PERGAMON

Carbon 39 (2001) 451463

Uncatalysed and catalysed CO 2 reaction using metal catalysts and binary vanadium mixtures supported on activated carbon
Sonia A. Carabineiro, Douglas W. McKee, Isabel F. Silva*
Departamento de Qumica, C.Q.F.B, Universidade Nova de Lisboa, Faculdade de Ciencias e Tecnologia, 2825114, Monte de Caparica, Portugal Received 4 December 1999; accepted 3 June 2000

Abstract The kinetics of the reaction of CO 2 with activated carbon without catalyst and impregnated with precursor salts of Mg, Ba, Pb, Cu and Fe and their binary mixtures were investigated. Binary mixtures of those metals with vanadium oxide were also studied. The conversion of CO 2 was studied (3008C to 9008C) using a TGA apparatus and a xed bed reactor. The reactor efuents were analysed using a GCMS on line. CO was the main product together with some unreactant CO 2. The best synergetic effects were observed for samples doped with Ba1V, Mg1V, Fe1V, Cu1V and Ba1Fe oxides. Adsorption of CO 2 (208C to 1008C) increased considerably in the presence of catalysts but binary oxide mixtures had no synergistic effects. In situ XRD was a useful tool for interpreting catalyst behaviour and identifying phases present during reaction conditions. The active phases appear to be metal carbonates and / or metal oxide phases. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: A. Activated carbon; B. Catalyst; C. Adsorption,TGA, X-ray diffraction

1. Introduction CO 2 is a major source for the so-called greenhouse effect, leading possibly to changes in climate. To reduce the emission of CO 2 carbon gasication can be used as an important process in producing CO, a useful product, and chemical feed stocks [17]. If carbon is reacted with CO 2 , CO is obtained by the reverse Boudouard reaction: CO 2 (g) 1 C(s) 2CO(g) The use of catalysts has been proposed for low temperature gasication to overcome the slow reaction of carbon with CO 2 [1,35,7]. Group VIII metals as well as alkali and alkaline earth catalysts are effective catalysts [1,35,7]. Mechanisms which have been proposed to account for the catalytic effects of alkaline earth carbonates in the CCO 2 reaction include carbonateoxide cycles, in which the carbonate reacts with the carbon substrate to produce CO and the metal oxide, followed by reaction of the oxide
*Corresponding author. Tel.: 1351-212-95-0929; fax: 1351212-94-8385. E-mail address: iss@dq.fct.unl.pt (I.F. Silva).

phase with ambient CO 2 to reform the metal carbonate [1]. Alternatively, oxygen may be transferred from the carbonate to the carbon to form an oxidized site which subsequently decomposes producing CO [5]. Several studies have shown that alkaline earth species are able to chemisorb CO 2 and are capable of catalyzing oxygen exchange reaction [35]. The aim of the present work was to study the behaviour of several metal oxides and binary oxide mixtures as catalysts for the C / CO 2 reaction on activated carbon. In situ XRD is used to identify the phases present under reaction conditions. This technique combined with kinetic measurements is a useful tool for interpreting catalyst behaviour.

2. Experimental Charcoal Activated GR MERCK (powder) was used to carry out isothermal kinetic studies and adsorption of CO 2 . This activated charcoal had a surface area of 1011 m 2 g 21 and a pore total volume of 0.54 cm 3 g 21 . The charcoal was impregnated with diluted solutions of acetates of Mg, Ba, Pb, Cu and Fe by the Incipient Wetness Method. Metal

0008-6223 / 01 / $ see front matter 2001 Elsevier Science Ltd. All rights reserved. PII: S0008-6223( 00 )00151-2

