz plate inside the inner tube and the reactor was insulated with refractory bricks. The reaction feed gas was fed into the outer annulus and was allowed to ow through the foam absorber disk into the inner tube of the reactor. A 50% CH4/50% CO2 gas mixture was fed into the reactor at a ow rate of 1.34 dm3 min1 (GHSV of 25,000 h1) for the foam with a diameter of 20 mm and 1.50 dm3 min1 (GHSV of 25,000 h1) for the foam with a diameter of 30 mm,

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powder catalyst
Sampling to GC(TCD)

catalytically-activated foam absorber

Thermocouple

Foam Parabolic mirror Absorber Thermocouple Xe-arc Gas exit Fixed porous quartz plate Shutter Lamp Sampling to GC (TCD) Gas exit

Electric furnace Catalyst layer (powder)

Spacer

Quartz Ceramic window insulation Gas inlet Flow controller Heat absorbing filter

Alumina tube CH4/CO2 gas mixture G as inlet

Fig. 1 e Schematics of the experimental setup for testing the activity of (a) powder catalyst in a tubular quartz reactor and (b) absorber by solar-simulated Xe-light irradiation.

after which the absorber was irradiated with solar-simulated Xe light in order to carry out the CO2 reforming of methane. A Xe-arc lamp house set (CINEMECCANICA, 5 kW ZX8000H, Milan, Italy) was used to simulate concentrated solar radiation. The energy ux distribution of the simulated incident light on the front surface of the absorber was measured previously using a heat ux transducer with a sapphire window attachment (Medherm, 64-1000-21). The temperature of the absorber was measured by a K-type thermocouple shielded with a glossy metal cover at the center of the front surface of the absorber. The steam in the efuent gas mixture from the reactor was condensed in a cooling trap connected to the outlet of the reactor, after which the composition of the gas mixture was analyzed using a gas chromatograph (Shimadzu, GC-8A) equipped with a TCD detector.

CH4 (1 x)CO2 (2 x)CO (2 x)H2 xH2O(g) H298 K 1 (6) (overall) 247 41x kJ mol where x indicates the contribution of the reverse wateregas shift reaction. The value of x was determined from the experimental H2/CO ratio in the product gas. Thus, the power stored as chemical enthalpy by the overall reaction, Wchem(kW), can be experimentally estimated from: Wchem fCH4 $X$DH298Koverall
1

(7)

where fCH4 (mol s ) indicates the molar ow rate of methane into the reactor inlet. The chemical storage efciency, hchem, of the incident light with respect to the chemical enthalpy is dened as: hchem Wchem =Winc (8)

3.6.

Calculation of efciencies

The methane conversion (X ) was estimated from the following equation: X yCO yH2 4yCH4 yCO yH2 (4)

where YCH4 , yCO, and YH2 are the respective mole fractions of CH4, CO, and H2 in the efuent gas [36,37]. Next, the conversion from light to chemical energy, i.e., the chemical storage efciency (hchem), was estimated as follows. First, the overall reaction occurring in the gas phase was determined from the experimental data. The CO2 reforming of methane, as described in Eq. (2), is frequently associated with a reverse wateregas shift reaction

where Winc (kW) is the total power of the incident light on the absorber. The chemically absorbed power density, Pd (kW m2), of the absorber was dened by the power absorbed in the chemical reaction, Wchem, divided by the irradiated surface area, S, of the absorber. The power of the reformed gas (CO and H2), HHVreformed gas (kW), was estimated from the following equation: HHVreformed gas Fout $PCO $DHCO Fout $PH2 $DHH2 (9)

where Fout, PCO, PH2 , DHCO, and DHH2 are the molar ow rate of the outlet gas (mol s1), the partial pressure of CO and of H2 (%), and the combustion heat of CO and of H2 (kJ mol1), respectively. The combustion heat of CO and H2 are written as follows: CO 1/2O2 (g) CO2 DHCO 282.98 kJ mol1,
1

H2 CO2 CO H2O(g) H298

41 kJ mol1

(5)

(10) (11)

and the H2/CO ratio in the product gas becomes lower than the stoichiometric ratio of 1. In this case, the overall reaction in the gas phase is written as:

H2 1=2O2 H2 Ol DHH2 285:83 kJ mol

The molar ow rate of the outlet gas,Fout, is expressed using the molar feed rate of CH4,fCH4 , and CO2, fCO2 , (mol s1),

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methane conversion, X, and H2/CO ratio in the outlet gas as follows: Fout fCH4 fCO2 2X$fCH4 2 1 H2 =CO 1 H2 =CO ! $X$fCH4 (12)

4.

