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Applied Catalysis A: General 423424 (2012) 176184

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Applied Catalysis A: General


journal homepage: www.elsevier.com/locate/apcata

Dimethyl ether (DME) reforming by microreactor using Cu and Cr as active components over alumina
Rehana Kousar a,b , Do Hyung Kim a , Byung-Yong Yu a , Heon Phil Ha a , Sang Hoon Kim a , Ji Young Byun a,
a b

Interfacial Engineering Research Center, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea School of Science, University of Science and Technology, 176 Gajung-dong, 217 Gajungro, Yuseong-gu, Daejeon, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
A series of plate type anodic alumina (-Al2 O3 ) supported Cu and Cr catalysts were employed to investigate their reactivity in the partial oxidation (PO) of dimethyl ether (DME) in a microreactor. The effect of metal concentration and reaction temperature on DME conversion to hydrogen was assessed. It was found that conversion of DME to hydrogen by PO depends both on reaction temperature and active metal concentration. The catalysts were characterized by surface area (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) techniques. The metal loading as active component was investigated by electron probe micro analysis (EPMA) and X-ray uorescence spectroscopy (XRF). The results showed that Cu as active component on -Al2 O3 possessed better activity than Cr. Further, the catalytic activity of Cu was enhanced in the presence of Cr. The XRD and XPS analysis indicated that enhanced Cu activity in the presence of Cr could be correlated to the partial existence of CuCr2 O4 along with CuO. 2012 Elsevier B.V. All rights reserved.

Article history: Received 18 September 2011 Received in revised form 7 February 2012 Accepted 21 February 2012 Available online 3 March 2012 Keywords: alumina Dimethyl ether Reforming Hydrogen production Cu Cr Catalyst

1. Introduction Fuel cells are being considered as a promising source for generating clean energy. Fuel cells developed for automotive applications [1,2] utilize hydrogen or hydrogen rich gas as main fuel. Although these are a charming and promising prospect to meet future power needs, it is still a challenge to develop reliable technologies which ensure a steady supply of hydrogen to the market. The unacceptably high cost of producing hydrogen is another limiting factor for this technology. Therefore a strong need exists for systems which could alternatively produce hydrogen through the processing of hydrogen rich fuels. Besides various fuels, e.g. hydrocarbons [37], alcohols [810], and biomass as hydrogen source, dimethyl ether (DME) has been recognized as a potential hydrogen source for power generation [1117]. Production of hydrogen from DME is favored due to its various properties including, (a) high hydrogen to carbon ratio, (b) non-toxic and non corrosive nature, (c) high energy density, (d) no C C bond/low reforming temperature of 200400 C, and (e) similar physical properties to LPG that possibly enable adoption of LPG infrastructure to process DME. Moreover, DME can be easily synthesized from natural gas, coal, crude oil, and biomass. Steam reforming [1821] and partial oxidation [1315,22,23] of

Corresponding author. Tel.: +82 2 958 5468; fax: +82 2 958 5391. E-mail address: jybyun@kist.re.kr (J.Y. Byun). 0926-860X/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2012.02.038

DME have been investigated extensively using conventional techniques/packed bed type reactors. Microreaction technology or microprocess engineering is one of the tremendously growing technologies used for processing hydrogen fuels. It has gained utmost importance in comparison with packed bed reactors due to several reasons. Microreactors are normally operated continuously that avoids typical batch workup delays. Also pressurization of materials within microreactors is generally easier than within traditional batch reactors. Moreover, high mass and heat transfer rates in microreactors lead to development of small and compact fuel processing systems. Continuous processes in chemical/pharmaceutical industry are based mainly on microreactor technology [24]. Increasing importance of microreactors is also related to industrial applications of this technology [25,26]. Therefore, this technology is being widely used including the reforming of diesel fuel [27]. The objective of this work is to demonstrate a microreactor system as an efcient and sustained source of hydrogen fuel using Cu and Cr as efcient catalytic materials. In the literature, alumina supported catalysts have been applied for partial oxidation (PO) of DME using conventional xed/packed bed type reactor systems. For instance, Wang et al. [13] investigated PO of DME using a packed bed reactor. Ni, Rh, Ru, Pt, and Ag on Al2 O3 were used as active materials. The oxidation of DME was observed above 300 C and 100% DME conversion occurred at 500 C. It resulted in 76% H2 yield along with the formation of CO, CH4 , HCHO, CO2 , and H2 O as by products. 0.5 wt% Pt/Al2 O3 , 0.2 wt% Rh/Al2 O3 , and 6 wt% Ni/Al2 O3 [14] were also studied as catalysts for partial oxidation of DME in a

