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The of Rhenium and Its Role in -Rhenium Reforming Catalysts

By Robert Burch Department of Chemistry, University of Reading

The increasing environmental concern Contained within these various proposals about the pollution caused by motor vehicles are two important questions. First, is the has focused attention on rhenium reduced to the ? Second, if as a means of improving the octane number rhenium metal is produced, does it form an of -free petrol. Much research has been with platinum ? carried out in recent years aimed at improving the conventional platinum-alumina reforming The Interaction between Rhenium catalysts. The most significant advance has and the Support turned out to be the discovery of a new family Unsupported rhenium are easily of catalysts in which a second metal, usually reduced to the metal by at 400 to rhenium, is added to the platinum (I). A 500°C. With alumina supported oxides, bimetallic platinum-rhenium reforming cata- however, the situation is complicated because lyst was first introduced (2, 3) by Chevron in of a strong interaction with the support (IS). February 1967, but several such catalysts are Evidence for such an interaction in Re/AI,O, now available. catalysts which have been calcined is found Rhenium activated catalysts have many in the fact that Re20,, which is a volatile advantages over conventional catalysts, but in compound, is not detected in the gas particular they offer greatly improved temper- even when these catalysts are regenerated in ature stability and product distribution air at 550°C (16-18), On the other hand, selectivity (4, 5) (Figure I). Some of the Bolivar et a1 (7) claim that there is a loss of applied aspects of platinum-rhenium catalysts rhenium from catalysts that have not been have been described previously in this calcined before reduction. The calcination Journal (4), but the purpose of this review is treatment is obviously important and will be to examine rhe experimental evidence that is referred to again. available concerning the oxidation state of rhenium and its role as a promoter in platinum Oxidation State of Rhenium reforming catalysts. before Hydrogen Treatment The influence of rhenium in prolonging the Yao and Shelef (18) have presented evi- lifetime of platinum-rhenium catalysts has dence from chemisorption experiments which variously been ascribed to (i) the formation of shows that prior to calcination the rhenium on an alloy which is less active than pure an alumina support is probably present in two platinum for dehydrogenation (6-9); (ii) the forms, a crystalline three-dimensional phase presence of Re4+ which is active for the of Re,O,, and a dispersed two-dimensional of deposits (10, I I) ; phase containing Re4+. Calcination would be or (iii) the stabilisation of platinum crystallites expected to lead to the evaporation and loss against (12, 14). of the crystalline Re,O,. However, if there

Platinum Rev., 1978, 22, (2), 57-60 57 difficult to reduce but in dry hydrogen reduction proceeds slowly at 5oo0C, and complete reduction can be obtained (IS, 19, 20). On the other hand, in moist hydrogen it appears that reduction of rhenium below the 4+ oxidation state is difficult, if not impossible (10, 21). Effect of Calcination Treatment on the Minimum Temperature for Reduction In the Absence of Platinum The calcination treatment has an im- portant influence on the reducibility of' rhenium oxides on alumina. After drying at IIOOC(7-9) or after calcining at 330°C (IS), rhenium on alumina can be reduced at 320 to 330°C. However, Yao et a1 (IS) found that the maximum rate of reduction occurred at 550°C after a dispersion treatment which involved heating the catalyst for 16 hours in nitrogen at 500°C. Further calcination in air at 50o"C for two hours produced two re- duction maxima, one at 350°C and the other at 550°C (Figure 2). McNicol (19) observed a single reduction peak at 550°C after cal- cining his samples in air at 525OC for two hours before reduction. The absence of a low is available a sufficiently large surface of free temperature peak is probably because the alumina, an evaporated crystal of Re,O, amount of rhenium present was only 0.2 per could react with this surface to produce more, cent as compared with 1.2 per cent in the dispersed, Re4+.This would account for the samples used by Yao et al. low loss of Re,O, during oxidative regener- The conclusions are that low temperature ation. It would also mean that in a typical calcination results in an easily reduced form commercial catalyst, having a rhenium con- of rhenium (Re,O,?) but that calcination tent of only about 0.2 per cent, the majority above soo"C converts much of the rhenium of the rhenium would be present initially in to a more stable oxide form (Re4+?), particu- the dispersed form as Re4+. It should be larly in catalysts containing small amounts of noted, however, that McNicol (19) has found rhenium. that for a catalyst containing 0.2 per cent rhenium, the oxidation state of rhenium is 7 +- In the Presence of Platinum after calcination in air at 525°C. Platinum is well known as a catalyst for the reduction by hydrogen of a number of metal Are Both Forms of Rhenium oxides. Such a catalytic effect has been Reducible? observed for platinum-rhenium catalysts The crystalline form of Re,O, is easily dried at 110°C (7). In the presence of reduced to the metal at around 300 to 350'% platinum the reduction of rhenium com- (7,8,9, 18). The dispersed Re4- is much more mences at much lower temperatures, 160 to