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salts were diluted in a small amount of distilled water and the obtained solutions were added dropwise to the carbon, mixing thoroughly and the obtained product was evaporated on a hot plate. The additive loading was 4 wt% (calculated as metal). Binary mixtures of these salts were also prepared according to the same method. Vanadium oxide was shown in a previous study to be a good catalyst for CO 2 reaction with carbon [8] so binary mixtures with it and the metal salts described above were also prepared using ammonium monovanadate as precursor. This salt would decompose to vanadium oxide at low temperatures. In order to prevent diffusional limitations, thermogravimetric sample weight was around 2 to 3 mg. Isothermal kinetic studies were carried out using a thermobalance system (CI Electronics MK II microbalance) with continuous recording of change in weight between 3008C and 9008C, with CO 2 , with a ow-rate of 3.3 cm 3 s 21 . For the adsorption studies 10 mg of sample were weighted using the same apparatus, using CO 2 , with a ow-rate of 3.3 cm 3 s 21 . For comparison purposes, rates of gasication referring to 20% burn-off range were used. The gasication rates at each temperature were derived from the relation: rate(s 21 ) 5 (2Dw /Dt) /w o where w o is the initial weight of the sample. Before each experiment of adsorption and kinetics, Ar was introduced with a ow-rate of 3.3 cm 3 s 21 , for 30 min, in order to eliminate traces of air. The samples were heated in owing Ar to 5008C to decompose precursor salts (used in sample preparation) and eliminate volatiles adsorbed in carbon, until baseline sample weight was constant. The temperature was then adjusted to the desired value (208C9008C) and Ar was switched to CO 2 . Before use the gases were passed through a molecular sieve bed to remove the water. The total gas pressure was always 1 bar (0.1 MPa). The catalyst phases detected by in situ XRD after pre-treatment in inert atmosphere at 5008C were: BaCO 3 / BaO / BaO 2 for sample doped with Ba; CuO / Cu for sample doped with Cu; MgO / MgCO 3 for sample doped with Mg; Pb 3 O 4 / PbO for sample doped with Pb; Fe 2 O 3 / Fe 3 O 4 for sample doped with Fe and V2 O 5 / V6 O 13 for sample doped with V as shown in Fig. 1. Binary mixtures were found to contain mixtures of the active phases present in the individual catalyst systems as reported in an earlier study in NO and N 2 O atmospheres [9]. In situ XRD studies were conducted in a Rigaku D/ max III C diffractometer with a Cu (Ka) radiation source (50 kV, 30 mA), equipped with a high temperature special chamber. All the experiments were carried out at exactly the same experimental conditions as in the thermogravimetric studies, including the pre-treatment of samples in inert gas at 5008C. CO 2 conversion was studied using a xed bed reactor.

The reactor efuents were analysed using a GCMS (Fisons MD800) apparatus, equipped with a column of GS-Molesieve (30 mx0.541 mm) type. These essays included heating of sample at 28C min 21 (TPR) from 208C to 9508C in CO 2 . The ow-rate was 3.3 cm 3 s 21 . All samples were pre-treated in He at 5008C for 30 min.

3. Results and discussion Fig. 2 shows that by adding a metal oxide additive CO 2 adsorption capacity appeared to increase at lower temperatures when compared with the carbon parent sample, with the exceptions of samples doped with Cu, Co and Pb. Adsorption amount decreased with increasing temperature characteristic of physical adsorption. It can be that the nely divided metal oxides on the carbon surface enhanced the adsorption of CO 2 because they reacted with it at low temperatures to form carbonates. The best additive was Fe oxide followed by Mg, V and Ba oxides. Binary oxide mixtures had no synergetic effects. Figs. 3a, b, c, d show some TGA curves at several temperatures for carbon parent sample and samples doped with Ba, V oxides and Ba1V oxide mixture. The curves seem linear at lower temperatures, however at higher temperatures an S shape is visible in the end when all carbon is almost consumed. A similar behavior has been reported before with different catalysts [10]. The catalytic activity of the mixture of catalysts (Fig. 3d) was higher than the ones of the catalysts alone. Other catalysts and mixtures studied showed similar behavior. Figs. 4a, b, c, d show the Arrhenius plots for CO 2 reaction for the vanadium binary mixtures, which showed the best oxide synergetic effects (Ba1V, Cu1V, Fe1V, Mg1V). Activation energy values shown in those plots were calculated by the Arrhenius law from these isothermal kinetic studies. For comparison purposes activation energies were calculated from the temperature program reaction (TPR) proles for CO 2 conversion. Both results are shown in Table 1. Values derived from the TPR are lower than those derived from isothermal kinetic studies. The differences might be due to the different conditions of essays (isothermal and dynamic). A substantial decrease in activation energy for the catalysed reactions compared to the uncatalysed was observed with all systems unlike the results obtained by other authors in which catalysed and uncatalysed reactions have similar values of activation energies [4,11]. The value obtained (290 kJmol 21 ) for the uncatalysed reaction is within those reported in the literature [4,1012]. In previous studies it was said that 130 kJmol 21 was probably the lowest activation energy reported for CO 2 reaction with activated carbon (using Mo as a catalyst) [10] while the activation energy for the uncatalyzed reaction was 272 kJmol 21 up to 8508C. The values obtained for Ba, Fe and Mg oxides showed to have similar values to that of Mo catalysed

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Fig. 1. In situ XRD data obtained in N 2 at 5008C for samples doped with Ba (a), Cu (b), Mg (c) Pb (d), Fe (e) and V (f) oxides.

Fig. 2. CO 2 (c) adsorption for carbon parent sample and samples doped with several catalysts, at different temperatures.

