Chemically Modified Surfaces in Catalysis and Electrocatalysis

15 S e l e c t i v i t y A s p e c t s of the

Fischer-Tropsch

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Synthesis with Supported Iron Clusters FRANÇOIS HUGUES, BERNARD BESSON, PAUL BUSSIERE, JEAN-ALAIN DALMON, MICHEL LECONTE, and JEAN-MARIE BASSET I.R.C. C.N.R.S. 2 av. A. Einstein, 69626 Villeurbanne Cédex, France YVES CHAUVIN and DOMINIQUE COMMEREUC I.F.P. 2 av. de Bois-Préault 92000 Rueil-Malmaison, France The catalysts derived from supported iron clusters exhibit in Fischer-Tropsch synthesis a high selectivity for propylene. Those catalysts are also selective for the stoechiometric homologation of ethylene to propylene and of propylene to n and iso butenes. The results are explained on the basis of a new mode of C-C - olefin coordination bond formation which implies to surface methylene fragments or methylene insertion into a metal alkyl bond. The mechanism of carbon-carbon bond formation i n FischerTropsch synthesis (1) has not yet been f u l l y understood at the moment (2) (3). Three types of mechanisms have been proposed: (i) insertion of CO into a metal-alkyl bond to produce a metalacyl species which undergoes further steps of hydrogénation(2c); ( i i ) insertion of a methylene fragment i n a metal a l k y l bond(2b); ( i i i ) hydroxy-methylene condensation between two hydroxy-carbenes. We propose here a new mechanism of carbon-carbon bond f o r mation i n Fischer-Tropsch synthesis which i s based on the recent discovery of a highly selective catalyst (3e) derived from molecular iron clusters (5). The catalyst which i s selective for propylene i n Fischer-Tropsch synthesis i s also selective for ethylene homologation to propylene which suggests for Fischer-Tropsch a mechanism derived from the mechanism of o l e f i n homologation recently proposed by Schröck (6a) and v e r i f i e d by others (6b)^ Chemisorption of Fe^CCO)-^ magnesia support (96 m /g) previously dehydroxylated at 15o °C under vacuum (10~ Torr) for 16 hours, (magnesia 150), leads to the formation of the anionic supported clusters HFe^CO)^"" and F e ( C 0 ) j (ads) according to the following reactions (7) : o

n a

3

2

0097-6156/82/0192-0255 $6.00/0 © 1982 American Chemical Society Miller; Chemically Modified Surfaces in Catalysis and Electrocatalysis ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

256

CHEMICALLY MODIFIED SURFACES

Reaction (a) w i l l occur mainly on a f u l l y hydroxylated support whereas equilibrium (b) w i l l occur on a f u l l y dehydroxylated support (7) (8). Thermal decomposition of the adsorbed clusters under vacuum (10"^ Torr) for 16 hours at 130°C leads, inter a l i a (9), to the formation of very small p a r t i c l e s of zerovalent iron. These very small iron p a r t i c l e s exhibit a super paramagnetic behaviour as determined by Mossbauer spectroscopy (9) ferromagnetic resonance (10) and magnetic measurements (12). The average partjcle size deduced from the magnetic measurements was found to be 14 A which corresponds to ca. 130 Fe atoms which i s much larger than the nuclearity of the starting cluster (11). These very small part i c l e s supported on magnesia exhibit interesting s e l e c t i v i t i e s when they are contacted either with CO + H^, or with C2H4 or with C3H5 as indicated i n the following examples. In a typical example Fe3(CO)j2 (0.026 g ; 0.052 m.mole) was chemisorbed i n a sealed tube on a magnesia(|50). The supported cluster was thermally decomposed as previously. The resulting catal y s t contained 1.8% wght Fe/Mg0. Introduction of CO + H (760 Torr) i n a molar r a t i o 2 : 1 i n the glass equipment was followed by a stepwise increase of temperature from 25 up to 200°C. Analysis of the gas phase gave the results represented on Figure l a . At 176°C the conversion of CO to hydrocarbons i s close to 1 % with mainly propylene (32%), methane (26,1 %) ethylene (9,2 % ) , 1-butene (7,3 % ) , cis-2-butene (3,6 % ) , trans-2-butene (5,5 % ) , isobutene (1 %) and C- hydrocarbons (7 % ) . A l l the paraffins except methane are present i n much smaller amount than o l e f i n s . Figure (lb) represents typical results obtained i n Fischer-Tropsch synthesis i n a dynamic reactor using a catalyst derived from Fe (CO) /Al 0o (3e). The high s e l e c t i v i t i e s for propylene which can be as high as 45 % (12) and the low s e l e c t i v i t i e s for ethylene suggest that ethylene could be a primary product i n Fischer-Tropsch which could undergo a secondary reaction leading s e l e c t i v i t y to propylene. I t was therefore l o g i c a l to study the behaviour of ethylene on such catalysts. In another experiment Fe3(CO)i2 (0.100 g ; 0.20 m.mole) was chemisorbed i n a sealed tube on a magnesia(]50) and then thermally decomposed as previously to give a catalyst containing 2 % wgth Fe/Mg0. Introduction of C2H4 into this catalyst was followed by a thermal treatment at low temperature to avoid secondary reactions and high conversions. At 170°C, Figure l c , ethylene i s converted (about 3 %) to ethane (2 %) (seIf-hydrogénation) and to Cj and C3-C4 products (1 % ) . These Cj and C3-C4 products are propylene (70 % ) CH4 (5.9 % ) , 1-butene (11.3 % ) , c i s - 2 butene (4,5 % ) , trans-2-butene (5,7 %) and isobutene (1 % ) . Since high s e l e c t i v i t y for propylene can be reached on the same catalyst and at the same temperature either from a mixture of CO + H2 or from C2H4 alone, some elementary steps leading to propylene i n both cases are l i k e l y to be the same : ethylene would be a primary product formed from CO + H2 which would undergo a secondary reaction leading s e l e c t i v i t y to propylene (13). 2

