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Temperature-programmed oxidation of coked noble metal catalysts after autothermal reforming of n-hexadecane
E.I. Kauppi a,*, R.K. Kaila b, J.A. Linnekoski a, A.O.I. Krause a, M.K. Veringa Niemela a
a

Aalto University, School of Science and Technology, Department of Biotechnology and Chemical Technology, Research Group Industrial Chemistry, P.O. Box 16100, FI-00076 Aalto, Finland b VTT Technical Research Centre of Finland, Biologinkuja 7, Espoo, P.O. Box 1001, FI-02044 VTT, Finland

article info
Article history: Received 23 February 2010 Received in revised form 25 April 2010 Accepted 8 May 2010 Available online 16 June 2010 Keywords: ATR TPO Mono- and bimetallic Rh Pt Zirconia

abstract
Autothermal reforming (ATR) of n-hexadecane was carried out on zirconia-supported mono- and bimetallic noble metal (Rh, Pt) catalysts at 600, 700, and 800  C. After ATR, the reactivity of coke deposits (2.8e9.9 wt%) on the catalysts was investigated by temperatureprogrammed oxidation (TPO). Analysis of the results obtained from ATR and TPO experiments at various temperatures and on the different catalysts gave information on the reaction conditions where the detrimental coke can be minimized and allows estimating the nature of carbon deposits. H2 production increased with temperature on the tested Rh-containing catalysts and the ZrO2 support, but decreased as a function of temperature on the Pt catalyst. The formation of coke was least at 800  C, evidently due to the intensifying reaction of carbon and steam with increasing temperature, as well as to the better activity of the catalysts. The amount of coke formed was highest at 700  C. Comparison of the TPO proles obtained for the monometallic Rh and Pt catalysts with the bimetallic RhPt revealed differences in the nature of carbon deposits on their surface. At 600  C, the coke formed on the monometallic Rh and Pt catalysts was located mostly on the support, whereas on the bimetallic RhPt catalyst the formation of this type of coke was suppressed. The bimetallic RhPt catalyst also exhibited better tolerance toward coking at 700  C. Therefore, although the selectivity toward hydrogen was not related to the amount of coke formed, the deactivation patterns differed on the mono- and bimetallic catalysts. 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Fuel cells, where hydrogen functions as the prominent energy carrier, are currently the most efcient devices for converting chemical energy to electricity [1]. When they are introduced to the energy supply system in the transportation sector, emissions to air and noise can be reduced locally. Thus far, infrastructure for H2 storage and production is lacking, which is a critical issue for establishing a hydrogen fuel distribution

system. An attractive option is on-site H2 production with a local distribution network [2,3]. Conventional hydrocarbon fuels benet from the wellestablished infrastructure and provide a source of chemically bound hydrogen in very dense form. Autothermal reforming (ATR) of a renewable fuel such as renewable diesel is thus considered as a promising way for producing H2-rich gas onsite since the existing infrastructure for production and distribution can be utilized [3,4]. At the high temperatures

* Corresponding author. Tel.: 358 9 451 22666; fax: 358 9 451 22622. E-mail address: inkeri.kauppi@tkk. (E.I. Kauppi). 0360-3199/$ e see front matter 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2010.05.046

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required in this process, however, the long-chained hydrocarbons and aromatics in the fuel tend to form coke on the catalysts thus modifying their selectivity and leading to deactivation in elongated use [5,6]. The ATR process is a hybrid of partial oxidation (POX) and steam reforming (SR) reactions [7]. Several studies on coke formation and catalyst deactivation in reforming processes (ATR, POX, SR) have been published [4,5,8e14]. The coke has been reported to be either catalytic or non-catalytic. The catalytic coke is a result of catalyzed reactions on the surface, whereas the non-catalytic coke is formed as the result of gas phase reactions, such as thermal cracking of hydrocarbon chains. Thermal cracking produces alkenes and free radicals that form polymerized deposits on the catalyst surface [6,10,11]. In addition, elemental carbon may be formed in the ATR process via reactions (1)e(3) [4,6,9e11,15]:

2CO 5 C(s) CO2 (Boudouard reaction) Dr H0 700  C 171 kJ=mol CO H2 5 C(s) H2O Dr H0 700  C 136 kJ=mol CH4 4 C(s) 2H2 Dr H0 700  C 89 kJ=mol (3) (2) (1)

Temperature-programmed oxidation (TPO) has been widely used to study coke formation [17,19]. TPO enables characterization of coke deposits through oxidation of the coke on the catalyst surface. The temperature at which oxidation occurs is determined by the location and chemical nature of the coke species. Since metals catalyze oxidation, the location is represented by the distance from the active metal. Moreover, the more graphitic forms of coke oxidize at high temperatures [20]. Different forms of coke can thus be classied with respect to their chemical nature and location on the catalyst. We used TPO to investigate the differences in the reactivity of coke formed on noble metal catalysts and their zirconia support in ATR of n-hexadecane, which was taken as a model compound for diesel fuel. Comparing the results obtained from ATR and TPO experiments makes it possible to evaluate coke formation at various reaction temperatures and to elucidate the type of coke formed on different catalysts. The reaction conditions minimizing coke formation can be dened and, more importantly, understanding is gained of the factors affecting characteristics of coke. Thermodynamic calculations were performed in support of the experimental observations.