Results and discussion

4.1. Activity of Ni/MgOeAl2O3 and NieMgeO powder catalyst

The XRD patterns of the original hydrotalcite and the hydrotalcite that was pre-calcined at various temperatures ranging from 800 to 1200  C are shown in Fig. 2(a). Hydrotalcite powder was transformed after pre-calcination at 800  C into an MgAlO4 (MgOeAl2O3)-like phase with broad peaks. After precalcination at 1000  C, obvious MgOeAl2O3 peaks appeared in the pattern. In addition, the intensity of the MgOeAl2O3 peaks increased due to crystalline growth at increasing pre-calcination temperature ranging from 800 to 1200  C. Fig. 2(b)

shows XRD patterns of Ni-loaded MgOeAl2O3 (Ni/MgOeAl2O3) powder catalyst calcined at various temperatures ranging from 600 to 1000  C. The loading amount of Ni catalyst on the MgOeAl2O3 support was xed at 12 wt%. Strong peaks due to metallic Ni were not observed, but a very weak peak was found at a diffraction angle 2q of around 50 in all the XRD patterns. The results indicate that well-distributed ne Ni particles are loaded on the MgOeAl2O3, although MgOeAl2O3 powder after Ni impregnation was calcined at high temperatures in the range of 600e1000  C. Fig. 3 shows XRD patterns of Ni/MgOeAl2O3 and NieMgeO powder catalysts before use in activity tests. As seen in Fig. 3(a), the peak intensities due to metallic Ni for Ni/MgOeAl2O3 catalyst were not enhanced after H2 reduction at 800  C. Thus, the Ni/MgOeAl2O3 powder catalyst for use in the activity test was prepared at a precalcination temperature of 1000  C for hydrotalcite regent, and was subsequently treated at 800  C after Ni impregnation by the wash-coating method. Ni/MgOeAl2O3/SiC foam absorber was also prepared using the powder catalyst. On the other hand, for NieMgeO catalyst, the peaks due to metallic Ni were not observed in the XRD pattern (Fig. 3(b)). The high

10000
Mg6Al2(OH)16CO34H2O MgAl2O4

8000

Intensity / cps

6000

1200 C

4000

1100 C 1000 C

2000

800 C Original hydrotalcite

0 20

30

40

50

60

70

80

2 (Cu-K) / degrees

6000 5000 4000

1000 C MgAl2O4 Ni

Intensity / cps

3000
900 C

2000
800 C

1000 0 20

700 C 600 C

30

40

50 60 2 (Cu-K) / degrees

70

80

Fig. 2 e XRD patterns of (a) original and pre-calcined hydrotalcite at various temperatures of 800e1200  C and (b) Ni-loaded MgOeAl2O3 (Ni/MgOeAl2O3) powder catalyst pre-calcined at various temperatures of 600e1200  C.

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Ni/MgO-Al2O3
1800 1600 1400
MgAl O Ni

b
Intensity / cps

Ni-Mg-O
7000 6000 5000 4000 3000 2000 1000
MgO

Intensity / cps

1200 1000 800 600 400 200 0 20 30 40 50 60 70 80

20

30

40

50

60

70

80

2 (Cu-K ) / degrees

2 (Cu-K ) / degrees

Fig. 3 e XRD patterns of (a) Ni/MgOeAl2O3 and (b) NieMgeO powder catalysts before activity testing. The Ni/MgOeAl2O3 powder catalyst was prepared using the calcined temperature of 1000  C for original hydrotalcite and at 800  C for Ni loading. The NieMgeO powder catalyst was prepared using calcination temperature of 1200  C.