Platinum Metals Rev., 1978, 22, (2) 58 180°C instead of 330°C. On the other hand, after high temperature calcination no cata- lytic effect due to the platinum is observed (Io, I9). The conclusion to be drawn from this is that platinum can catalyse the reduction of three-dimensional crystalline supported rhenium oxide, but has little effect on the reduction of dispersed rhenium oxide. Con- sequently, in an industrial catalyst with a metal content of about 0.2 per cent the interaction between platinum and rhenium during reduction is likely to be minimal. Do Rhenium and Platinum Form an Alloy? Under the most favourable conditions- low calcination temperature, high rhenium loading-it has been clearly estabiished (8, 9) that there is an interaction between rhenium and platinum leading. ultimately to alloy formation. For calcined catalysts there are some discrepancies in reported work. Sovostin et a1 (13) and Bursian (12) claim that rhenium increases the dispersion of platinum on alumina, which implies some form of interaction, although not necessarily to the activity of the catalyst ir is difficult to see how extent of alloy formation. However, McNicol this could occur if the only function of (19) reports no interaction between platinum rhenium was to hydrogenate carbon residues. and rhenium during reduction, although sub- A number of other workers have argued sequent alloy formation between migrating that it is the formation of a platinum-rhenium and coalescing particles could still occur, alloy that is responsible. Assuming that alloy albeit slowly (22). formation occurs, the influence of rhenium It appears that platinum and rhenium can could arise either because of a change in the form alloys on an alumina surface and do SO electronic charge at the platinum atoms, or when there is an interaction during the re- because the rhenium atoms dilute the duction stage. Whether alloy formation occurs platinum atoms on the surface. in industrial catalysts is not certain, although The direction of electron transfer between some form of direct interaction between rhenium and platinum is difficult to predict platinum and rhenium seems probable. and both Pt6- (8) and Pt6' (23,24) have been suggested. Electron withdrawal from plat- The Role of Rhenium inum seems more likely since the magnetic Johnson (10,21) has suggested that Re4+ susceptibility of platinum is increased by species on the alumina surface can hydro- alloying with rhenium, Pts+ would have a genate carbon residues and thus increase the high activity for reforming reactions since lifetime of the platinum catalyst. However, these tend to proceed through carbonium ion since the addition of rhenium increases not intermediates which are formed with electron only the lifetime but also the selectivity and donation to the metal atom.

Platinum Metals Rev., 1978, 22, (2) 59 A diiution effect will arise because rhenium a clear answer. The basic question is whether atoms in the surface of an alloy particle will or not platinum and rhenium form an alloy reduce the number of platinum atom clusters. under the conditions likely to be encountered At least two and probably three or more in an industrial reactor. The answer obtained contiguous platinum atoms are required fcr is that under dry laboratory conditions an coke formation, whereas reforming may occur alloy may be formed. However, bearing in on isolated platinum atoms (23). Therefore, mind the ubiquity of water and its influence the effect of adding rhenium would be to on state reactions, one should perhaps decrease the rate of coking without affecting be cautious in assuming that the results of the reforming reaction. It is probable that carefully controlled laboratory experiments rhenium exerts both an electronic and a struc- will be applicable in an industrial context. tural influence on platinum. The electronic Perhaps the clearest indication that there is effect will result in an increase in the intrinsic at least some form of interaction between plat- activity of the platinum, and may also affect the inum and rhenium under industrial conditions selectivity. The geometric effect will result in comes from the fact that platinum-rhenium an increase in the lifetime of the catalyst, and catalysts are more active in reforming may again affect the selectivity, reactions than pure platinum catalysts. 111 conclusion, the balance of the available Conclusions evidence supports the existence of a direct Recent research on platinum-rhenium interaction between platinum and rhenium. reforming catalysts illustrates how pure Whether this interaction results in alloy research aimed at giving a better understand- formation, or involves, for example, the ing of an industrial system can completely formation of a more highly dispersed form circumscribe the problem and yet not provide of platinum, is still not certain.

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Platinum Metals Rev., 1978, 22, (2) 60