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packed bed reactor. The results showed 100% DME conversion over the catalysts but maximum H2 yield obtained was less than 80% along with a considerable amount of C containing products (CO, CO2 , and CH4 ). Chen et al. [15] presented results of DME PO over 1.5 wt% Pt/CeZrO catalyst at 500700 C using a packed bed reactor. The results indicated maximum 77.8% DME conversion. The reaction temperature had a signicant inuence on catalytic performance with maximum 86.7% yield of H2 with CH4 , CO, and CO2 as by products. Although Cu based spinels [19,21,28,29] have also been used as active materials for this reaction, the development of Cu based spinels is a complex process and requires a lot of time and effort. In the present study, we have prepared porous anodic aluminum oxide plates (Al2 O3 ) as catalytic support and used Cu and Cr as active components over the support as catalyst in a microreactor. Our approach to oxidation of DME by microreactor is a new idea and not reported elsewhere as far as we know. We chose Cu and Cr as possible active materials for this reaction as Ismagilov and coworkers showed high efciency of CuCr oxide in microreactors for oxidation of n-butane [4].

2. Experimental 2.1. Support preparation Porous anodic aluminum oxide (AAO) was rst reported about 57 years ago [30] and has a long history. It is used as catalyst itself and as support also in many processes. Many investigations of alumina properties have been carried out to understand its responsibility for a variety of catalytic reactions [31,32]. Development of electron spectroscopy helped a lot to understand its structure and function. The structure of porous AAO is usually described as a defect cubic spinel with the aluminum ions somewhat randomly distributed between the octa- and tetrahedral sites. Generally, catalytic properties are related to surface area, pore volume, and pore diameter of the surface. The low surface energy and, hence, high surface area of alumina make its extensive use as catalyst support [3,4,18,31,33]. A commercial aluminum plate (A1050, 99.5% purity from CHOIL Aluminum) with a thickness of 1 mm was used as the substrate to prepare alumina support (26 m thickness) for the microreactor. An aluminum plate was rst cut into 2cm 4 cm and rinsed with acetone. Each rinsed plate was pretreated in a 20 wt% sodium hydroxide solution (1 L) for 3 min at 60 C followed by being rinsed with deionized water. It was further treated in 30 vol.% aqueous solution of nitric acid (1 L) for 1 min at room temperature followed by being rinsed with deionized water and air shower. This pretreated plate was anodized in a 4.0 wt% oxalic acid solution (2000 ml) at 30 C at electric current density of 150 A/m2 to form a porous alumina support layer for a microreactor. Thickness of the alumina was controlled by controlling the current density and the time of anodization. Anodic oxidation process can be considered as a combination of alumina formation and dissolution. A graphite plate was used as cathode against aluminum plate. Polyimide tape was used for masking the unrequired area for anodization. A magnetic bar was used for agitation with a speed of 240 rpm to prevent defects caused by air bubbles on aluminum surface in the electrolyte. After formation of porous alumina layer, pore widening treatment (PWT) was carried out at 30 C for 4 h in the same oxalic acid solution used for anodization. After completion of PWT, plate was washed in an ultrasonic cleaner at room temperature for enough time to remove residual oxalic acid. Immediately after the ultrasonic washing, it was subjected to hot water treatment (HWT) in deionized water at 85 C for 1 h. Finally, the alumina layer with a high surface area was obtained by calcination in air at 500 C

Fig. 1. The ow scheme of the support preparation for microreactor.