temperature calcinations of 750e1300  C in the preparation make it possible that the Ni ions were incorporated into the lattice of the MgO support to form an NieMgeO solid solution. The BET surface areas of the NieMgeO powder catalyst that was calcined at 750e1300  C are listed in Table 2. The surface areas of the NieMgeO catalyst were at a maximum value at 1200  C calcination. XRD patterns of the NieMgeO catalyst calcined at 750e1300  C were observed in addition to the measurement of BET surface area. The XRD peaks due to NieMgeO particles broadened after the calcination at 1200  C in comparison to the other calcination temperatures. This result means that the calcination at 1200  C caused a formation of ne particles of an NieMgeO solid solution. The catalytic activities of the NieMgeO powders calcined at various temperatures ranging from 750 to 1300  C were 1 1 in the time span examined at a GHSV of 165 Ndm3 g cat h from 60 to 130 min. The activity tests were performed under homogeneous heating with an electric furnace. The time variations of methane conversion for the NieMgeO powders calcined at 750e1300  C are presented in Fig. 4. The NieMgeO catalyst after calcination at 1200  C exhibited the greatest activity among those calcined at temperatures of 750e1300  C. In addition, the NieMgeO catalyst with H2 reduction (solid circles) showed activity that was substantially higher than that without the H2 reduction (open circles). Fig. 4 also represents time variations of methane conversion for Ni/ MgOeAl2O3 powder catalyst during 70 min of reforming (open squares). The Ni/MgOeAl2O3 powder catalyst sustained 1 1 a 100% methane conversion at a GHSV of 165 Ndm3 g cat h through the time period of reforming, and showed a higher degree of methane conversion than NieMgeO powder catalysts.

In order to optimize a preparation of Ni/MgOeAl2O3 powder catalyst and evaluate the superiority of its catalytic activity to NieMgeO powder catalyst, the catalytic activity of Ni/MgOeAl2O3 powder was examined using MgOeAl2O3 powder pre-calcined at various temperatures ranging from 800 to 1200  C. The activity tests were performed using a GHSV 1 1 of 1155 Ndm3 g cat h , which is 7 times higher than was used 1 1 in the reforming test at a GHSV of 165 Ndm3 g cat h , as shown in Fig. 4. Fig. 5(a) shows the average methane conversion during the time period of reforming and the BET surface area of Ni/MgOeAl2O3 powder catalyst after the activity test. Nevertheless, methane conversion and the BET surface area reached their highest values of 72% and 60 m2 g1, respectively, at a calcination temperature of 1000  C. Next, the catalytic activity of Ni/MgOeAl2O3 powder after Ni

100

Ni/MgO-Al2O3 (1000 C)

80

Methane conversion / %

60
750 C 1000 C

40

1100 C 1200 C 1200 C (without H2 reduction) 1300 C

20

0
Table 2 e BET surface area of NieMgeO powder catalyst after H2 reduction.
Calcination temperature ( C) 750 1000 1100 1200 1300 32.9 14.4 12.4 20.5 0.2 BET surface area (m2/g)

20

40

60

80 100 Time / min

120

140

Fig. 4 e Time variations of methane conversions for the Ni/ MgOeAl2O3 and NieMgeO powder catalysts at GHSV of L1 1 . 165 Ndm3 gL cat h

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a
Average methane conversion / %
80 80

b
BET surface area / (m2/g) Methane conversion / %
60 60

80

60

40

40

40
600 C 700 C 800 C 900 C 1000 C

20

20

20

800

1000

1100

1200

20

40

60

Calcination temperature / C

Time / min

1 L1 Fig. 5 e Reforming performances for Ni/MgOeAl2O3 powder catalyst at GHSV of 1155 Ndm3 gL . (a) Average methane cat h conversion during reforming time of period and BET surface area after the activity test. The hydrotalcite calcined at various temperatures of 800e1200  C was used for a preparation of the catalyst. (b) Time variations of methane conversion. The powder catalysts after Ni loading were calcined at various temperatures of 600e1000  C.

impregnation (Ni 12 wt%) calcined at various temperatures ranging from 600 to 1000  C was examined. Fig. 5(b) shows the time variations of methane conversion for the Ni/MgOeAl2O3 powder catalyst. After Ni impregnation, the maximum methane conversion was obtained at a calcination temperature of 800  C. Therefore, hydrotalcite was calcined at 1000  C, and the obtained mixed oxide of MgOeAl2O3 was subsequently treated for Ni impregnation at 800  C. The resulting

Ni/MgOeAl2O3 powder catalyst was used for irradiation testing of the Ni/MgOeAl2O3/SiC foam absorber.

4.2. Activity of absorbers by solar-simulated Xe-light irradiation

Photographs of the original SiC foam (non-coated) and three kinds of catalytically activated SiC foam absorbers before the

Fig. 6 e Photographs of (a) original SiC foam and (bed) the prepared catalytically activated foam absorbers. (b) Ni/MgO, (c) NieMgeO and (d) Ni/MgOeAl2O3-activated SiC foam absorbers before activity testing.

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700 600

500 400 300 200

20 mm foam
100

30 mm foam
-20 -15 -10 -5 0 0 5 10 15 20

X-axis (mm)

Fig. 7 e Energy ux distribution of incident Xe light on the irradiated surface of the absorber. The total power and ux density for the Xe-light irradiation condition are shown in Table 3.

