Utilization of Carbon Dioxide for Direct, Selective Conversion of

Chapter 6

Utilization of Carbon Dioxide for Direct, Selective Conversion of Methane to Ethane and Ethylene with Calcium-Based Binary Catalysts 1,2

Downloaded by UNIV OF ARIZONA on May 22, 2013 | http://pubs.acs.org Publication Date: January 24, 2002 | doi: 10.1021/bk-2002-0809.ch006

Ye Wang

and Yasuo

1,*

Ohtsuka

1

Research Center for Organic Resources and Materials Chemistry, Institute for Chemical Reaction Science, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577, Japan Current address: Department of Applied Chemistry, Hiroshima University, Kagamiyama, Higashi-Hiroshima 739-8527, Japan

2

Utilization of CO for the direct conversion of CH to C H and C H has been studied under ambient pressure with a fixed bed quartz reactor. Ca-based binary catalysts, prepared by impregnating CeO , Cr O , or MnO with Ca(NO ) solution, show remarkable synergistic effects on C formation at 850°C. C selectivity and C yield increase with increasing partial pressure of CO , irrespective of the kind of catalyst, and the selectivity reaches 65 - 75% at 70 kPa. These catalysts provide stable performances with time on stream of 8 - 10 h. The T P D , XRD and X P S measurements strongly suggest that CO first adsorbs on Ca sites and the activation subsequently occurs on neighboring Ce , Cr or Mn sites to yield active oxygen species, which work as the oxidant for selective formation of C hydrocarbons. 4

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2+

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3+

3+

2+

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© 2002 American Chemical Society In CO2 Conversion and Utilization; Song, C., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2002.

85

86 Simultaneous activation and utilization of CH4 and C 0 have attracted increasing attention from environmental and practical points of view, since these gases show green house effects and natural gas frequently contains a high concentration of C 0 in addition to CH4. The present authors' group has been focusing on the novel use of C 0 as an oxidant for the direct conversion of CH4 to C H Ô and C2H4 ( C hydrocarbons) (1-7). Although the oxidative coupling of CH4 with 0 has been studied extensively for the same purpose, the inevitable formation of C 0 appears to be one of the most serious issues in this process (8). Overall equations for formation of C hydrocarbonsfromCH4 and C 0 can be expressed as follows: 2

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2

2

2

2

2


2

2

2CH4 + C 0 = C H6 + CO + H 0 2

2

2CH4 + 2C0 = C2B4 2

(1)

2

+ 2CO + 2H 0

(2)

2

Figure 1 shows the results of thermodynamic considerations about these equations under total pressure of 0.1 MPa (2,9). Yields of C He and C H4 at equilibrium depend on feed composition as well as reaction temperature and exceed 15% and 25% at C0 /CH4 ratio of 2 above 800°C, respectively. The sum of these values, if attainable, is comparable to the economically feasible C yield, about 30% (10) estimated for the oxidative coupling of CH4 with 0 . Our systematic study to identify the criteria for catalyst selection for the above reactions has shown that praseodymium and terbium oxides are more active among 30 metal oxides examined, but C yield is as low as 1% (1-3). As is seen in Figure 2 (2) this pioneering work has also suggested that redox property of a metal oxide, such as, Ce, Cr, or Mn oxide, activates ŒL* and C 0 , and that its basicity affects C selectivity. It is thus expectable that a combination of two metal oxides with the different functions leads to a binary catalyst effective for C formation. The present paper features the catalytic performances of three binary systems prepared on this principle, clarifies the key factors controlling C formation, and elucidates the reaction mechanisms. 2

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Experimental Section Catalyst Materials and Preparation An alkaline earth metal nitrate, mainly Ca(N0 ) , was used as a precursor for one component of a binary catalyst, because the corresponding oxide formed after calcination has strong basicity. Ce0 , C r 0 or M n 0 was selected as 3

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In CO2 Conversion and Utilization; Song, C., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2002.