for 3 h. Density of the synthesized alumina was found to be 1.74 g/cm3 . 2.2. Catalyst preparation Cu(NO3 )2 3H2 O and Cr(NO3 )3 9H2 O were used as precursors for PO of DME. Anodic alumina supported metal catalysts with metal loadings of 3, 6, 9, and 12 wt% (based on the weight of the alumina layer) were prepared by impregnation method. The support was impregnated with an aqueous solution containing required amount of the metal nitrates followed by drying and calcination at 500 C for 3 h. The alumina plates were referred to according to their loadings with the active components. In the rst set of experiment, only Cu(NO3 )2 3H2 O was used as catalytic material. In the second set of experiment, only Cr(NO3 )3 9H2 O was used and in the third set of experiment, physical mixture of both salts with the Cu and Cr

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Fig. 2. SEM images of anodic alumina support surface (a) after anodization, (b) after PWT, (c) after HWT, and (d) after calcination.

ratio of 1:2 was used. Index Cu/Al2 O3 in the sample name stands for copper loaded alumina plates and index Cr/Al2 O3 stands for chromium loaded alumina plates and CuCr/Al2 O3 stands for alumina plates loaded with physical mixture of both Cu and Cr (with the Cu and Cr ratio of 1:2). Fig. 1 shows ow scheme of the support preparation. For a relevant comparison between DME PO in a microreactor with that in a packed bed reactor, a reference sample of CuCr catalyst was prepared by impregnation of spherical alumina granules (1.72.0 mm, the BET surface area 300 m2 /g) with an aqueous solution of the same amount of CuCr as used for 9 wt% impregnated alumina plates for the microreactor. This was followed by drying under IR lamp for 30 min and calcination in air at 500 C for 3 h. The catalytic activity of this CuCr impregnated alumina granules was determined using a conventional packed bed reactor. The quartz tube reactor (8 mm i.d.) was mounted vertically in an electric furnace. 0.45 g of impregnated alumina granules was used to evaluate the catalytic activity. The overall ow rate of the inlet reactants was kept similar to the microreactor system. 2.3. Characterization of support and catalyst The alumina support and catalyst materials were fully characterized by various techniques. The BET surface area and pore diameter of support and catalyst were determined by nitrogen adsorption method (SA3100, Beckman Coulter, Inc.). The thickness of alumina lm was measured by binocular microscope. The

morphology of the anodic alumina support was examined by scanning electron microscope (HR-LV-SEM, Hitachi, Ltd.). The SEM images of anodic alumina support surface are given in Fig. 2 (top view) and in Fig. 3 (cross section). Anodic alumina formed just after anodization was observed to have pores with smooth pore walls (Figs. 2a and 3a). Specic surface area of 0.44 m2 /g was measured for this anodic alumina which is quite low compared with traditional alumina powders. This surface area was improved by applying PWT, HWT and drying technologies. PWT widened the pore diameter that helped the bottom layer of alumina to effectively react with hot water. Clear widening of pores is observed in Figs. 2b and 3b. HWT resulted in the formation of hydrated alumina by hot water and anodic layer interaction. Al2 O2 + nH2 O Al2 O3 nH2 O The interaction of anodic layer with hot water further resulted in hydrated alumina sol that accumulated on pore skeleton and made appearance of the surface as akes (Figs. 2c and 3c). Calcination after HWT (500 C, 3 h) resulted in packing of the pore skeleton by alumina particles (Figs. 2d and 3d). All these surface treatments of anodic alumina layer resulted in a drastic increase of BET area from 0.44 m2 /g to 129 m2 /g. The metal loading as active component was investigated by electron probe micro analysis (EPMA) (JXA-8500F, Jeol Ltd.) and X-ray uorescence spectroscopy (XRF). XRD (ATX-G, HR XRD, Brooder

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Fig. 3. SEM images of anodic alumina support (cross section) (a) after anodization, (b) after PWT, (c) after HWT, and (d) after calcination.