Xe-light irradiation test are shown in Fig. 6. The color of the original SiC foam was gray, and this did not change after application of the Ni/MgO, NieMgeO, and Ni/MgOeAl2O3 powder catalysts. In addition, many obvious open pores on the prepared SiC foam absorbers were observed that were not clogged by agglomeration of their powder catalysts. Thus, their powder catalysts were successfully well-distributed and loaded onto the SiC foam. Fig. 7 shows the energy ux distribution of the incident solar-simulated Xe light on the irradiated surface of the absorbers. The total power input (Winc) and average ux density of the incident Xe light input into absorbers that had different diameters of 2 and 3 cm are shown in Table 3. The total power input (Winc) of the incident Xe light into the absorbers was 0.120e0.204 kW, and the peak ux density of the incident Xe light on the exposed surface of the absorbers was 547 kW m2. The average ux density (r) on the exposed surface of the absorbers was 289e383 kW m2, which is dened as r Winc/S, where S is the surface area of the irradiated absorbers.

The catalytic activity of the Ni/MgOeAl2O3/SiC, NieMgeO/ SiC, and Ni/MgO/SiC foam absorbers was examined at a GHSV of 25,000 h1(1.34 Ndm3 min1) during Xe-light irradiation for 60 min. The irradiation tests were performed under the abovementioned irradiation condition (Fig. 7). Fig. 8(a) shows the time variations of methane conversion for the Ni/MgOeAl2O3/ SiC foam absorber with a diameter of 2 cm. The loading amount of Ni/MgOeAl2O3 catalyst varied from 1 to 4 wt% with respect to the mass of the SiC foam matrix. As seen in Fig. 8(a), the methane conversion gradually increased with increasing irradiation time for all the foam absorbers, and almost plateaued at an irradiation time of 60 min. The 2 wt% Ni/MgOeAl2O3/SiC foam absorber provided the highest degree of methane conversion among them, which was twice as high as that of the NieMgeO/SiC foam absorber, as described below. Time variations of methane conversion for the Ni/MgO/SiC prepared by the previous method [37] and the NieMgeO/SiC foam absorbers prepared by the present study were examined, and a comparison on the basis of their activity is presented in Fig. 8(b). According to the previous method that employed two wash-coatings for MgO loading and subsequent Ni loading, the methane conversion initially increased but then gradually decreased with increasing irradiation time. In addition, the methane conversion was hardly enhanced at all, although the loading amount of Ni/MgO catalyst was increased. On the contrary, in the case of the present study that used a washcoating of prepared NieMgeO catalyst, the methane conversion increased with an increasing loading amount of NieMgeO catalyst, and deactivation was not observed for the foam absorbers. It can thus be expected that much further loading of NieMgeO catalyst would enhance methane conversion. Fig. 9 shows time variations of temperature and methane conversion for the Ni/MgOeAl2O3/SiC and NieMgeO/SiC foam absorbers when SiC foam with a diameter of 3 cm was used as a foam matrix. The testing of catalytic activity involved examination at a GHSV of 25,000 h1 (1.34 Ndm3 min1) during Xe-light irradiation of 60 min. The temperature was measured in the center of the irradiated surface of the foam absorber. Both foam absorbers displayed nearly constant temperatures of 1070e1080  C for the NieMgeO/SiC foam and 1000e1010  C for the Ni/MgOeAl2O3/SiC foam during the time period of

Table 3 e Results for CO2 reforming with catalytically activated foam absorbers used in this study under the irradiation by high ux Xe light. Foam absorber Dimensions (mm) Total power input (kW)
0.120 0.204 0.120 0.204

Flux density / kW-m-2

Average ux density (kW m2)a

383 289 383 289

Peak ux density (kW m2)b

547 547 547 547

GHSV (104 h1)

Temperature ( C)c

Power of reformed gas (kW)

0.21 0.44 0.11 0.30

Maximum methane conversion (%)

37 35 19 23

Ni/MgOAl2O3/SiC NieMgeO/ SiC

20 10 30 10 20 10 30 10

2.5 2.5 2.5 2.5

995e1033 1002e1008 1030e1084 1067e1085

a Mean ux density of solar-simulated Xe light for irradiation. b Peak (or central) ux density of solar-simulated Xe light for irradiation. c Temperature at the center of the irradiated surface of the absorber.