3

l2

2

y

Miller; Chemically Modified Surfaces in Catalysis and Electrocatalysis ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

15.

HUGUES E T AL.

257

Fischer-Tropsch Synthesis

TABLE I COMPARATIVE ACTIVITY OF VARIOUS IRON BASED CATALYSTS

Catalyst Fe (CO) /Al 0 3

12

2

*Fe(CO) /Al 0 5

2

3

3

*Fe(CO) /*fgO 5

Fe(NO) ) /Al 0 3

3

2

3

% Fe Wt

T°C

Selectivity to HC

0.82

270

3.3

100

57

1.85

260

3.3

100

43

0.50

265

1.4

100

60.3

8.1

270

19.4

% Conv.

Selectivity to olefins

62.6

38

* Mainly as (HFe (CO) ) . Flow reactor; amount of catalyst : 40 g. selectivity and conversion are taken after 5 hours on stream. 3

l

n

V Conversion = 100 x —

1

Selectivity to HC

(C

f

C

H

+

H

+

A

m

1 0 0x

m

C

°°2 —

H

n 2 n + 2 2 m 2m

- 100 x + yn C H, + j n 2n + 2

Selectivity t o , olefins

+

n 2 n • 2> — — CO input

0

y

1 m C H + C0 £ m 2m 2 0

o

2 m

__T ° * 5 „„ .5 _ „ y n C L ^ + y m CH ^ n 2n + 2 £ m 2m 0

0


258


Figure 1. Selectivities in the reactions CO + H (a-b) or C H (c) or C$H (d) with catalysts Fe/MgO (a,c,d) or Fe/Al O (b). Temperatures: a, 176°C; b, 270°C; c, 170°C; d, 140°C. In c and d products larger than C have been neglected. In c C H in excess and C H produced by self-hydrogenation of C H is not represented. Key: O, olefin; • , paraffin. t

9

t

h

6

s

5

9

k

2

6

t

h

Bath reactor. Amount of catalyst 400 mg, reaction time ca. 10 h. The catalysts are thermally and irreversibly decarbonylated at 150°C before catalytic run.


15.

HUGUES

ET

AL.


259

Since butènes were also produced from CO + H or C2H4 on the same Fe/MgO catalyst i t was l o g i c a l to study the behaviour of propylene on such catalyst. In a third experiment Feo(CO)\2 (40 mg ; 0.08 m.mole) was chemisorbed on a magnesia^Q (1.1. g) and thermally decomposed under vacuum as previously described. C3H6 (140 Torr) was introduced into this supported catalyst which was heated stepwise from 25 up to 200°C. At 140°C propylene was converted to propane (0.3 %) (self-ydrogenation) and to a mixture of Cj, C2> C4, C5, mainly o l e f i n i c , hydrocarbons (0.1 % ) . In the C j , C2> C4, C5 fraction the s e l e c t i v i t y for butènes was 65 % (CH4 : 5.9 %, C2H4 : 5.9 %, C4H3 : 65 %, CSHIQ : 17 %) which indicates that homologation of propylene to butènes occurs v i a a " C j " surface fragment (2b). At 140°C the butene fraction contains 1-butene (79 % ) , trans-2-butene (6 % ) , cis-2-butene (12 %) and isobutene (3 % ) . At 168°C the butene fraction contains 1-butene (15 % ) , c i s 2-butene (32,6 % ) , trans-2-butene (44,9 %) and isobutene (9,1 %) ; the pentene f r a c t i o n contains 90 % linear pentene and 10 % of isopentenes ( f i g . Id). The above results indicate that small iron p a r t i c l e s , having sizes close to 14 A, exhibit i n Fischer-Tropsch synthesis a rather high s e l e c t i v i t y for propylene and a low s e l e c t i v i t y for methane. Even higher s e l e c t i v i t i e s have been observed with Feß (CO)i2Ml203 (3e) (45 %) or with Co clusters encapsulated within the pores (11 1) of "A type" zeolites (100 %) (14). Such high sélectivités have probably a mechanistical o r i g i n with respect to the mode of C-C bond formation. Selective formation of propylene from CO + H2 or from C2H4 as well as selective formation of butènes from propylene on the same catalyst suggest the following mechanism for propagation. Formation of CH4 from C2H4 (or from C3H5) can be accounted for by homolytic cleavage of C2H4 (and C3H5) into surface carbene species most l i k e l y methylene, which can be further dehydrogenated to carbyne l i k e and surface carbon fragments (15). I t i s not unreasonable to assume that during Fischer-Tropsch experiment, CO i s dissociated (16) to surface carbon (17) and "Fe2 oxo species" (18). The surface carbon would undergo the reverse of reaction (1) that i s hydrogénation to methylene and coupling of methylene to give ethylene (19). Propagation involves coordination of the d-olefin to the surface carbene giving r i s e to a metallo-cyclobutane transition state followed by (i-H transfer. Similar reaction has been observed recently by P e t t i t (20) who selectively obtained propylene from the reaction of ethylene with an octacarbonyl-|*-methylened i i r o n complex. The next propagation step involves propylene coordination to the surface carbene with formation of n-butene reaction (3) or isobutene reaction (4) . The high s e l e c t i v i t y for n-olefin, i n our experiments as well as i n conventional Fischer-Tropsch cat a l y s t s , must be accounted for by a selective coordination and (or) reaction of the o l e f i n (21) according to reaction (3) which i s probably due to the e l e c t r o p h i l i c character of the surface 2