Ltd.) and XPS (Shimadzu ESCA) were used to analyze the oxidation state of the support and catalyst. The XPS was equipped with an Al K radiation source (1486.6 eV) and operated at 10 kV. Each binding energy was referenced to the C 1s peak (284.3 eV). 2.4. Evaluation of catalytic activity in DME PO Evaluation of the catalytic activity was carried out using a microreactor. A DME reforming system was set to analyze catalytic activity associated with the prepared porous anodic alumina support layer using Cu and Cr as the active metals. The microreactor was designed to accommodate two synthesized alumina plates

in a parallel manner. A detailed arrangement of the plates in the microreactor is shown in Fig. 4. A spacer was inserted between the alumina plates to maintain a distance of 1 mm between the two plates. Gas leakage was prevented by inserting a piece of graphite sheet between the frame and the alumina plates. This microreactor system was mounted horizontally in an electric furnace. DME PO reforming was carried out in the temperature range between 20 C and 550 C at atmospheric pressure. The reaction gases (DME, oxygen, and nitrogen) were supplied to the microreactor through mass ow controllers. The ow rate of DME:O2 :N2 was xed to 3:5:20 ccm. Hydrogen yield and carbon products of DME reforming were measured using gas chromatography (CP3800, Varian).

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100 80

3wt% Cu 6wt% Cu 9wt% Cu 12wt% Cu

DME Conversion (%)

60 40 20 0

Fig. 4. Microreactor containing alumina plates for partial oxidation of DME.

50 10 00 150 200 250 300 3 350 400 450 500 550 600

Tem mp( C)
3. Results and discussion 3.1. Performance of catalysts in DME PO Cu(NO3 )2 3H2 O and Cr(NO3 )3 9H2 O were used as precursors for PO of DME in a microreactor. Cu/Al2 O3 , Cr/Al2 O3 , and CuCr/Al2 O3 were comparatively investigated for the titled reaction. For each experiment, standard gas with a composition of 20.9% H2 , 14.8% CO, 19.9% CO2 , 14.9% CH4 , and 29.5% N2 was used as reference. Figs. 5 and 6 show DME conversion rates and hydrogen yields obtained through PO of DME using selected amounts (3, 6, 9, and 12 wt%) for each of the Cu/Al2 O3 , Cr/Al2 O3 , and CuCr/Al2 O3 , respectively. When we compare graphs in Fig. 5 to graphs in Fig. 6, we can see that the hydrogen production is directly related to the DME conversion rates as discussed below. The DME conversion rates to hydrogen in Fig. 5 show that high DME conversions were obtained on all catalysts. It started around 200 C and increased with increasing reaction temperature of the microreactor system. However, difference in the DME conversion rates became smaller when the temperature increased up to 400550 C. DME was highly reactive for oxidation and maximum conversion rates achieved were 95.5% for both of Cu/Al2 O3 and Cr/Al2 O3 , and 100% for CuCr/Al2 O3 . This result showed that these catalysts were actively involved in PO reaction. But it is also obvious that Cu/Al2 O3 and Cr/Al2 O3 have comparatively lower reactivity and higher reaction temperature for PO of DME than CuCr/Al2 O3 . Moreover, among the various selected metal loadings of all the three types of catalysts, an increase in DME conversion rate was found from 3 wt% to 9 wt% of metal content. However a decrease in DME conversion rate was obtained with further increase of metal content to 12 wt%. We suspect that the highest metal loading (12 wt%) might have caused blocking of some pores by high metal contents. It could have lead to aggregation/agglomeration of active materials and decrease of exposed active sites of the catalyst and consequently reduced the hydrogen production for 12 wt% of the metal loading. The hydrogen yields in Fig. 6 show that it depends upon metal content and reaction temperature, too. The three catalyst systems for hydrogen yield fall in the order of CuCr/Al2 O3 > CuAl2 O3 > Cr/Al2 O3 . The maximum yield of hydrogen was achieved over a temperature range of 400550 C. The highest yield of hydrogen produced was 97.11% (at 400 C), 86.12% (at 400 C) and 18.88% (550 C) for the CuCr/Al2 O3 , Cu/Al2 O3 , and Cr/Al2 O3 , respectively. With further increase in temperature, the selectivity to hydrogen decreased. As the CuCr/Al2 O3 showed the highest selectivity towards hydrogen, it suggested that addition of Cr enhanced the catalytic reactivity of Cu in the reaction. Concerning the hydrogen yield, it was also affected by metal loading concentration. The hydrogen yield increased with increasing metal

b
100 80
DME conversion (%)