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Ni/MgO-Al2O3

a
Methane conversion / %

40
2 wt% 4 wt%

b
Methane conversion / %
3 wt% 1 wt%

Ni-Mg-O
30
Ni/MgO/SiC (previous study) Ni-Mg-O/SiC (present study)

30

20

4 wt%

4 wt%

20

3 wt%

3 wt%

10

2 wt% 2 wt%

10

10

20

30

40

50

60

10

20

30

40

50

60

Time / min

Time / min

Fig. 8 e Time variations of methane conversion for (a) the Ni/MgOeAl2O3/SiC foam absorber and (b) the NieMgeO/SiC foam absorber with diameter 20 mm. The loading amount for the powder catalysts varied in 1e4 wt% and 2e4 wt% with respect to the mass of SiC foam matrix.

irradiation. It should be noted that the foam temperature for the Ni/MgOeAl2O3/SiC foam was lower than for the NieMgeO/ SiC foam under the same irradiation condition. The resulting methane conversion was 1.5 times higher for the Ni/MgOeAl2O3/SiC foam than for the NieMgeO/SiC foam during the 2-h period of reforming. These results indicate that Ni/MgOeAl2O3/SiC foam exhibits stable and high catalytic activity during direct irradiation with concentrated Xe light throughout an entire period of at least 2 h. Thus, the Ni/ MgOeAl2O3-activated SiC foam absorber is preferable for use at a relatively high average ux. In the next step of this study, the irradiation time period is much longer, and the thermal endurance, deactivation, and local-overheating of the foam absorber is necessary to be studied for long-term light irradiation at the level of 100 h. The power stored as chemical enthalpy by the overall reaction (Wchem) is plotted against the irradiation time period for the SiC foam absorbers activated with Ni/MgOeAl2O3 and NieMgeO catalysts. The results are shown in Fig. 10. The

Wchem values for the Ni/MgOeAl2O3/SiC foam absorber were 1.8 times greater in the 2-cm foam and 2 times greater in the 3cm foam than those for the NieMgeO/SiC foam absorber. Thus, the higher catalytic activity of the Ni/MgOeAl2O3/SiC foam absorber makes it preferable for use at relatively high values of average ux (r 289e383 kW m2). Fig. 11 shows a comparison of the chemically absorbed power density (Pd) of the SiC foam absorbers activated with Ni/ MgOeAl2O3 and NieMgeO catalysts. The Pd value was plotted against the irradiation time period. The CH4eCO2 mixture was passed through the absorbers at a GHSV of 25,000 h1. The Pd values reached 82e97 kW m2 for the NieMgeO/SiC foam absorbers and 145e151 kW m2 for the Ni/MgOeAl2O3/SiC foam absorbers. The Pd values for the NieMgeO/SiC foam absorbers were 1.8 times greater in the 2-cm foam and 1.5 times in the 3-cm foam than those for the NieMgeO/SiC foam absorber. In order to evaluate the catalytic activity of the present foam absorbers, the Pd values and the light-tochemical energy conversion efciency, hchem, were compared

a
Temperature / C

Temperature

1200

b
Methane conversion / % Ni-Mg-O/SiC

Methane conversion

50 40 30
Ni-Mg-O/SiC Ni/MgO-Al2O3/SiC

1100

1000

Ni/MgO-Al2O3/SiC

20 10 0

900

800

20

40

60
Time / min

80

100

120

20

40

60
Time / min

80

100

120

Fig. 9 e Time variations of (a) temperature and (b) methane conversion for the Ni/MgOeAl2O3/SiC and the NieMgeO/SiC foam absorbers with diameter of 30 mm.

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0.12

Power density absorbed In the chemical reaction (P ) / kWm

Power stored as a chemical enthalpy by the overall reaction (W ) / kW

200
Ni/MgO-Al O /SiC (2 cm)

Ni/MgO-Al O /SiC (3 cm)

0.1

150 100
Ni-Mg-O/SiC (2cm)

Ni/MgO-Al O /SiC (3 cm)

0.08
Ni-Mg-O/SiC (3cm)

Ni-Mg-O/SiC (3cm)