2.
2.1.

Experimental
Catalyst preparation

All three reactions are reversible [15]. Surface carbon (C(s)) is considered to be a reaction intermediate in reforming of hydrocarbons, which adopts chained forms with high molar mass unless it is gasied from the surface. Gasication of C(s) occurs in reactions with H2O, H2, O2, and CO2, the rate being dependent on the stability of C(s). The formation of coke is thus determined by the relative rates of formation of C(s) and gasication [10,11]. In addition to catalytic activity and selectivity, coking is affected by reaction conditions, such as water content in the feed, reaction temperature and reaction time. Temperature will often have the greatest effect on the type of coke formed, and it varies from polymerized, aromatic structures to more graphitic types of coke with low H-content [16,17]. In sum, coking involves a complicated series of reactions, which are affected by various factors in the process, as well as by the catalyst itself. Noble metal catalysts are more tolerant toward coking than conventional nickel catalysts. In addition, their better activity means that less metal is needed. Higher activity together with the better resistance toward coking extends catalyst lifetime, making the use of noble metals feasible [18]. Despite the better activity of noble metals, coke formation remains a challenge for the advent of fuel-cell-integrated reformers to be used in energy generation. In a fuel-cellpowered device, the reforming catalyst must remain active and selective and coking cannot be tolerated [7]. Thus, better understanding of the phenomena affecting coke formation in ATR is required to develop the noble metal catalysts applicable for ATR devices.

Monometallic noble metal (Pt, Rh) catalysts were prepared by dry impregnation on ZrO2 support (MEL Chemicals EC0100) with solutions of Pt(NH)2(NO2)2 (SigmaeAldrich, 3.4 wt% Pt) and Rh(NO)3 (SigmaeAldrich, 10 wt% Rh). The bimetallic RhPt catalyst was prepared by two sequential dry impregnations of these precursors. The intended metal loading of the RhPt catalyst was 0.26 wt% of Rh and 0.24 wt% of Pt. The support was ground and sieved to particle size of 0.25e0.42 mm and calcined at 900  C for 16 h (temperature ramp 5  C/min). The thus pretreated support was dryimpregnated with the above mentioned precursors. After impregnation, the catalysts were equilibrated at room temperature for 4 h and dried in an oven (100  C) overnight. During drying, catalysts were not removed from the glass vessel they were impregnated in. Catalysts were then calcined in a plug ow reactor under air ow (107 ml/min, AGA, 80% N2, 20% O2) at 900  C for 1 h (temperature ramp 1.3  C/min). The total noble metal loading obtained by this method is 0.5 wt% [4]. The physicochemical characteristics of the noble metal catalysts have been evaluated previously by Kaila et al., who determined for example the catalysts BET-surface area and metal loadings. Moreover, scanning electron microscopy (SEM) was used to examine the surface morphology of the catalysts [4].

2.2.

Catalyst testing in ATR of n-hexadecane

ATR reactions of n-hexadecane were carried out on noble metal catalysts and the support material (0.2 g) in a tubular

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quartz reactor (din 10 mm) at 600e800  C and atmospheric pressure. The reactor feed consisted of n-hexadecane (Merck, !99%), distilled water, and air (AGA, 80% N2, 20% O2), whose cumulative ow rate was 300 ml/min (NTP). Argon (AGA, 99.999%, 600 ml/min NTP) was used to dilute the reaction mixture thus resulting in a total ow of 900 ml/min (NTP). Feed line was kept at 250  C, which was estimated to be a sufcient temperature to maintain the n-hexadecane vaporized yet avoiding thermal cracking of the hydrocarbon chains. When preparing the feed mixture, n-hexadecane and distilled water were fed separately via high performance liquid chromatography pumps (HPLC, Agilent Technologies) to a vaporizer. The compounds were vaporized at 300  C and after that mixed with air. The optimized values for O2/C and H2O/C molar ratios in the feed mixture were 0.34 and 3.00, respectively [18]. Air and argon were fed via mass ow controllers (Brooks 5850). The reactor was equipped with a furnace (Carbolite) that allowed temperature control. Temperature of the catalyst bed was measured via a thermocouple inserted in a thermo well in the middle of the bed. This provided information on the actual reaction temperature. Figures represent the calculated values against the set reaction temperature. However, it is recognized that this is not the actual temperature of the reaction.