3wt% Cr 6wt% Cr 9wt% Cr 12wt% Cr

60 40 20 0 0 50 100 150 200 250 300 350 400 450 500 550 600

Temp( C)

100

80

DME Conversion (%)

3wt% CuCr 6wt% CuCr 9wt% CuCr 12wt% CuCr P.Bed (9wt%)

60

40

20

0 0 100 200 300


0

400

500

600

Temp ( C)
Fig. 5. DME conversion over (a) Cu/Al2 O3 , (b) Cr/Al2 O3 , (c) CuCr/Al2 O3 catalyst for PO of DME under reaction conditions of DME:O2 :N2 3:5:20 ccm at atmospheric pressure.

loading from 3 wt% to 9 wt% but a decreased value was obtained for 12 wt%. It was the same trend as that of the DME conversion rate. The highest hydrogen yield was produced by 9 wt% of metal loadings. This trend was observed with all the three types of metal catalysts. In view of the fact that DME conversion rates and H2 yields over the dual CuCr/Al2 O3 catalysts (9 wt%) were higher than those over the individual Cu/Al2 O3 and Cr/Al2 O3 , the CuCr/Al2 O3 could be successively used for PO of DME. Therefore, the CuCr/Al2 O3 catalyst was selected for further study described below.

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100

Table 1 The BET surface area and pore properties of CuCr/Al2 O3 catalyst.
0

H2 Yield (%)

85.32%, 400 C 0 88.38%, 400 C 0 86.12%, 400 C 0 60 74.93%, 400 C


80 40

3wt% Cu 6wt% Cu 9wt% Cu 12wt% Cu

Sample (wt%) alumina 3 6 9 12

BET surface area (m2 /g) 129 87.39 78.11 74.08 81.59

Average pore diameter (nm) 7.6 3.11 2.23 1.72 1.06

20

0 0 50 100 150 200 250 300 350 400 450 500 550 600

Temp (C)

30

12.25%, 550 0 C 14.25%, 550 C 0 18.88%, 550 C 20 11.64%, 550 0C


H2 Yield (%)

3wt% Cr 6wt% Cr 9wt% Cr 12wt% Cr

10

in pore diameter continued with the increase of metal contents on the alumina surface. Therefore, the decreased surface area and pore diameter for the catalysts cannot be correlated to the decreased hydrogen production or DME conversion rate for 12 wt% of metal content [11]. Again, the highest metal loading (12 wt%) might have caused the blocking of some pores by high metal contents. It could have lead to aggregation/agglomeration and decrease of the exposed active sites of catalyst and consequently reduced the reactivity. Fig. 7 shows the effect of temperature on the yields of C containing byproducts for 9 wt% of the CuCr/Al2 O3 catalyst. The yields of carbon products are in the order of CO2 > CO > CH4 . From the yields of C containing products, it was concluded that formation rate of CH4 increased with increasing reaction temperature. Below 400 C, no CH4 was observed and its formation started around 400 C. It increased from 0.60% to 12.28% when the temperature was increased from 400 C to 550 C. The following two reaction routes are considered as responsible for the formation of CH4 involving decomposition of DME and second hydrogenation of CO. CH3 OCH3 CH4 + CO + H2 (1) (2)

50 100 150 200 250 300 350 400 450 500 550 600

CO + 3H2 CH4 + H2 O

Temp (C)

100 79.78%, 500 0C

86.90%, 400 0C 97.11%, 400 C 0 80 80.77%, 550 C 0 52.04%, 300 C


60 40 20

3wt% CuCr 6wt% CuCr 9wt% CuCr 12wt% CuCr P.Bed (9wt%)