87 60 CO /CH =y

C2H4

2

4

/y


-

400

500

600

ι

ι

700

800

900

Temperature, °C Figure 1. Dependence of yields of C H and C H at equilibrium on ratio and temperature. 2

6

2

4

C0 /CH 2

60 Nd

P(CH ) = 50 kPa 4

Ο

P(C0 ) = 50 kPa 2

l O ^ T b Ca

Τ = 850°C

X

40 h >

G

ο ω

rvT

S m

Φ

CM

ϋ

_

_

20

4

19

Mn

ο

Ci,

5

10

15

CH conversion, % 4

Figure 2. Relationship between CH conversion and C selectivity in the reaction of CH and C0 with various metal oxides (Reproduced from reference 2 with permission from Elsevier Science). 4

4

2

2


4

88 another component, since they showed high conversions of CH4 and C 0 when used alone, as shown in Figure 2 (2) and their valences are readily changeable. The method of preparing a binary catalyst has been reported elsewhere (4,6) and is thus simply described. Powdery Ce0 , C r 0 , or Mn0 , was impregnated with an aqueous solution of Ca(N0 ) , and then the resulting mixture was dried, followed by air calcination at 850°C. The calcined catalyst was sieved to 0.5 - 1 mm before use. A physical mixture of both CaO derived from Ca(N0 ) and Ce0 was also prepared as a reference of a Ca-Ce system. 2

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Catalytic Runs and Product Analysis All runs were carried out with afixed-bedquartz reactor under ambient pressure. The detailed procedure has been described elsewhere (6). In a typical run, 2 g of the granular catalyst loaded onto quartz wool was calcined again under flowing air at 850°C, and, after complete replacement with high purity He (>99.9999%), a mixture of CH4 (>99.999%) and C 0 (>99.995%) was passed over the catalyst at 850°C. Partial pressure of CH4 or C 0 , denoted as P(CTL0 or P(C0 ), was 30.3 or 70.7 kPa, respectively, unless otherwise stated. The effluent after removal of H 0 was sampled at 5-min intervals, and C H , C H4, CO and H as products were analyzed with a high-speed micro GC. GC data were processed on the assumption that the C in CH4 was converted to C H , C H4, and CO, and the C in C 0 to CO. Since CO is formed from CH4 and C 0 , each contribution is separated by the previous method (1) in which almost all of side reactions involving CH4 and C 0 are taking into account. ŒU conversion and C selectivity can thus be calculated by the following equations (6) and C yield is defined as the product of both values. 2

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CH4 conversion (%) = {2[C H ] + 2[C H4] + [CO from CH4D/UCH4] + 2[C H ] + 2[C H4] + [CO from CTLJ} χ 100 2

2

6

6

2

2

C selectivity (%) = {2[C H6] + 2[C H4]}/{2[C H6] + 2[C H4] + [CO from CH4]}xlOO 2

2

2

2

2

Catalyst Characterization Fresh and used catalysts were characterized by several methods, such as N adsorption at 77 K, X-ray diffraction (XRD) with Ni-filtered Cu K radiation, and X-ray photoelectron spectroscopy (XPS) with Mg K radiation. Binary a

a


2

89 catalysts after 2 h reaction of CH4 and C 0 at 850°C were also subjected to the C 0 temperature programmed desorption (TPD) measurements. In a TPD run, the catalyst after reaction under PiŒU) of 30.3 kPa and P(C0 ) of 70.7 kPa was first quenched to 100°C in a stream of feed gas with the same composition, then held for 30 min at this temperature after replacement with pure He, and finally heated at 2.5°C/min up to 950°C under flowing a mixture of He and C 0 with different PCCCb) in the range of 0 - 70.7 kPa. It took about 5 min for quenching the used catalyst to 100°C. The change in C 0 concentration during the TPD run was monitored with the micro GC. The reproducibility of the change at a desorption peak was within ±5% under the highest P(C0 ) of 70.7 kPa. 2