Calculation of the CO to CO2 ratio allows evaluating the occurrence of the Boudouard reaction (reaction (1)) and the WGS reaction (reaction (6)) [21]. Thermodynamic calculations were performed using HSC Chemistry version 6.12 [22].

2.4.

TPO of catalysts after ATR experiments

2.3.

Product analysis

After the reactor, the product stream was diluted with nitrogen (AGA, 99.999%, 900 ml/min NTP) to facilitate accurate detection of hydrocarbons. The stream was analyzed with a Fourier transform infrared spectrometer (FTIR) (Gasmet Cr2000, Temet Instruments), equipped with a Peltier-cooled MCT detector and analysis software. The compounds measured were H2O, CO, CO2, CH4, alkanes (C2, C12, and C16), alkenes (C2eC5), C2H2, alcohols (C1eC4), benzene, and toluene. Water and heavier hydrocarbons were condensed after FTIR analysis and the dry gas ow rate was measured. Element balances for C, H, and O were calculated to determine the amounts of H2 formed, the product distributions and the conversion of reactants. Product distributions were calculated at steady state using equation (4): Pi Fi $100%; j X Fn
n1

(4)

where Pi is the molar concentration of component i and Fi is the ow rate (mol/min). The distribution of H2 is presented as the selectivity toward H2. Selectivities of the catalysts toward reforming reactions were compared by calculating the ATR/OX ratio with equation (5). In the reforming process, H2 is not only produced via reforming reactions (POX and SR), but also via the wateregas-shift reaction (WGS) reaction (reaction (6)) [21]. FH2 FCO ATR=OX FH2 O FCO2 CO is consumed in the WGS reaction (reaction (6)): (5)

After ATR experiments (5 h), the catalysts were characterized by TPO in the same tubular quartz reactor. After each ATR experiment, the reactor was ushed with argon and thereafter cooled down to room temperature to remove any hydrocarbons adsorbed during the reaction. Because the catalyst was regenerated during TPO, the same catalyst could thus be tested at different ATR temperatures. That is, TPO was followed by second and third ATR and TPO cycles starting from ATR reaction temperature of 700  C and continuing to 800  C and nally to 600  C. Care was taken that catalysts were not in contact with air after ATR experiments. To nish, used catalysts were analyzed with a Leco SC-444 equipment. There the carbon was burnt from the surface in O2 at 1370  C to determine the amount of carbon left (the analytical error being 5%). In the TPO experiments, the coke formed during the ATR reactions was oxidized in air (3 vol-% of O2 in the resulting gas mixture) with a temperature ramp of 5  C/min from room temperature to 700  C. The total ow rate was 707 ml/min, which comprised 600 ml/min of Ar and 107 ml/min of air. The nal temperature of 700  C was maintained for 1 h to ensure complete coke burning. The amount of CO2 resulting from coke oxidation was determined by FTIR as a function of time. Temperature increase was also measured as a function of time. Results were combined, and the CO2 generation was presented as a function of temperature. The result for each catalyst is referred to as a TPO prole of this particular catalyst. The constant conditions (ow rate, temperature ramp, O2 concentration, equipment) used in the TPO experiments enable reliable comparison of the TPO proles. It should be noted that CO formation was not detected during TPO experiments indicating that the oxygen content was high enough for complete coke burning. The amount of water formed was too small to allow reliable reporting of the results. The area under a TPO prole represents the total amount of CO2 formed in the course of one TPO experiment. Areas were determined by integrating the proles (MATLAB, version 7.1). The total amount of CO2 was used to calculate the relative amount of coke deposited on the catalyst during ATR reaction.

3.
3.1.

Results
Thermodynamic calculations

CO H2O 5 CO2 H2 (WGS)

(6)

The calculated DG values (kJ/mol) for the reactions (1)e(3) as a function of temperature are presented in Fig. 1. In the gure it can be noted that the reaction (1) is not favored above temperature 701  C and reaction (2) is not favored above 673  C.

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Fig. 1 e DG (kJ/mol) for the reactions (1)e(3) as a function of temperature [22].