H2 Yield (%)

Fig. 7 also shows that the decomposition of DME into CH4 was favored at high reaction temperatures. Since chemical equilibrium does not favor CO methanation (Eq. (2)) at higher temperatures, formation of CH4 may be due to DME decomposition. It was reported [34] that DME decomposition at high temperature resulted in production of methyl and methoxy species. These methyl species can be further hydrogenated to form methane (Eqs. (3) and (4)). Therefore, an increase in CH4 formation was observed with the increase of reaction temperature. CH3 OCH3 CH3 O + CH3 CH3 + H CH4
100

(3) (4)

0 0 100 200 300 400 500 600 80 60 40 20 0 150 200

CO CO2 CH4

Temp (C)
Fig. 6. Hydrogen yield over (a) Cu/Al2 O3 , (b) Cr/Al2 O3 , (c) CuCr/Al2 O3 catalyst for PO of DME under reaction conditions of DME:O2 :N2 3:5:20 ccm at atmospheric pressure.

Although for packed bed reactor 99.35% of DME conversion was achieved (Fig. 5c) the hydrogen yield was limited to 52.04% which is much lower compared to microreactor system under the same reaction conditions (Fig. 6c). Table 1 summarizes the BET surface area and pore diameter of the CuCr/Al2 O3 catalysts. Both the surface area and pore diameter of the CuCr/Al2 O3 decreased clearly with increase of the metal contents. Pore diameter decreased rapidly from 7.6 nm to 3.11 nm with the introduction of metal contents to the alumina. This decrease

Yield (%)

250

300

350

400

450

500

550

600

Temp (C)
Fig. 7. Distribution of C-products for CuCr/Al2 O3 for PO of DME under reaction conditions of DME:O2 :N2 3:5:20 ccm at atmospheric pressure.

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8000 Cu 80 Cr 6000
4Cr

(K alpha)

meas.concen.(nor.)

CuCr 60

1= 3wt% 2= 6wt% 3 = 9wt% 4 = 12wt%

4000

2 4 3 2 1

yield (%)

40

2000

Cu (K alpha)

0 20 4 0 CO CO2 CH4 6

KeV

10

Fig. 9. XRF data showing the measurement of Cu and Cr concentration in the metal impregnated alumina plates for CuCr/Al2 O3 catalysts.

Fig. 8. Comparison of C-products for 9 wt% of Cu/Al2 O3 , Cr/Al2 O3 , CuCr/Al2 O3 catalyst for PO of DME under reaction conditions of DME:O2 :N2 3:5:20 ccm at atmospheric pressure.

samples of CuCr/Al2 O3 , the metal loadings were incorporated mostly within 20 m of alumina layer. 3.3. XRD and XPS characteristics of CuCr/Al2 O3 catalysts The oxidation states of Cu and Cr in the catalysts were determined by XRD and XPS analysis. Fig. 11a shows XRD patterns of the CuCr/Al2 O3 catalysts with various wt% of catalyst before reaction (BR). Fig. 11b shows those after reaction (AR). After calcination in air at 500 C, the Cu precursor was mainly transformed to CuO (Fig. 11a). The intensity of CuO increased with increasing metal concentration. Other phases of Cu such as CuCr2 O4 were also formed in the presence of Cr species along with CuO. Alumina was present in phase for all the catalyst samples. The peaks at 2 of ca. 37 , 46 , and 67 are characteristic of alumina (the CuCr2 O4 peaks were overlapped by the alumina peaks). The diffraction peaks of CuO were observed at 39 and 82.5 . The peak for Cr2 O3 was observed at 42 . Although the weak peaks of CuCr2 O4 were not observed for the lowest metal content (3 wt%), these were developed and sharpened with increasing metal contents. The peak for CuCr2 O4 appeared at 54 and its second peak at 82.5 was overlapped by that of CuO. This observation indicated that Cu was partially transformed to CuCr2 O4 in the presence of Cr species resulting in the partial existence of Cu in the form of CuO and CuCr2 O4 . Meanwhile, no diffraction peaks for Cu and Cr appeared, among which the strongest peak should appear at ca. 74 and 81 for Cu and Cr, respectively. This suggested that metal particles were dispersed very well on the supports and
12 10 8 3wt% 6wt% 9wt% 12wt%