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2

Results and Discussion Catalyst Composition The effect of catalyst composition on the performance of binary Ca-Ce catalysts under P(CH0 of 30 kPa and P(C0 ) of 30 kPa is illustrated in Figure 3, where the composition is expressed as [Ca/(Ca + Ce) χ 100] in atomic percent (at%). CH4 conversion was 12% or 0.1% with Ce0 or CaO alone, respectively. The conversions over the binary catalysts were lower than the arithmetic mean of those over each component. C selectivity was nearly zero with Ce0 alone, but it steeply increased when a low content of CaO coexisted. C selectivity was higher over the binary catalysts than over CaO alone. As shown in Figure 3B, C yield was < 0.1% with Ce0 or CaO alone, whereas it was much higher in the coexistence of both components. In other words, there was a synergistic effect on C formation (4,6). The maximal yield reached 3.2%, which was about 30 times that observed with the single oxide. Table 1 summarizes the results when Ce0 power was impregnated with other nitrate solutions than Ca(N0 ) . Surface areas of the binary oxides prepared, determined by the BET method, were almost independent of the kind of the alkaline earth metal. CH4 conversion at 850°C increased in the sequence of Ba - Sr < Ca < Mg, whereas C yield did in the order of Mg < Ba - Sr < Ca (6). Thus, the Ca-Ce system showed the highest activity for C formation. When CaO and Ce0 were physically mixed at Ca/Ce ratio of 0.5, as shown in Table 1, surface area and CH4 conversion were almost the same between the resulting mixture and the corresponding binary catalyst. On the other hand, C yield was much higher with the latter. These observations indicate that catalyst preparation by the impregnation method is more effective for C formation. 2

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90


91 On the basis of the results described above, the impregnation method using Ca(N0 ) solution was used to prepare a binary catalyst containing Cr or Mn element. Figure 4 shows the effect of catalyst composition on CH4 conversion at 850°C with the Ca-Cr (5) or Ca-Mn system. The conversion - composition profiles observed were quite similar as that (Figure 3) over the Ca-Ce catalyst; CH4 conversion with C r 0 or M n 0 alone decreased steeply by addition of a small amount of CaO and it leveled off with further increase in CaO. As is seen in Figure 5, C yield with C r 0 or M n 0 alone was low. On the other hand, Ca-Cr and Ca-Mn catalysts enhanced remarkably C yields, which were at highest 4.0% and 4.7%, respectively. As observed in Figure 3. synergy also existed in C formation over these binary systems. It should be noted that the maximal C yields over Ca-Ce, Ca-Cr, and CaMn systems are 3 - 4 times those observed with the single Pr or Tb oxide that is most effective for C formation (3). With regard to a binary catalyst reported earlier, a PbO-MgO system enhanced C yield in the oxidative coupling of CH4 with 0 in the coexistence of C 0 , but it readily lost the activity without 0 (11). Although a La 0 -ZnO system was also communicated to catalyze C formation from CH4 and C 0 (12), it was less active than the present binary catalysts. Since no mechanistic work to clarify not only the role of C 0 but the reaction mechanism has been carried out so far, the following sections focus on them. 3

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Partial Pressure of C 0

2

The profiles for the reaction of CH4 alone with the Ca-Ce (4) or Ca-Cr system are illustrated in Figure 6, where CH4 diluted with He is used at P(CYU) of 30 kPa. In the absence of C 0 , H and CO were mainly produced with the molar ratio of approximately 2 by the reaction of CH4 with lattice oxygen atoms, and formation rates of H and COfinallyapproached to zero within 2 h. Figure 6 also revealed negligibly small amounts of C hydrocarbons even at the early stage of reaction, which indicates that the lattice oxygen of these oxide systems does not work as an oxidant for C formation. In the presence of C 0 , C formation proceeded readily. As shown in Figure 7, with the Ca-Ce catalyst, C yield became steady immediately after the start of reaction and did not change even when time on stream was prolonged to 10 h (6). Although it took 1 - 2 h for the yield to be steady with the Ca-Cr or Ca-Mn catalyst, their performances after the induction periods were sustainable, as with the Ca-Ce system. It is thus evident that oxygen species derived from C 0 play a crucial role in coupling reactions of CH4. The effect of P(C0 ) on CH4 conversion and product selectivity over the Ca-Ce catalyst is provided in Figure 8, where P(CKU) is kept constant (30 kPa) and inert He is used as a balance gas (6). The conversion increased steeply with 2

