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by F r a n k L. Kester*

Hamilton Standard Division of United A i r c r a f t Corporation Windsor Locks. Connecticut 06096 INTRODUCTION The ever i n c r e a s i n g demand for n a t u r a l gas a s a fuel and raw material h a s stimulated renewed efforts t o find other ways of producing methane. With more and m o r e evidence of an "energy c r i s i s " upon us. alternative approaches such a s catalytically synthesizing methane from hydrogen and carbon dioxide m e e t with m o r e promise of development. A fairly complete s u m m a r y of the r e s e a r c h on carbon dioxide methanation has been given by E m m e t t (5), and details of the carbon monoxide-hydrogen reactions by K i r k and Othmer (10). Recent studies on the reaction between hydrogen and carbon dioxide over a supported nickel catalyst have been (3). Hydrogenation of conducted by Binder and White (1) and by Dew carbon monoxide over a nickel catalyst h a s also been investigated ( 6 ) A few y e a r s ago, Karn and h i s a s s o c i a t e s (9) studied ruthenium a s a possible methanation catalyst. In a recent experiment, Lunde and Kester (13) studied the reaction r a t e s of methane production f r o m hydrogen and carbon dioxide. The work described h e r e i s a n extension of t h i s effort, and p r e s e n t s the kinetics and possible mechanisms for the reaction between hydrogen and carbon dioxide.


It i s believed by many w o r k e r s (5) that carbon monoxide is a critical intermediate in carbon dioxide methanation. The following reactions summarize the overall reduction process. CO,

+ Hz



C O +3Hz t CH4 +H,O

Because the equilibrium f o r Equation 1 is somewhat unfavorable a t the reaction t e m p e r a t u r e s (200'-400' C ) . it can be argued that this reaction path i s somewhat unlikely. A way out of this difficulty is to require that a t these t e m p e r a t u r e s the methanation of carbon monoxide (Reaction 2 ) proceeds much f a s t e r than carbon monoxide production (Reaction 1). Reaction 2 could be i n equilibrium. If carbon monoxide were rapidly consumed a s it formed, no carbon monoxide would be observed in the reactor exit s t r e a m . T h i s w a s the c a s e with the data t r e a t e d h e r e (13). However, in h i s work with a ruthenium catalyst. Karn f9) did observe 1.5-24 carbon monoxide i n t h e exit stream. The reason for h i s observation

Present a d d r e s s : Institute of Gas Technology, 3424 S. State Street, Chicago, Illinois 60616


is not clear. It is possible that because of the extended operation (80 days) t h e catalyst may have become deactivated f o r t h e reaction converting carbon monoxide t o methane.

REACT ION MECHANISMS Mechanism I The reaction mechanism outlined h e r e follows t h e work of Oki and Mezaki (14, 15) f o r the water-gas-shift reaction over i r o n oxide. CO, (g)

i coz


HZO (ad)

i J

H O (g) ,

Hz (g)

2 H (ad)

Reactive coZle:[ CO (ad) CO (9) To Methane

The absorbed carbon monoxide is ultimately reduced t o methane by s o m e reaction path not examined here. F o r t h e r a t e model developed i n t h e next section, t h e reaction of 2H(ad) and CO(ad)(step iii) is assumed t o offer the controlling resistance. The other reactions a r e assumed t o be i n equilibrium. Mechanism 1 1 An alternative mechanism, f i r s t suggested by Doehlemann (4) in 1938 and subsequent1 by Kul'kwa and h i s coworkers (11,12), h a s been described by Wagner (177. The catalyst was a l s o i r o n oxide: however, the reaction t e m p e r a t u r e s were much higher (87Oo-ll22"C) than i n Oki and Mezaki's work (40O0-45O0C) and higher than i n t h e s e data (207"-371"C) on ruthenium. This mechanism i s included because it displays t h e observed dependence on both hydrogen and carbon dioxide, each to the f i r s t power (Table 2); it does not contain t h e hydrogen adsorption constant i n its expression (which was found t o be very small o r zero); and it does not r e q u i r e the presence of t h r e e active s i t e s indicated i n Mechanism I(which may be somewhat improbable). The alternative mechanism (17) is -

co, (9 i co, (4
CO, (ad) %CO

(ad) +O(ad)

Adsorbed oxygen atoms r e a c t with molecular hydrogen i n a single step:

H (9) Z

iiib O ( a 4 -H,O
H,O (g)