In the case of CO, its formation started around 350 C and below this temperature no CO was observed. CO yield was increased from 4.64% at 350 C to 35.51% at 550 C. As for CO2 , higher yields were observed than those of CO. Its formation started around 300 C. The maximum CO2 yield (87.16%) was observed at 350 C and a clear decrease in CO2 yield occurred with further increase in temperature, reaching 67. 36% at 500 C. Fig. 8 shows a comparison of distribution of carbon containing products for 9 wt% of the Cu/Al2 O3 , Cr/Al2 O3 and CuCr/Al2 O3 catalysts at the temperatures where maximum hydrogen yield was obtained. The yields of carbon products are in the order CO2 > CO > CH4 . Their yield increased with increasing temperature corresponding to the DME conversion rates. The CuCr/Al2 O3 produced lesser amount of CO compared to the individual catalysts of the Cu/Al2 O3 and the Cr/Al2 O3 . This observation suggests that the CuCr/Al2 O3 will serve better for fuel cell technology being less harmful due to less CO content. Concerning the amount of CO2 produced, these catalyst systems fall in the order Cu > CuCr > Cr supported on alumina. CO2 may also be formed by the oxidation of CO. In contrast to CO and CO2 , the amount of CH4 produced was very little and no other higher hydrocarbons were detected. The CH4 yield over CuCr/Al2 O3 was 0.6% which was less than that of the individual Cu/Al2 O3 (1.88%) or Cr/Al2 O3 (0.89%). The minute amount of CH4 produced at the reaction temperature of interest that produced maximum hydrogen (400 C) suggested that the CuCr/Al2 O3 catalyst is efcient for hydrogen production. It also indicated that main reaction occurring at this temperature is PO of DME (Eq. (5)) and not decomposition (Eq. (1)) CH3 OCH3 + (1/2)O2 2CO + 3H2 3.2. Metal content on the alumina surface (5)

wt%

6 4 2 0 0 5 10 15 20 25

The concentration and distribution of metal contents in the anodic alumina support were monitored by XRF and EPMA analysis. Fig. 9 shows the concentration of metal contents in the impregnated alumina plates measured by XRF. The analysis indeed showed that metal contents are increasing with increasing wt% of metal loadings. The EPMA point analysis studies of the CuCr/Al2 O3 were also performed after impregnation and calcination at 500 C but before performing the PO reaction, i.e., before reaction (BR) (Fig. 10). These results show that metal contents are highest at the surface and decrease with the depth of the alumina layer. For all the catalyst

m
Fig. 10. EPMA point analysis of CuCr/Al2 O3 for metal content distribution along the depth of anodic alumina support (a) before PO reaction and (b) after PO reaction.

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Fig. 11. XRD patterns of CuCr/Al2 O3 catalysts: (a) BR and (b) AR.

dispersion was not affected signicantly by the metal content concentration. Moreover, the bulk structure of alumina was kept well during the reaction. We can assume that the oxidation state of Cu species from the transformed phase would remain considerably stable since the catalytic activity of the catalysts remained highly efcient. This was proved from XRD patterns of the AR catalysts (Fig. 11b). All the AR catalysts were consisted of three phases of CuO, Cr2 O3 , and CuCr2 O4 along with alumina. The copper crystallites maintained their existence in the form of mixed oxides of CuO and CuCr2 O4 after reaction. The diffraction patterns of the catalysts in the AR samples were almost unchanged. The copper oxides were stable under the present oxidation reaction conditions. We suspect that the stability of these species could be a reason for the catalytic efciency of the CuCr/Al2 O3 catalysts. For the highest metal content (12 wt%), the peaks were quite intense and sharp and some extra peaks were also observed. These extra peaks may be due to diffraction from the CuCr2 O4 phase. We believe that the decreased efciency of 12 wt% metal content for DME PO could be correlated to some agglomeration effects and this was supported by XPS results as discussed below (Fig. 12). Similar behavior of the temperature induced transformation was observed for Cr species. The active phase for DME PO was mainly assigned to the CuO phase that could be transformed to CuCr2 O4 in the presence of Cr2 O3 . These results suggested that Cr enhanced the catalytic activity of Cu due to CuCr2 O4 type structure formation. The increase in activity with the increased active metal content would be attributable to the enhanced CuCr2 O4 formation. This indicated that Cu species was not reduced to zero valence or mono-valence and existed only in mixed oxide form. Fig. 12 shows the XPS spectra of Cu 2p3/2 for the CuCr/Al2 O3 . For the BR catalysts in Fig. 12a, the divalent oxidation state of Cu (Cu2+ ) mainly existed in the catalysts. At 12 wt%, the observed