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Table L Surface Areas and Catalytic Performances of Binary Oxides of Alkaline Earth Metal and Ce Elements Surface area CH conversion C yield (%) (%) (m /g)

v

Alkaline earth metal M/Ce

2

4


2

}

Mg Ca Sr Ba

0.2 0.2 0.2 0.2

1.4 0.6 n.a* 0.5

Ca Ca"

0.5 0.5

0.4 1.4

11.6 4.9 3.1 2.8

0.2 2.5 1.6 1.3

5.8 5.4

3.2 0.7

2

Atomic ratio. ^Not analyzed. ^Physical mixture.

0

25

50

75

100

[Ca/(Ca+M)x100], at% Figure 4. Effect of catalyst composition on CH conversion with binary Ca-Cr and Ca-Mn catalysts at 850°C 4



93

Ο

25

50

75

100

[Ca/(Ca+M) χ 100], at% Figure 5. C yield at 850°C over Ca-Cr and Ca-Mn catalysts with different compositions. 2


94

Ca-Cr "θ


ε 5—1

-co\

c ο

C

2

150

200

Time on stream /min Figure 6. Formation rates of products in the reaction at 850°C ofCH with Ca-Ce and Ca-Cr oxides.

4


alone

95

6

Ca-Mn Ca-Ce


^Ca-Cr

ϋ

1 2

1 4

1 6

1 10

1 8

Time on stream /h

Figure 7. Effect of time on stream on C yield at 850°C over Ca based binary catalysts. 2

0

20

40

60

80

P(C0 ), kPa 2

Figure 8. Dependence ofCH conversion and product selectivity on partial pressure ofC0 over a Ca-Ce catalyst (Reproducedfrom reference 6 with permission from Academic Press). 4

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96 increasing P(C0 ) up to 10 kPa but leveled off beyond 20 kPa. This Langmuiriype curve indicates the involvement of C 0 chemisorption in the present reaction. With product selectivity, CO formation was predominant at low P(C0 ) below around 20 kPa, whereas C selectivity increased with increasing P(C0 ) and reached 70% at 70 kPa. As shown in Figure 9, the Ca-Cr and CaMn catalysts showed the similar CH4 conversion - F(C0 ) curves as with the Ca-Ce system, that is, the Langmuir-type relationship between the two. Furthermore, the Ca-Cr or Ca-Mn system provided almost the same dependency of C yield on P(C0 ); the yield increased almost linearly with P(C0 ). The observations in Figures 8 and 9 point out that high P(C0 ) is essentially needed for selective formation of C hydrocarbons. Since C 0 rather deactivates basic catalysts effective for the oxidative coupling of CH4 with 0 due to the strong adsorption ability, higher C selectivity under higher P(C0 ) is peculiar to the present reaction system. When time on stream was prolonged to 8 - 10 h, as shown in Figure 7, C yields were almost unchanged except for the early stage of reaction, irrespective of the kind of a binary oxide system. Such the stable performances mean that there is no catalyst deactivation by C 0 adsorption and carbon deposition. 2

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Chemisorption of C 0 and Catalyst State 2