Fig. 3 e Catalyst selectivity toward hydrogen in ATR of n-hexadecane at reaction temperatures set to 600, 700, and 800  C (H2O/C [ 3.00 mol/mol, O2/C [ 0.34 mol/mol). toward H2 at all temperatures tested being at best 31.3 mol-% at 800  C. As expected, H2 production was lowest but still detectable on the zirconia support at all temperatures in accordance with previous studies [4]. At 800  C, the difference in H2 production between the Pt catalyst and zirconia support was only 1.8 mol-%. The ATR/OX ratio was calculated to compare the catalyst selectivities toward reforming reactions. The results are shown in Fig. 4. The selectivity toward reforming reactions increased with increasing temperature on the Rh and RhPt catalysts and on the zirconia support, but it remained at constant level on the Pt catalyst. The greatest differences among the monometallic Pt- and the Rh-containing catalysts were found at 700 and 800  C, where the reforming selectivities of the Rh-containing catalysts were over 50 mol-%. The monometallic Rh catalyst was the most selective catalyst at all temperatures studied. Table 1 shows the calculated CO/CO2 ratio in the product stream on the noble metal catalysts. As can be seen, the values for the Pt catalyst and zirconia are higher than those for the Rh and RhPt catalysts. Thus, the CO2 content in relation to CO content is higher on the Rh-containing catalysts than on the Pt catalyst. Thermal cracking products of n-hexadecane (mostly ethene and methane) were present in the product streams at 600, 700, and 800  C (Figs. 5 and 6). The formation of thermal

In view of the selectivity to hydrogen, the thermodynamic calculations predict an increase in H2 production with increasing temperature for a reaction mixture in which H2O/ C 3.00 mol/mol and O2/C 0.34 mol/mol.

3.2.

Catalyst performance in ATR of n-hexadecane

Complete conversion of n-hexadecane was obtained on the noble metal catalysts and the support material in the temperature range studied (600e800  C). Oxygen was assumed to react completely. Fig. 2 presents the conversion of water, which increases with the increasing temperature. In all cases, water conversion was negative at 600  C implying it was formed in the reaction. On the Pt catalyst and zirconia support, conversion was also negative at 700 and 800  C, while on Rh-containing catalysts, conversions were in the range of 6e12 mol-%. The reaction temperature and catalyst composition indeed had a signicant effect on product selectivities: see Fig. 3 for the selectivity toward H2 at 600, 700, and 800  C. While H2 production did increase on the Rh and RhPt catalysts, as well as on the zirconia support, it nevertheless decreased on the Pt catalyst. At reaction temperature of 600  C, Rh and Pt catalysts exhibited the highest selectivity of about 15 mol-%. It should also be noted that Rh catalyst showed the highest selectivity

Fig. 2 e Water conversion (mol-%) in ATR of n-hexadecane on noble metal catalysts at temperatures set to 600, 700, and 800  C (H2O/C [ 3.00 mol/mol, O2/C [ 0.34 mol/mol).

Fig. 4 e Calculated ATR/OX ratios (mol/mol) for the studied catalysts (Rh, Pt, RhPt) and their support (ZrO2) (H2O/ C [ 3.00 mol/mol, O2/C [ 0.34 mol/mol).

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Table 1 e Calculated molar ratios of CO to CO2 in ATR of nhexadecane on Rh, Pt, and RhPt catalysts and their support at 600, 700, and 800  C (H2O/C [ 3.00 mol/mol, O2/ C [ 0.34 mol/mol). Catalyst Rh
600 C 700  C 800  C


CO/CO2 ratio (%) RhPt

0.35 0.90 0.87

Pt
1.27 1.16 2.91

ZrO2
1.66 4.28 10.75

0.90 1.00 0.91

cracking products increased with temperature on the Pt catalyst and zirconia support. Instead, on the Rh-containing catalysts the cracking products rst increased when temperature was increased from 600 to 700  C and decreased thereafter. The measured reaction temperatures at 600  C were higher for the studied noble metal catalysts (620e640  C). At 700 and 800  C the values for the Rh-containing catalysts were very close to the set value, but for the Pt catalyst higher values were recorded (20  C). Measured values of the reaction temperature for the zirconia support were 10  C below the set value.

Fig. 6 e Amounts of methane in product streams on Rh, Pt, and RhPt catalysts and ZrO2 support at temperatures set to 600, 700, and 800  C in ATR of n-hexadecane (H2O/ C [ 3.00 mol/mol, O2/C [ 0.34 mol/mol).

3.4.

Catalyst characterization by TPO proles

3.3.

Total coke deposited in ATR of n-hexadecane

At all temperatures, coke formation was greatest on the Pt catalyst, see Table 2. The difference in the amounts was most signicant at 700  C, where the relative amount of coke on the Pt catalyst was 9.9%, while on the Rh and RhPt catalysts it was 7.7% and 6.3%, respectively. At 600 and 800  C the formation of coke increased in the order Rh < RhPt < Pt, whereas at 700  C the order was RhPt < Rh < Pt. Coke formation was always least on the ZrO2 support, except for 800  C, where the amount of coke on the Rh catalyst was minor. For all catalysts, coke formation was greatest at 700  C and least at 800  C. In contrast, coke formation on the support was lowest at 700  C. Evidently, however, not all coke was removed from the support during the TPO experiments, since some of the particles were black in color even after the TPO. Total carbon analysis with Leco indicated minor amounts of coke on the support (0.31 wt%) but also on the used catalysts (0.22e0.44 wt%).