0.06
Ni/MgO-Al O /SiC (2 cm)

50 0

0.04
Ni-Mg-O/SiC (2cm)

0.02

50
Time / min

100

150

50

100

150

Time / min

Fig. 10 e Chemically absorbed power (Wchem) as a function of irradiation time for the Ni/MgOeAl2O3/SiC and the NieMgeO/SiC foam absorbers. with those reported elsewhere. The results for the Pd and hchem values were plotted together with those from the references shown in Fig. 12. The result by Buck et al. [7] was reported in regard to the CAESAR project that was selected as a reference for evaluation of the present results. In most of the literature, the solar demonstration of catalytically activated ceramic absorbers was carried out in much larger volumetric reactors and at higher solar input levels. Thus, their Pd values and hchem values cannot be directly compared with the current results. However, according to the report [7], in the CAESAR project, an Rh/g-Al2O3-activated ceramic absorber with a diameter of 64 cm was mounted in a large-scale volumetric receiverereactor and tested with a higher solar input level of 74e115 kW. Both uniform and non-uniform ceramic absorbers were tested using the absorber design that modeled a at plate foam disk. The results obtained by the uniform absorber were selected and used for comparison in the present paper. As seen in Fig. 12(a), the Pd values for the Ni/MgOeAl2O3/SiC activated ceramic absorber were comparable with those of the CAESER absorber. On the other hand, those of the NieMgeO/ SiC activated ceramic absorber were relatively lower than

Fig. 11 e Power density absorbed in the chemical reaction (Pd) as a function of irradiation time for the Ni/MgOeAl2O3/ SiC and the NieMgeO/SiC foam absorbers. The CH4eCO2 mixture was passed through the absorbers at a GHSV of 25,000 hL1.

those of the CAESER absorber at a high average ux density of irradiation. However, the Pd value could be signicantly improved by the Ru/NieMgeO/SiC activated ceramic absorber in the case that an NieMgeO/SiC absorber loads Ru catalyst on the surface [37]. The chemical storage efciencies, hchem, for the Ni/MgOeAl2O3/SiC and NieMgeO/SiC activated ceramic absorbers were compared with those of the CAESER absorber. As seen in Fig. 12(b), the hchem values for both absorbers increased with an increase in the foam size of the absorber. In addition, the hchem values were 50% for the Ni/MgOeAl2O3/SiC and 34% for the NieMgeO/SiC activated ceramic absorber with the larger foam absorber (Table 3). The hchem value of 50% is comparable with those reported for the CAESER absorber. The present Ni-based catalytic absorbers are more cost effective than conventional Rh/g-Al2O3 and Ru/g-Al2O3 catalyzed SiC foam absorbers. The Ni/MgOeAl2O3 catalyzed SiC foam absorber, in particular, will be desirable for use in solar receiverereactor systems for the conversion of concentrated high solar uxes to chemical fuels via endothermic naturalgas reforming at high temperatures.

a
Power density absorbed in the chemical reaction (P ) / kWm-2

250 200 150 100 50 0 200

Ru/Ni-MgO/SiC CAESAR (Rh/ -Al O /Alumina)

Light-to-chemical energy conversion efficiency / %

Present study (Ni/MgO-Al O /SiC) Present study (Ni-Mg-O/SiC)

80
Present study (Ni/MgO-Al O /SiC) Present study (Ni-Mg-O/SiC) Ru/Ni-MgO/SiC CAESAR (Rh/ -Al O /Alumina)

60

40

20

250

300

350

400

450

0 200

250

300

350

400

450

Average flux density of irradiation / kWm

Average flux density of irradiation / kWm

Fig. 12 e Comparison of (a) chemically absorbed power densities of Pd and (b) chemical storage efciencies of hchem. Symbols: Solid squares and circles are respectively for the Ni/MgOeAl2O3/SiC foam absorber and the NieMgeO/SiC foam absorber in the present study. Asterisk is for Ru/NieMgeO/SiC foam absorber in the previous study [37]. Triangles are for the Rh/g-Al2O3-activated alumina foam absorber in the CAESAR project, estimated from data in [7].

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5.

Summary

For the absorption and chemical conversion of high energy uxes into fuels, Ni/MgOeAl2O3 and NieMgeO activated SiC absorbers were tested by the application of concentrated Xelight radiation (around 280 and 380 kW m2 of average ux density) and examined as to their reforming performance. The Ni/MgOeAl2O3 catalyzed SiC foam absorber is comparable in its chemically absorbed power densities (Pd) and chemical storage efciencies (hchem) to that of the conventional Rh/gAl2O3. Furthermore, the new absorber is more cost effective than the Ru/NieMgeO catalyzed SiC absorber reported in the previous paper. Ni/MgOeAl2O3 catalyzed SiC foam absorber is found to be a promising solar absorber for a volumetric receiverereactor or reformer.

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