Fig. 12. XPS spectra of CuCr/Al2 O3 : (a) Cu 2P3/2 BR and (b) Cu 2P3/2 AR.

peak could be related to the known peak at 933.6 (CuO) and at 934.6 eV (CuCr2 O4 ). On the other hand, the characteristic peak of Cu(NO3 )2 at 935.5 eV was absent, indicating that it was converted to an oxide form. This observation indicated that during calcination at 500 C the Cu species was essentially transformed to CuO and some CuCr2 O4 and that metallic Cu was not formed. Fig. 12 also shows that the peak intensity decreased with decreasing metal content down to 3 wt%. Further, a small peak shift from the bulk value was observed as the metal content was decreased from 12 wt% to 3 wt%. This shift occurred probably because of the size effect of the metal oxide particles. While the peak retained the bulk position at 12 wt% BR, it was also shifted from the bulk values in the AR catalyst sample (Fig. 12b). This observation suggested that the agglomerated particles at 12 wt% were decomposed into smaller particles during the reaction. Except this peak shift at 12 wt%, we did not observe any other changes in the XPS peaks between the BR and AR catalysts. The dominant appearance of Cu2+ species as CuO and CuCr2 O4 in both the BR and AR catalysts conrmed the stability of the catalyst. Cu species were difcult to reduce under the conditions employed and therefore the oxidation state of copper remained stable. 4. Conclusions The catalytic performances of Cu and Cr over alumina in DME PO were investigated using a microreactor. Cu and Cr were impregnated over the prepared alumina support. The catalyst and support were characterized by means of SEM, XPS, XRD, EPMA, XRF, and N2 adsorption techniques. The conclusions based on the present ndings are as follows

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I Cu was highly active for dimethyl ether partial oxidation (DME PO) for production of hydrogen. Cr exhibited much lower catalytic activity than Cu for DME PO. However, the addition of Cr to Cu on the anodic alumina support enhanced the catalytic activity of Cu. II The hydrogen production was temperature dependent and its highest yield was obtained at the temperature range of 400550 C. The DME conversion and hydrogen production were also affected by active component concentration and increased with increase of the active component concentration over alumina up to 9 wt%. With further increase of active materials up to 12 wt%, however, the reactivity decreased. III By investigating the oxidation state of Cu, we could conclude that Cu(NO3 )2 3H2 O was transformed to CuO during calcination at 500 C in air. The calcination in the presence of Cr(NO3 )3 9H2 O resulted in the co-existence of CuO with CuCr2 O4 . The high catalytic activity of Cu in the presence of Cr could therefore be attributed to the presence of CuCr2 O4 . IV The maximum hydrogen yield produced was 97.11% for the CuCr/Al2 O3 catalyst. Therefore, it can be claimed that present suggested catalyst of Cu and Cr over alumina exhibited excellent activity for DME PO. V The direct use of Cu and Cr over alumina in microreactors as well as its availability and cheaper rates would contribute effectively to the facilitation/downsizing of the system and reduction of H2 costs. Acknowledgement This work was supported by a grant from the Fundamental R&D Program for Core Technology of Materials funded by the Ministry of Knowledge Economy, Republic of Korea. References
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