TPO proles tell us the temperature at which coke species on the catalyst surface are oxidized. Information is thereby obtained about both the location of the coke and its chemical nature. Coke species differ in their reactivity to oxygen according to their aromatic, polymeric, or graphitic nature and their distance from the active metal [8,19,20]. The purpose of our TPO study was to evaluate coke formation on noble metal catalysts at different temperatures. Figs. 7e9 present TPO proles (temperature ramp of 5  C/min from room temperature to 700  C) for coke formed in the ATR of n-hexadecane at 600, 700, and 800  C. TPO proles for the different catalysts at each ATR temperature are presented in the same gure to enable comparisons among catalysts and evaluation of the effect of reaction temperature on the type of coke formed. Fig. 7 shows TPO proles for the coke formed in ATR of n-hexadecane at 600  C. The dominant CO2 maxima for the monometallic Rh and Pt catalysts are seen at 500e650  C although coke oxidation begins after 250  C. In the prole of the RhPt catalyst, sharp CO2 maxima appear at 195 and 360  C. The coke on the support oxidizes at 450 and 600  C. TPO proles for the coke formed in ATR of n-hexadecane at 700  C are presented in Fig. 8. The most intense maxima on the noble metal catalysts appear at about 400  C, where also the largest amount of coke is oxidized. The intensity of these maxima decreases in the order Pt > Rh > RhPt. The Pt-containing catalysts also show coke oxidation at high temperatures of 600  C, whereas the Rh catalyst lacks this behavior. These high-temperature maxima were likewise detected for

Table 2 e Total amount of coke after ATR of n-hexadecane as a function of ATR temperature. Catalyst Fig. 5 e Amounts of ethene in product streams on Rh, Pt, and RhPt catalysts and ZrO2 support at temperatures set to 600, 700, and 800  C in ATR of n-hexadecane (H2O/ C [ 3.00 mol/mol, O2/C [ 0.34 mol/mol). Rh
600 C 700  C 800  C


Coke (masscoke/masscat, %) RhPt

5.7 6.3 3.4

Pt
6.6 9.9 3.7

ZrO2
4.7 2.4 3.0

5.2 7.7 2.8

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Fig. 7 e TPO proles for the coke formed in ATR of n-hexadecane at 600  C on mono- and bimetallic noble metal catalysts (Rh, Pt, RhPt) and their support (ZrO2).

Fig. 9 e TPO proles for the coke formed in ATR of n-hexadecane at 800  C on mono- and bimetallic noble metal catalysts (Rh, Pt, RhPt) and their support (ZrO2).

the monometallic catalysts after ATR experiments at 600  C, where they were also more intense. Fig. 9 shows TPO proles for the catalysts and support after ATR reactions carried out at 800  C. The Rh and RhPt catalysts show strong maxima at 300 and 350  C, whereas the coke on the Pt catalyst is oxidized at 250e550  C. On the Pt catalyst, CO2 generation is most intense at 500  C. Coke on the zirconia support is oxidized at 350e600  C, and CO2 maxima appear at 400, 500, and 580  C. CO2 generation was less intense after ATR reactions at 800  C than after ATR reactions at 600  C and 700  C.

4.

Discussion

ATR reactions of n-hexadecane, distilled water, and air were carried out on noble metal catalysts and the support material at 600e800  C. The conversions of n-hexadecane and oxygen were complete, and the conversion of water increased with

Fig. 8 e TPO proles for the coke formed in ATR of nhexadecane at 700  C on mono- and bimetallic noble metal catalysts (Rh, Pt, RhPt) and their support (ZrO2).