H O (ad) ,
CO (ad) -o T

& CO



This mechanism a s s u m e s that s t e p iiib is rate-controlling and that the o t h e r steps a r e in equilibrium. * RATE EQUATIONS The model follows Hougen and Watson (7, 8) and employs a LangmuirThe modifications n e c e s s a r y Hinshelwood r a t e model f o r Mechanism I. f o r Mechanism I1 a r e given i n the footnote below. Assuming reaction s t e p iii , Mechanism I, a s rate-controlling, and with , iv, v. and vi i n equilibrium, the following r a t e expression can be written:
i, ii

r = kF 92 0COz H


where r is t h e f o r w a r d reaction r a t e , kF i s the forward reaction rate coefficient, and Pi r e p r e s e n t s the fraction of catalyst surface coverage of the ith species. The s u r f a c e concentrations i n equilibrium with t h e gaseous r e a c t a n t s o r products can be represented by = KHz PH, bZv

eCO, =



'HZO = KH20 'HZO




, e

where Bv is the f r a c t i o n of vacant catalyst surface, P.is the equilibrium p a r t i a l p r e s s u r e , and Kii s t h e equilibrium absorptlon'constant of the ith species. Inserting relationships 4 and 5 into Equation 3 gives r = k 8 3 P P V H2 COZ where = kF KHz KCOz


The total f r a c t i o n s u r f a c e coverage is equal t o t h e sum of all occupied and unoccupied s i t e s , which equals unity

Mechanism II would modify the r a t e expression by reducing the exponent in t h e denomin t o r of Equation 1 4 ( p r e s e n t e d l a t e r ) t o one and a l s o eliminate PH ZKH '1' f r o m t h e denominator of t h i s expression.



On inserting Equations 4, 5, 6, and 7 into Equation 10, one obtains

which, on solving f o r e$.yields





H '2



K C O z + 'COKCO


Given the Arrhenius relationship

k = Ae- E a / R T


and upon inserting Equations 12 and 13 into Equation 8, the final relationship obtained f o r correlation with the experimental d a t a is -

r = Ae

-Ea/ RT

pH, pC O2 c1 + P K 'I2 PCOzKC02 + PCOKCO + PH20KHz0 + H 2 Hz




reaction r a t e = - dpc4 dt


A = pre-exponential f a c t o r


E a = activation energy, cal/mole

R = 1.987 cal/deg-mole

T = degrees Kelvin

To evaluate t h i s equation and t o determine unknown constants, Equation 14 was rearranged as follows -

Other constants a r e t h e s a m e a s defined e a r l i e r .


Y t Ea I d - - R

After Y has been evaluated, the r a t e expression i s then of the form Y = mX + b, so that a plot of Y v e r s u s 1 / T f o r s e v e r a l runs f o r m s a line with a slope -Ea/R and a 1 / T = 0 intercept of Ink. If the correlation i s good. the plot will show minimum s c a t t e r and good linearity when a p r o p e r f o r m the rate equation h a s been chosen or a p r o p e r value of an adsorption coefficient h a s been obtained. A l e a s t s q u a r e s calculation of a number of data points will give 0, the standard deviation. The 62 data points shown i n Table 1 contained experimental information on space velocity, average methane p a r t i a l p r e s s u r e (P ), average w a t e r vapor p a r t i a l p r e s s u r e (PH o), and reactor temperatu%'(T). The equilibrium carbon monoxide p a r t i a l p r e s s u r e , Pco; was obtained f r o m pC H4pH20
p 3



H 2 using average experimental p a r t i a l p r e s s u r e s and K2, the equilibrium constant f o r Reaction 2. The value K, was calculated a s equal t o exp 17688. T-2 + 17.600-6.7441nT) f r o m ( l / l . 987)(0.00266T + 23095. T data contained in Reference 16.

The experimental reaction rate, r, was calculated a s

r = Sv


i s the experimental space velocity, i s the p a r t i a l p r e s s u r e of CO, a t the reactor inlet, and i s the p a r t i a l p r e s s u r e of GO2 a t the r e a c t o r outlet.




DISCUSSION Determination of F o r m of Rate Equations The minimum l e a s t s q u a r e s standard deviation, 0 , was taken a s a quantitative m e a s u r e of a f i t of the data when correlating various f o r m s of the driving f o r c e portion of the r a t e equation. Adsorption coeffients a r e t r e a t e d below. The r a t e data t r e a t e d a r e summarized i n Table 1..