+



260 CH

CH

0

I

C H. 2 4

+H

+ n Fe

0

I

Fe - Pe 4 -H

0

-5

+H

Fe 4

CH. 4

+ n Fe (1)

I

CH C / l \ -H Fe - Fe - Fe — F e - Fe - Fe - Fe

CH Fe - Fe

+ C H. 2 4

Fe - Fe

Fe - Fe

+ C-H^ —> 3 6

Fe - Fe -» n-C„H 4o

+ C H

Fe - Fe —>

0

C-H,. 36

+

n Fe

(2)

(3)

0

CH

/ \ Fe - Fe

3

6

CH Fe - Fe

+ R-CH=CH -* Fe - Fe 2

2

(5)

-*• R-C(CH )=CH

(6)

—•

(7)

2

K

CH Fe - Fe CH.

/ \

-* R-CH -CH=CH

2

+ R-CH=CH -»- Fe - Fe 2

S

CH.

I

2

Fe - Fe - Fe

3

2

-CH -R CH» 2 R

I

2

Fe

R-CH=CH

2

Possible mechanisms f o r C-C bond formation i n Fischer-Tropsch.


15.

HUGUES E T A L .


261

carbene. This e l e c t r o p h i l i c character of surface CH^ species has been shown to occur on metal surfaces by work-function measurements (22) as we 1 as with "carbidic iron clusters" which were found to be carbocationic i n character (17a). Such electropositive carbene would be the reason for reaction (3) to occur rather than reaction (4) which should be favored for s t e r i c reasons. The high s e l e c t i v i t y for * - o l e f i n s may be due to the select i v e (Î-H transfer from the C carbon of the metallo-cycle to the most substituted carbon of the metallo-cyclobutane. Such s e l e c t i v i t y i n the ß-hydrogen transfer was observed when ethylene or propylene was reacted with TaCp(CHCMe3)Cl2 (23). I t i s impossible to decide whether or not the metallo-cyclobutane involve a single Fe atom, two iron atoms as suggested by P e t t i t ' s experiments (19) or an "ensemble" of many iron atoms. However thermal decomposition of platinacyclobutanes (24) or tungsta-cyclobutanes (26) lead to a ^-hydrogen transfer leading to the corresponding olefins (16). Mechanistically i t i s l o g i c a l to observe high s e l e c t i v i t y for propylene i f we assume that coupling of methylene to ethylene as well as ethylene coordination to surface carbene are fast reactions. Propylene for s t e r i c hindrance would react more slowly than ethylene with surface carbene reaction (3) whereas reaction (4) would be less favored for electronic reasons. I t i s d i f f i c u l t at this point to speculate why the s e l e c t i v i t y for propylene i s associated with small iron p a r t i c l e s . One p o s s i b i l i t y i s that the small iron particles displace the equilibrium olef i n ( j j i=± o l e f i n / \ and prevent thus further steps of propagation v i a the o l e f i n + carbene mechanism ; besides these small Fe particles would have small hydrogénation properties which thus avoid methane formation from the carbene and saturated hydrocarbon formation from the o l e f i n . In conclusion, although our results do not rule out the mechanism of carbene insertion into a metal-alky1 bond (2b), the p o s s i b i l i t y of making C - C bonds i n Fischer-Tropsch v i a a carbene-olefin mechanism should be considered as an alternative path. Further studies are i n progress to decide between both types of mechanisms• 2

a

Chemically Modified Surfaces in Catalysis and Electrocatalysis

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