the increasing temperature since the endothermic SR reaction was enhanced. Enhancement of SR was also indicated by an increase in H2 production with temperature on Rh and RhPt catalysts and the zirconia support. On the Pt catalyst, however, H2 production decreased with increase in temperature, showing that Pt was not as selective toward H2 as Rh in SR reactions. The decrease in H2 production on Pt catalyst also indicated that unwanted side reactions occur, or else there is a decrease in the rate of the WGS reaction. For the WGS reaction, a study of Panagiotopoulou and Kondarides, 2006, showed that Pt catalysts are generally more active toward WGS when compared to Rh catalysts [23]. In this light it can be assumed that the decrease in H2 production on the Pt catalyst is a consequence of unwanted side reactions, rather than the decelerating WGS reaction. At 600  C, the observed negative water conversions on all catalysts also indicate that hydrogen reacts to water via side reactions at this temperature. On the Pt catalyst and zirconia support, water conversion remained negative with increase in temperature. Thus, unwanted side reactions continue to occur on the Pt catalyst even at higher temperatures than 600  C. Possible reactions generating water in ATR are oxidation reactions and reaction (2), which produces elemental carbon on the surface of the catalyst. Complete oxidation also generates water, but this should be seen as an increase in the amount of CO2, and thus as a decrease in the CO/CO2 ratio, which was not detected. The calculated ATR/OX ratio (Fig. 4) indicated differences in the selectivity of the noble metal catalysts. Only half of the equilibrium amount of H2 was present in the product streams at 600  C, which, together with the low ATR/OX ratios, shows the side reactions to be intense at this temperature. The higher actual reaction temperatures observed with all catalysts at 600  C also indicate the occurrence of exothermic reactions, such as reaction (1). When the reaction temperature was elevated to 700  C, Rh and RhPt catalysts showed distinctly higher selectivities toward reforming reactions than did the Pt catalyst. Also, water conversions on the Rh catalysts were positive, and we can conclude that, on these catalysts,

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side reactions leading to water were inhibited. The highest selectivities toward H2 on the Rh and RhPt catalysts were reached at 800  C, whereas for the Pt catalyst the selectivity toward H2 was lowest at 800  C. It was also noticed that, at this temperature, the ATR/OX ratio calculated for the zirconia support was even higher than that for the Pt catalyst. This data show Pt to be selective toward oxidation reactions, which might have a benecial effect in minimizing coke formation since the gasication of coke should be easy. Rh was thus conrmed to be the more selective metal toward SR reactions, as already recognized by Kaila and Krause [18]. The superior selectivity of Rh seems to prevent coke formation better than the good oxidation properties of Pt. The calculated CO/CO2 ratio was higher on the monometallic Pt catalyst than on the Rh catalysts. This, in combination with the decreasing amount of H2 in the product stream as a function of temperature, shows that the activity of Pt toward the WGS reaction was lower than that of Rh and RhPt. The lower values of the CO/CO2 ratio for the Rh catalysts might also be due to a more intense oxidation of CO (CO O2 CO2), which was shown to be more favorable on Rh than Pt catalysts by Oh and Sinkevitch, 1993 [24]. More intense oxidation of CO, together with the higher activity toward the WGS reaction, evidently is benecial in minimizing coke on the catalyst, as smaller amounts of coke were formed on the Rh catalysts. A possible reason for this is that a smaller decrease in the amount of CO affects the equilibrium of reaction (1) so that less carbon is formed on the surface. Ethene and methane were detected in the product streams of all catalysts and the changes in the amounts as a function of temperature were concurrent. Therefore, we can conclude that methane is formed in the ATR reactions via thermal cracking of n-hexadecane in the gas phase rather than in the methanation reaction (CO 3H2 CH4 H2O), for which DG < 0 when T < 616  C [22]. Qi et al. [25] noted in their study on ATR of gasoline compounds on monolithic Rh-based catalysts that methane is formed by thermal cracking in the ATR of hydrocarbons [25]. In general, this thermal cracking of the hydrocarbon chains increases with temperature. Gas phase reactions are assumed to occur in this kind of reaction and affect the product distribution. Previously, Kaila and Krause [18], reported thermal experiments of single hydrocarbons. The main products were H2, carbon oxides, ethane, methane and propane. The formation of ethane was found to accelerate with temperature. Also, it was noted that light hydrocarbons do form via thermal cracking the formation being accelerated with temperature [18]. In our experiments, the selectivities toward H2 of the Rh and RhPt catalysts improved as the temperature was raised, and amounts of thermal cracking products decreased; however, a maximum amount was detected at 700  C. In a study on the effect of temperature in SR of n-hexadecane over a temperature range of 600e900  C, Goud et al. [14] likewise observed a maximum amount of thermal cracking products at 700  C. Corresponding behavior was not observed on our Pt catalyst or zirconia support, whose activities toward ATR were not high enough to prevent thermal cracking at elevated temperatures; rather, the amounts of ethene and methane continuously increased with temperature. This