In order to make clear the behavior of C 0 adsorption upon C formation, the three catalysts after reaction were subjected to the TPD runs. Figure 10 shows typical TPD profiles for the Ca-Ce system. The C0 -desorption peak appeared at 730°C under flowing pure He and shifted to 810, 850, and 910°C in a stream of C 0 with P(C0 ) of 10, 30 and 70 kPa, respectively (4,6). In other words, a pool of the C 0 chemisorbed existed on the catalyst in the process of C formation at 850°C under P(C0 ) of 70 kPa, whereas it almost disappeared under P(C0 ) of 10 kPa. The Ca-Cr and Ca-Mn catalysts after reaction also provided almost the same TPD profiles as in Figure 10. No significant desorption of C 0 from any fresh catalysts were observed. The comparison of Figures 8 and 10 suggests that the occurrence of C 0 chemisorption leads to high C selectivity. To ensure this point, the amount of C 0 chemisorbed at 850°C was estimated by integrating the peak area observed in Figure 10 between 850°C and 950°C. The estimated value is plotted in Figure 11 as a function of P(C0 ) used for the TPD run. The amounts chemisorbed on all of the binary catalysts showed almost the same dependencies on P(C0 ); the values were very small at around 10 kPa but larger at higher P(C0 ). It should be noted that such dependencies are quite similar as the C selectivity - P(C0 ) curves in Figure 8. It is thus likely that C 0 chemisorption plays a key role in selective formation of C hydrocarbons. 2

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P(CC>2), kPa Figure 9. Dependence ofCH conversion and C selectivity on partial pressure ofC0 over a Ca-Cr or Ca-Mn catalyst. 4

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Figure 10. Profiles for C0 desorption during TPD measurements in different atmospheres of the Ca-Ce catalyst after the reaction of CH and C0 at 850°C. 2

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98 The largest amounts observed in Figure 11 were 0.8 - 1.1 mmol, which were only 10 - 15% of Ca contents. Since any C 0 desorbed was not detectable with the used Ce0 , C r 0 , or M n 0 alone, Ca species on the surface layer of each binary catalyst must work as the sites for C 0 chemisorption. Table 2 summarizes the results of catalyst characterization. The XRD measurements showed that the Ca-Ce, Ca-Cr, or Ca-Mn catalyst before reaction existed mainly as Ca Cei_ 0 _ , CaCr0 , or CaMn0 , respectively. The former was stable even when time on stream was prolonged to 10 h, whereas the latter two were transformed to Ca(Cr0 ) and Cao^Mno 0, which were unchanged after 8 h. This transformation took place at the early stage of reaction. The XPS spectra revealed the partial or complete transformation of Ce , Cr , and M n to the corresponding reduced species, such as Ce , C r and M n . No XRD lines attributable to any carbonates were detectable with all of the three systems. As is seen in Figure 7, the Ca-Cr and Ca-Mn catalysts showed the induction periods before the steady performances were attained. The XRD and XPS observations mentioned above suggest that the periods are caused by the changes in oxidation states at bulk phases, since any induction period was not observed with the Ca-Ce catalyst on which surface modification only took place (Table II). 2

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4+


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4 +

2+

Reaction Mechanisms Proposed The different mechanisms under low and high P(C0 ) may be proposed on the basis of the results mentioned above. At low P(C0 ), the main product from CH4 was CO (Figures 8 and 9), and the extent of C 0 chemisorption was very low (Figure 11), irrespective of the kind of a binary catalyst. Since CH4 reacted readily with the lattice oxygen to form CO and H (Figure 6), this reaction may proceed predominantly at low P(C0 ) through the following scheme: 2

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2

2

CH4 + CaMO —• CO + 2H + CaMO^ x

2

CaMOx.i + C 0 -> CO + CaMO 2

x

(3)

(4)

where M denotes Ce, Cr, or Mn element. At high P(C0 ) above 60 kPa, on the other hand, selective formation of C hydrocarbons took place, and C selectivity exceeded 60% on all of the binary catalysts examined (Figures 8 and 9). Almost the same dependencies of C selectivity and C 0 chemisorption on P(C0 ), observed in Figures 8, 9, and 11, 2

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99


1.2

P(C0 ), kPa 2

Figure 11. Amounts of the C0 chemisorbed on Ca-based binary catalysts after reaction under different partial pressures ofC0 . 2

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Table Π· Species Identified by XRD and XPS Measurements of Ca Based Binary Catalysts Catalyst

Before reaction XRD XPS 2;

Ca-Ce (0.5) Ca-Cr (l.0) Ca-Mn (1.0) 2)

1}

C^CeuA-y, CaCr0 CaMnQ

3)

Ca0

6 +

4

2;

3

2;

At a steady state. Atomic ratio.