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Fig. 3. TGA curves at several temperatures for carbon gasication in CO 2 for carbon parent sample (a) and samples doped with Ba oxide (b), V oxide (c) and Ba1V oxide mixture (d).

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Fig. 4. Arrhenius plots for carbon gasication in CO 2 for carbon parent sample and samples doped with V, Ba and Ba1V oxide mixture (a), samples doped with V, Cu and Cu1V oxide mixture (b), V, Fe and Fe1V oxide mixture (c) and V, Mg and Mg1V oxide mixture (d).

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Table 1 Activation energy values derived from the isothermal kinetic studies (EaI) and from the program temperature reaction proles (EaII) for CO 2 conversion EaI (kJmol ) Uncatalysed V oxide Cu oxide Ba oxide Fe oxide Mg oxide Cu1V oxide Ba1V oxide Fe1V oxide Mg1V oxide 290 200 190 117 124 119 122 110 101 104
21

If 80% of the CO 2 was decomposed, the Boudouard reaction would give: CO 2 /(CO 1 CO 2 ) 5 20 / 160 1 20 3 100 5 11.1% and CO /(CO 1 CO 2 ) 5 160 / 160 1 20 3 100 5 88.9% in reasonable agreement with the results shown in Fig. 6. A similar trend was obtained with all mixtures. Active phases play also an important role on the catalytic conversion of CO 2 . Figs. 7a, b, c, d show XRD patterns obtained in CO 2 at several temperatures for carbon doped with Ba1V, Cu1V, Fe1V and Mg1V oxide mixtures. Figs. 8 and 9, show XRD patterns of the individual catalysts for a better identication of active phases. The peaks show shifts to 2u with increasing temperature, which reects expansion of the crystal lattices. Pt peaks appear in the spectra resulting from exposure of the sample holder to the X-ray beam as carbon burned away or as part of the carbon sample falls down during sample preparation and / or pre-treatment as the sample holder stays in a vertical position inside the high temperature chamber. In situ XRD shows clearly that on heating with carbon in the CO 2 atmosphere the added oxides are decomposed to oxides and the latter may be reduced by reaction with the carbon substrate to lower oxidation states. Lower oxides such as V6 O 13 and Fe 3 O 4 were also detected after heating the samples in an inert atmosphere. It is possible that these oxides catalyze the CCO 2 reaction by means of oxidation / reduction cycles such as: M x O y11 1 C M x O y 1 CO M x O y 1 CO 2 M x O y11 1 CO giving the overall gasication reaction: C 1 CO 2 2CO Reported [1] catalytic effects of the alkaline earth carbonates in the CCO 2 reaction can be interpreted in a general way in terms of sequences of cyclic processes in which carbonate particles react with the carbon at points of contact to form oxides which subsequently react with ambient CO 2 to reform transient carbonate species. For example, MCO 3 1 C MO 1 2CO MO 1 CO 2 MCO 3 giving the overall gasication reaction: C 1 CO 2 2CO These sequential steps have been shown to be thermodynamically feasible for Ca, Sr and Ba carbonates at temperatures above 7008C [1]. However, this carbonate

EaII (kJmol ) 248 172 177 93 93 100 91 89 82 91

21

reaction (117, 124 and 119 kJmol 21 respectively) and the same happened with the mixtures, being the lowest value of 101 kJmol 21 for the mixture Fe1V. As for the other synergetic effects, the Pb1V oxide mixture showed a marked synergetic effect at high temperatures but the enhanced catalytic effect decreased with decreasing temperature to give gasication rates only slightly above those expected from the sum of the rates for the individual catalyst components. Ba1Fe oxide mixture showed a marked synergetic effect at both high and low temperatures. This effect was also reported and discussed in an earlier study in NO and N 2 O atmospheres [9]. Other mixtures studied showed synergetic effects only at higher temperatures, as at low temperatures the effects were merely those expected from the sum of the rates for the individual catalyst components. Synergetic effects of binary mixtures have been reported for catalytic gasication of carbon with steam. The synergetic effects of binary mixtures can also result from other benecial interactions between the mixture components and those between reactants and the individual components [13]. Figs. 5a, b, c, d shows the catalysed program temperature reaction prole for CO 2 conversion. These results are in agreement with the kinetic ones as the mixture converts the CO 2 at lower temperature (around 7008C) than the individual components (around 8008C). The analysis of the compositions of the reaction products for the reaction with CO 2 (Figs. 6a, b, c, d) using a GCMS on line show a similar trend with the only product of gasication is CO together with some unreacted CO 2 (as it would be expected by the Boudouard reaction). If 30% of the CO 2 was decomposed, the Boudouard reaction would give: CO 2 /(CO 1 CO 2 ) 5 70 / 60 1 70 3 100 5 53.8% and CO /(CO 1 CO 2 ) 5 60 / 60 1 70 3 100 5 46.2%.