proves for the poor selectivity of Pt and zirconia at higher temperatures. Thermal cracking products are precursors in coke formation [10,11,15]. Thus, the stronger thermal cracking at 700  C on Rh and RhPt may explain the increase in the amount of coke at this temperature. Although thermal cracking on Pt and ZrO2 was most intense at 800  C, this did not lead to the formation of larger amounts of coke. Rather, the amount of coke was minimized at 800  C, probably because the gasication of coke was pronounced. Coke may be gasied from the catalyst surface during ATR with interaction of the reformate components H2O, H2, and CO2. These components are nevertheless involved in many other reactions in the process. This shows the complexity of coking phenomenon and the fact that minimizing one parameter does not necessarily lead to minimization of the overall amount of coke. In studies on bimetallic catalysts in ATR of simulated gasoline, Kaila et al. [4] established the synergistic property of these RhPt catalysts in preventing carbon deposition. Based on this, it is suggested that differences also exist in the nature of coke deposits. Comparison of the TPO proles of our monometallic Rh and Pt catalysts with those of the bimetallic RhPt catalyst indeed revealed differences. After ATR reactions at 600  C, coke species were not oxidized on the Rh or Pt catalysts before 250  C, while intense coke oxidation was seen on the RhPt catalyst at about 200  C. Coke oxidized at 200  C is assumed to be located on the active metal since metals catalyze oxidation. The fact that coke oxidation at low temperature was not detected on the zirconia support further suggests that, on the noble metal catalysts, coke was located on the metal or metalesupport interface. The monometallic catalysts and the support showed strong coke oxidation maxima at 500e650  C, but no such maximum was seen for the RhPt catalyst. We conclude that the coke species oxidized at high temperature in the case of monometallic Rh and Pt catalysts were located on the support, and that the major part of the coke formed on these catalysts during ATR at 600  C was of this type. When ATR reactions were carried out at 700  C, RhPt suppressed the coke formation better than Rh and Pt, as indicated by the total amount of coke. Moreover, the amount of coke detected in the TPO proles at about 400  C was lowest on the RhPt catalyst, which shows that the bimetallic sites have benecial effects in preventing the formation of coke at 700  C. Probably the coke formed on the monometallic catalysts differs from that formed on the bimetallic catalyst. This could be the result of unlike interactions between the active metal and support or of a difference in the nature of sites where the coke is located. Also, the formation of surface carbon and its gasication may be differently catalyzed. It is nevertheless unclear from the results how the different types of coke affect the deactivation of the catalysts. Also earlier, bimetallic Ptcontaining catalysts were shown to be effective in preventing coke formation: differences in coke mobility and the interactions between Pt and the alloying metal led to differing locations of the coke on mono- and bimetallic catalysts [26]. The known relationship between reaction temperature and the nature of the coke formed in reactions involving hydrocarbons [17] is well represented in the TPO proles in Figs. 7e9. On the monometallic catalysts and on the support

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the coke formed in ATR at 600  C is oxidized at high temperatures (ca. 600  C). After reactions at 700  C coke oxidation at high temperatures was detected only in the presence of Pt. After ATR at 800  C high-temperature coke was not formed in notable amount on any catalyst. Coke oxidized at high temperatures is considered to be more graphitic and located on the support rather than on the active metal [8,27]. During reforming processes surface carbon (Cs) can form on catalyst active sites via equilibrium reactions (1)e(3) (Fig. 1). If its gasication from the surface is slow, Cs may form chained structures, which are difcult to gasify [10,11,27]. The formation of Cs via reactions (1)e(3) at the studied reaction temperatures was investigated by thermodynamic calculations. These suggested that the formation of Cs via reactions (1)e(2) is strongest at 600  C, and negligible at 800  C. [22] Thus, the gasication of Cs with water and CO2 is pronounced at 800  C. The formation of methane-derived coke via reaction (3) is also considered, but according to thermodynamics, there is no signicant change in the equilibrium in the studied temperature range. We propose, therefore, that coke was produced in smaller amounts at 800  C because of the shift in equilibrium of reactions (1) and (2). As a consequence, less high-temperature coke was accumulated (see TPO proles in Figs. 7e9). The stronger gasication of coke with water at 800  C is also evident in the increase in water conversion with temperature. Coke formation has also been estimated to decrease as a function of temperature, as coke is formed mainly via exothermic reactions, such as the Boudouard reaction (reaction (1)) [9]. Here, coke formation was greatest at 700  C due to the accumulation of coke oxidizing at 400  C. Although the origin of this type of coke is unclear, its uniform nature is apparent. This can be seen particularly in contrast to the coke formed at other temperatures, where multiple CO2 maxima appear over a wide temperature range. Coke formation should, therefore, be studied experimentally, since the process is complicated and involves reactions that cannot be accurately predicted by thermodynamic calculations. Considering fuel cell applications, the overall effect of carbon formation should also be taken into account. When evaporating the diesel fuel, there is a risk of its decomposition and consequently coke formation due to high temperatures used in the evaporation stage, as reported by Sarioglan et al. [28]. However, in our study, only the coke formation on the catalyst was studied. At all reaction temperatures the formation of coke was least on the support. This indicates either that the coke on the support was not completely oxidized during TPO due to lack of catalyzing metal or that the noble metal catalysts can tolerate larger amounts of coke on their surface. As has been noted, it is the balance between coke formation and removal that determines the amount of coking [11]. Our results also show that it is not only the activity of the metal toward reforming reactions that is important in ATR reactions, but also the coke gasication properties that assist coke removal and thereby preserve the activity. Although fairly large amounts of coke were formed during the ATR experiments, no signicant effect on the activity of the catalysts after the beginning of the reaction was detected. No relation between the rate of hydrogen production and the amount of coke was found