4+

Ce Cr Mn

3;

}

After reaction XRD XPS C a ^ e ^ C ^ y , Ca0 Ca(Cr0 ) , C a O Cao.48Mn . 0 j;

2

4 +

2

0

52

3;

4+

C e , Ce" Cr Mn

With very small XRD intensities.


3 +

2 +

100

indicate that C formation involves the chemisorption process. The following scheme may be proposed: 2

C 0 -> C 0 (a) -> CO + O*

(5)

CH4 + O* —• CH « + OH-

(6)

2CH - -> C H6 -+ C H4

(7)

2

2

3


3

2

2

where C0 (a) and O* designate chemisorbed C 0 and active oxygen species, respectively. The C 0 in feed gas first adsorbs on basic C a sites, and the reduced sites, such as Ce , C r and M n , then activate the C 0 chemisorbed to provide CO and active oxygen species adsorbed on the corresponding oxidized sites (6). These sites appear to be near Ca , since the three catalysts existed as the composite oxides (Table 2). According to equation (6), CH4 reacts with the oxygen species to form methyl radicals, which subsequently undergo coupling reactions. In the former process, the regeneration of Ce, Cr, and Mn sites take place (6). Since molar ratios of C H 4 / C H observed were almost independent on P(C0 ), C 0 seems to be hardly involved in the dehydrogenation of C H to C H4. Thus, C formation at a steady state proceeds probably through a cycle mechanism between the reduced and oxidized site of Ce, Cr, or Mn species. 2

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Conclusions Binary catalysts of CaO and Ce, Cr, or Mn oxide show remarkable synergistic effects on formation of C hydrocarbons from CH4 and C 0 at 850°C, and the maximal C yields are 30 - 70 times that over each component. As partial pressure of C 0 increases, C selectivity over all catalysts increases and reaches 65 - 75% at 70 kPa. Their performances are stable during 8 - 10 h reaction. The TPD, XRD, and XPS measurements strongly suggest that C 0 chemisorption on Ca sites and subsequent activation on neighboring Ce, Cr, or Mn sites provide active oxygen species that play a key role for selective formation of C hydrocarbons. 2

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Acknowledgement The present work was supported in part by a Grant-in-Aid for Scientific Research (B) from the Ministry of Education, Science, Sports and Culture, Japan (No. 10555275).


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References 1. Asami, Κ.; Fujita, T.; Kusakabe, Κ.; Nishiyama.Y.; Ohtsuka, Y. Appl. Catal. A: General 1995, 126, 245 2. Asami, K.; K., Kusakabe, K.; Ashi, N.; Ohtsuka, Y. Stud. Surf. Sci. Catal. 1997, 107, 279. 3. Asami, K.; Kusakabe, K.; Ashi, N., Ohtsuka, Y. Appl. Catal. A: General 1997, 156, 43. 4. Wang, Y.; Takahashi, Y.; Ohtsuka, Y. Appl. Catal. A: General 1998, 172, 203. 5. Wang, Y.; Takahashi, Y.; Ohtsuka, Y. Chem. Lett. 1998, 1209. 6. Wang, Y.; Takahashi, Y.; Ohtsuka, Y. J. Catal. 1999, 186, 160. 7. Wang, Y.; Ohtsuka, Y. J. Catal. 2000, 192, 252. 8. Lunsford, J.H. Angew. Chem., Int. Ed. Engl. 1995, 34, 970. 9. Ohtsuka, Y.; Asami,K.;Wang, Y. J. Chin. Inst. Chem. Engrs. 1999, 30, 439. 10. Kuo, J.W.; Kresge, C.T.; Palermo, R.E. Catal. Today 1989, 4, 470. 11. Nishiyama, N.; Aika, K. J. Catal. 1990, 122, 346. 12. Chen,C.;Xu, Y.; Li, G.; Guo, X.; Catal. Lett. 1996, 42, 149.


Utilization of Carbon Dioxide for Direct, Selective Conversion of

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