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Fig. 5. CO 2 conversion as a function of temperature (TPR) for samples doped with V, Ba and Ba1V oxide mixture (a), samples doped with V, Cu and Cu1V oxide mixture (b), V, Fe and Fe1V oxide mixture (c) and V, Mg and Mg1V oxide mixture (d).

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Fig. 6. Reaction products in TPR for carbon parent sample (a) and samples doped with V oxide (b), Ba oxide (c), and Ba1V oxide mixture (d).

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Fig. 7. In situ XRD data obtained in CO 2 on heating samples doped with Ba1V (a), Cu1V (b), Fe1V (c) and Mg1V (d) oxide mixtures at several temperatures.

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Fig. 8. In situ XRD data obtained in CO 2 on heating samples doped with Ba (a), Cu (b) and Mg (c) oxides at several temperatures.

oxide cycle is less likely for Mg carbonate which decomposes to oxide below 6008C, even in the presence of high ambient pressures of CO 2 . Previous studies with

alkaline earth carbonates as catalysts in the graphiteCO 2 reaction showed Mg carbonate to be much less active than the carbonates of Ca, Sr and Ba [1]. In the present work

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Fig. 9. In situ XRD data obtained in CO 2 on heating samples doped with Pb (a), Fe (b) and V (c) oxides at several temperatures.

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with activated carbon, the catalytic activity of the Mg salt was more marked than with graphite. It is possible that an oxygen transfer process occurs during the thermal decomposition of MgCO 3 leading to the formation of oxidized carbon sites which subsequently decompose to form CO: MgCO 3 -C MgOC(O) 1 CO MgOC(O) MgOC 1 CO A similar mechanism has been proposed by Cazorla Amoros et al. [5] to explain the catalytic effects of CaCO 3 in the CCO 2 reaction. No evidence of a new phase responsible for the synergetic effect was observed in the mixtures by in situ XRD as the same active phases were observed in the XRD patterns for the samples with two catalyst species as in the individual spectra for the single catalyst samples, however the addition of vanadium oxide seems to increase carbon reactivity at low temperatures. Various authors reported that V2 O 5 has the ability to spread and wet carbon surfaces [1,8,1315]. The reduction of V2 O 5 to V6 O 13 further reduces the melting point of the catalyst and could lead to more extensive spreading on carbon surface [1,8,1315]. In situ XRD carried out both in CO 2 and N 2 atmospheres showed clearly that both V2 O 5 and V6 O 13 are present under reaction conditions and with increasing temperature the peaks become less intense for both oxides suggesting that the catalyst is spreading to form an amorphous thin lm on carbon surface. It has been reported that melting of the catalysts improves wetting of the carbon surface promoting catalyst / carbon interaction [1,8,9,13,16,17]. Also Yang et al indicated that pitting and channelling of graphite was caused by the reaction between V2 O 5 and carbon in which V2 O 5 was reduced to V6 O 13 . Also a liquid-like behaviour of the vanadium oxide particles was observed [15]. Thus the reduction of the metal oxide seems to be a key factor that controls the catalytic activity of the metal. The synergistic effect of vanadium is probably the result of the low melting point (6708C) of V2 O 5 , the melting and spreading of which on the carbon surface enables the catalytically active carbonate species to achieve a high degree of dispersion on the substrate. Another important factor is the catalyst dispersion. As dispersion increases, the cyclic processes occur at more sites on the carbon surface, enhancing the overall rate of gasication. The liquid V2 O 5 phase wets the carbon and promotes the distribution of active catalyst particles over a wider area. In situ XRD showed the probable species involved in the reaction conditions. Active catalysts may act as oxygen acceptors from CO 2 , transferring oxygen to the carbon surface which then evolves CO. Similar behaviour has been reported by several authors in CO 2 and other atmospheres [1,7,8,1824].

4. Conclusions A sequential cyclic process, involving the conversion of metal carbonate catalysts to oxide, followed by the transfer of oxygen to the carbon surface and evolution of CO, appears to be the most likely mechanism for the catalytic effects of alkaline earth carbonates on the CCO 2 reaction. The ability of the nely divided oxide phase to chemisorb CO 2 is also a factor in promoting catalyst activity and the synergetic effect observed on addition of vanadium oxide is related to its ability to wet and spread on the carbon surface.

Acknowledgements Sonia Carabineiro acknowledges nancial support from Fundacao para a Ciencia e Tecnologia, Grant BD1275 / 95.

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