Since some of the data were collected at moderate t o high conversions,

an initial screening was conducted on all runs t o determine if any were

close t o the thermodynamic limit. Two runs were found to be c l o s e r than 5% (Runs 533 and 534 i Ref. 13) of the thermodynamic limit and were not n included in the final treatment. This m e a n s that any influence by the r e v e r s e reaction, Equation 1, on the r a t e data was no g r e a t e r than 5 $ and for most runs was much l e s s than 1%.

If one assumed that the adsorption of hydrogen i s rate-controlling (reaction path i). then U is found t o be equal to 0.3305 (Table 2); if the absorption of carbon dioxide i s assumed t o be controlling (reaction path ii), U is 0.4688. It a p p e a r s that assuming hydrogen to b e in equilibrium i s consistent with Bond (Z), who h a s summarized the activation energies and pre-exponential factors f o r hydrogen reactions on various transition metals. Bond indicates an activation energy f o r hydrogen adsorption generally around 5 kcal and never g r e a t e r than 10.6 kcal. It a p p e a r s that a lower activation energy than was observed for these data (18.33 kcal) i s n e c e s s a r y f o r the adsorption of hydrogen onto active m e t a l sites to b e controlling. Bond a l s o tabulates pre-exponential f a c t o r s that would indicate reaction r a t e s much f a s t e r than observed for these data.
Secondly, the adsorption of carbon dioxide was not considered to be rate-controlling, a s the resulting rate equation would not reflect the p r e f e r r e d dependence on the r a t e on p , t o the first power (Table 2). Oki H and Mezaki (14) also considered the possibility of only one adsorbed hydrogen atom reacting with one adsorbed carbon dioxide m o l e c a y This would reflect a dependence of PH to the one-half power with Pco2t o the f i r s t power in the r a t e equation.' This relationship, when correlated with the data, yields an unsatisfactorily high standard deviation of 0.3165. The most significant improvement and the best correlation of the data with the driving f o r c e expression were obtained with a dependence of pH,Pco, (both t o the f i r s t power) giving a U of 0.2113. This expression suggests a rate-controlling reaction of two adsorbed hydrogen atoms with one adsorbed carbon dioxide molecule (Mechanism I) o r the reaction of gaseous hydrogen with an adsorbed oxygen atom (Mechanism 11). Determination of Adsorption Coefficients With t h i s f o r m of the r a t e expression. further l e a s t squares calculations were performed t o evaluate the various adsorption constants. A constant such a s KCO would be systematically varied on a t r i a l - a n d - e r r o r b a s i s until a m i n i m u d w a s obtained i n the U v e r s u s KCO curve (Figure 1). 2 The other adsorption constants were also evaluated in t h s manner. The minimum values for the adsorption constants a r e given i n Table 3. Minimum values were obtained f o r a l l reaction g a s e s except hydrogen. The 0 v e r s u s KH curve (not shown) was quite broad and shallow in the region of KH bel& atm-I. Apparently t h e s e experimental data a r e not of s d f i c i e n t quality t o obtain a precise.value of KH,, which i s t h e r e f o r e reported t o be l e s s thap atm-' f o r this temperature range. No t e m p e r a t u r e dependence of the adsorption constants was included i n the evaluation.

15 3
FIT O F RATE EQUATION TO EXPEFUMENT DATA L e a s t Squares Standard Deviation. F o r m of Rate Equation" Table 2. Driving F o r c e Evaluation


0.3305 0.4688 0.3708 0.3165 0.2113


p 112 H Z

P JtP Hz coz
P P Hz COz

Adsorption Coefficient Evaluation pH, pC




pHzpCOz [1 + KcoPC0z12


pHz pC 0


pHz pCOz



KCOzPCOz + K c o P c o ~ 0.1650


Driving f o r c e and adsorption t e r m s only


Table 3.


Ad s o rption Constant


KHz %O

<io-3 475 0.160 MECHANISM I1


K C0 K H Z

2. 62

< 10-3
1490 0.491


Determined by the l e a s t squares t r i a l - e r r o r fit of the 62 d a t a points over a temperature range of 207"-358"C. These a r e average constants f o r t h i s temperature range.

For MechaniEquation 15 , t h e : c o r r e l a t i o n of U = The activation ene: exponential f a c t o r

For Mechanism 11, the values were slightly different, with A = 1.037 X 10'O atm-' hr-', and E a = 17.90 kcal/mole.

I, the various adsorption constants included i n st s q u a r e s calculation f o r the 62 data points, gave a 1144. The resulting curve is shown i n F i g u r e 2. y w a s found t o be 18.33 kcal/mole, and the p r e as 3.524 X 10" a t m h r -I.