either. Thus, the selectivity toward hydrogen seems not to be affected by the quantity of coke formed, which is in accordance with previous results reported by Kaila et al. [4]. Instead, some coke formation may even be desirable. Similarly, selective poisoning effect on reforming catalysts with sulfur has been well reported in the literature [13]. The results show that the noble metal catalysts tolerate relatively large amounts of coke without deactivation. It has also been demonstrated previously that reforming catalysts can support considerable coke formation and still retain their activity [10]. In summary, coke evidently forms extensively at the beginning of the reaction on-sites not active toward reforming. The deactivation by coking occurs only after very long reaction times [29].

5.

Conclusions

We studied the coking occurring in ATR of n-hexadecane (a model compound for renewable diesel fuel) by combining TPO cycles with ATR experiments at different reaction temperatures (600, 700, and 800  C). Studies were performed on three noble metal catalysts (Rh, Pt, RhPt) and their support (ZrO2). Through TPO analysis we obtained both total amounts of coke and qualitative information about its reactivity and heterogeneity. The catalytic performance of the mono- and bimetallic catalysts was compared at the tested reaction temperatures and results were analyzed along with the amount and nature of the coke formed. Reaction temperature and catalyst composition affected the catalyst selectivity toward H2 during ATR experiments and further the amounts of coke formed (2.8e9.9 wt%). Catalyst selectivity toward H2 increased with temperature on the tested Rh-containing catalysts and the ZrO2 support, whereas on the Pt catalyst a decrease as a function of temperature was observed. Also, the amount of thermal cracking products in the product streams was much dependent on reaction temperature and catalyst composition. On the Rh-containing catalysts, maximum amount of ethene and methane was detected at 700  C, whereas on the Pt catalyst and zirconia support those amounts were increasing with reaction temperature. Pt was the more selective catalyst toward oxidation reactions. Examining the total amounts of coke formed, it was interestingly noted that the amount of coke deposited on the noble metal catalysts during ATR was highest at 700  C and least at the highest reaction temperature tested (800  C). In sum, the superior selectivity of the Rhcontaining catalysts was assessed to prevent coke deposition on their surface. During ATR at 600  C, the formation of coke decreased in the order Pt > RhPt > Rh > ZrO2. The TPO proles after the ATR showed intensive coke oxidation maxima at 500e650  C for the monometallic catalysts and the support, whereas a strong maximum was seen at a signicantly lower temperature of approx. 195  C for the RhPt catalyst. We conclude that at 600  C, the coke species on the monometallic Rh and Pt catalysts were located mostly on the support, whereas the bimetallic RhPt catalyst was able to suppress the formation of this type of coke.

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During ATR at 700  C the formation of coke decreased in the order Pt > Rh > RhPt > ZrO2 and the role of thermal cracking was pronounced in coke formation. As shown in the TPO proles, the coke oxidation maxima were centered around one dominating temperature (400  C), indicating the more uniform nature of the carbonaceous species. This maximum was least intense on the bimetallic RhPt catalyst and accordingly, also at 700  C, the benecial interaction of Rh and Pt was demonstrated via lower accumulation of coke on the catalyst surface. During ATR at 800  C the formation of coke decreased in the order Pt > RhPt > ZrO2 > Rh and coke formation was at its lowest at this reaction temperature. It is concluded that the gasication of coke with water was enhanced at 800  C. Gasication together with improving catalyst selectivity with increasing temperature reduced coke formation and thus minimized the amount of coke at 800  C. Furthermore, the effect of the Boudouard reaction became negligible at 800  C. Although the amount of coke was low, signicant differences were observed in the type of coke. The TPO proles after ATR reactions carried out at 800  C showed multiple coke oxidation maxima over a broad temperature range. The Rh and RhPt catalysts show strong maxima at 300 and 350  C, respectively, while coke was oxidized on a broad temperature range on the Pt catalyst (250e550  C) and on the zirconia support (350e600  C). Comparison of ATR and TPO results accordingly provides understanding of coking in ATR reactions and assists in the optimization of the process conditions in order to avoid deactivation. Our results show the importance of experimental research in evaluating coke formation since thermodynamic calculations alone do not provide accurate knowledge about the outcome of the complicated set of reactions involved in coking.

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