CONCLUSION L i t e r a t u r e data on the r a t e s of carbon dioxide methanation collected over a 1 / 2 & ruthenium-on-alumina catalyst a t 1 atmosphere and temperatures f r o m 207" t o 371C have been interpreted to proceed stepwise first t o carbon monoxide and ultimately t o methane. Correlation of t h e data yielded a dependence on pH, and Pco , both t o t h e f i r s t power. Two possible m e c h a n i s m s consistent m t h previo6s l i t e r a t u r e studies have been suggested and discussed. Rate constants, activation e n e r g i e s , and adsorption constants w e r e determined.

LITERATURE CITED 1. Binder, G. G. and White, R. R., "Synthesis of Methane f r o m Carbon Dioxide and Hydrogen,'' Chem. Eng. Progr.&,563 -574 (1950) November. 2. 3. Bond, G. C . , Catalysis by Metals. New York: Academic P r e s s , 1962. Dew, J. N., White, R. R. and Sliepcevich, C. M., "Hydrogenation of Carbon Dioxide. on Nickel-Kieselguhr Catalyst," Ind. Eng. Chern. 47, 140 146 (195 5) January.


5. 6.

Doehlemann E . , "The Mechanism of t h e Water-Gas Reaction on a n I r o n Catalyst," -2. Elektrochem. 178-83 (1938)EChem. Abstr. 32, 4060 (1938) 3. Emmett, P. H., Ed., Catalysis, Vol. 2, 299-303. New York: Reinhold, 1951. Gilkeson, M. M., White, R. R. and Sliepcevich, C. M., "Synthesis of Methane by Hydrogenation of Carbon Monoxide i n a Tubular Reactor," Ind. Eng. Chem. 45. 460-467 (1953) February. Hougen, 0. A. and Watson, K. M., "Solid Catalysts and Reaction Rates. General Principles." Ind. Eng. Chem. 3 2 529-541 (1943) May. Hougen. 0. A. and Watson. K. M., "Kinetics." i n Chemical P r o c e s s Principles. New York: John Wiley, 1947. Karn, F. S., Shultz. J. F. and Anderson, R. B., "Hydrogenation of Carbon Monoxide and Carbon Dioxide on Supported Ruthenium C a t a l y s t s at Moderate P r e s s u r e s , " I & EC Product Res. Develop. 5,265-269 (1965) December


7. 8. 9.


Kirk, R. E. and Othmer, D. F., "Carbon Monoxide-Hydrogen Reactions," i n Encyclopedia of Chemical Technology. 2nd E d . , Vol. 2, 446-489. New York: Interscience Publishers, 1963. Kul'kova. N. V. and Temkin. M. I . , "Kinetics of the Reaction of Conversion of Carbon Monoxide by Water Vapor." Zh. F i z . Khim. 695-713 (1949)c Chem. Abstr. g, 7308 (1949)l.




Kul'kova. N. V., Kuznets, 2. D. and Temkin, M. I., "The Exchange of Oxygen Isotopes Between Carbon Monoxide and Carbon Dioxide on an Iron Oxide Catalyst, "Dokl. Akad. Nauk SSSR 9 3 1067-70 (1953) [ Chem. Abstr. 49. 8684 (1955) I.


14. 15.

Lunde. P. J. and Kester. F. L., "Rates of Methane Formation f r o m Carbon Dioxide and Hydrogen Over a Ruthenium Catalyst," J. Catal. 30, 423-429 (1973) September.

Oki, S. and Mezaki, R., "Identification of Rate-Controlling Steps f o r t h e Water-Gas Shift Reaction Over an Iron Oxide Catalyst." J. Phys. Chem. E, 447-452 (1973) F e b r u a r y 15.


Oki, S. and Mezaki. R. "Mechanistic Structure of the Water-Gas Shift Reaction in the Vicinity of Chemical Equilibrium." J. Phys. Chem. 77, 1601-1605 (1973) June 15.

"Heats. Wagman, D. D. etal., F r e e Energies, and Equilibrium Constants of Some Reactions Involving 0,. H , HzO, C, CO, CO,. and CH,. , R P 1634, J. Res. Nat. Bur. Stand. 34, 143-161 (1945). Wagner, C., "Adsorbed Atomic Species a s Intermediates in Heterogeneous Catalysis." m D. D. Eley, e t al., Eds., Advances i n New York: Academic Catalysis and Related Subjects, Vol. 2'. 323-81. P r e s s , 1970.



0.1280 0.5





10 .

K~~~ otm-'



1 0


1.6 17 .



f x 103 OK-I

2.0 2.1