Applied

Cc&&is,

47 (1989)

115-123

115

Elsevier Science Publishers

B.V., Amsterdam

Printed

in The Netherlands

Effect of Antimony (IV) Oxide, Bismuth Phosphate and Tin (IV) Oxide on the Catalytic Properties of Compound Oxide Catalysts in the Oxidative Dehydrogenation of n-Butene
FENG-YAN
Lanzhou

QIU

Institute

of Chemical

Physics,

Chinese Academy

of Sciences,

Lanzhou

(China)

and LU-TAO WENG, P. RUIZ and B. DELMON*

Catalyse et Chimie des Matdriaux (Belgium) Divi&s, Place Croix du Sud 1, 1348 Louvain-la-Neuve

(Received

1 July 1988, revised manuscript

received 11 October 1988)

ABSTRACT The synergism between oxide phases in the oxidative dehydrogenation of n-butene to butadiene was investigated. Pure compound oxides (single phase) ZnFe,O,, FeSbO,, Fe, (MoO,):~, NiMoO, CoMoO, and Bi2Mo~I0,2 were prepared using different methods, then mixed mechanically with Sb?O,, BiPO, and Sn02. It was found that (i) pure compound oxides, ZnFe.,O,, FeSbO, and Bi2Mo,3012, have a high activity and selectivity; (ii) Sb?O,, BiPO, and SnO,, in the mixed powders, have a positive effect on the properties of ZnFe,O,, particularly at 450C; and (iii) the properties ofFez(MoO,), can be improved by the addition of Sb,O, and BiPO,. Within the framework of the remote control mechanism. this shows that the active centres on the compound oxides can be modified (improved) owing to the action of spillover oxygen produced by Sb,O.,, BiP04 and sometimes SnO,.

INTRODUCTION

The oxidative dehydrogenation of n-butene to butadiene is one of the most challenging selective oxidation reactions owing to the two major industrial interests it represents. First, the main product, butadiene, is an important intermediate for the production of plastics, nylon, polybutadiene, maleic anhydride, etc. and second, the st.udy of this reaction may serve to develop new reactions with similar mechanisms, such as the dehydrogenation of Z-methylbutene to isoprene, which are important in the petrochemical industry. The catalysts used in this reaction are usually mixed oxides such as various ferrites, molybdates or oxides containing tin. These catalysts usually contain several phases. For instance, the analysis of ferrite catalysts indicates that a

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good catalyst contains a pure ferrite with a spine1 structure and some impurity, a-Fe,O, [ 11, the presence of which seems to impede the deactivation of the catalyst. We interpret the results of other work on oxide mixtures by assuming that at least one of these phases carries the functions nesessary for reaction while the others may be thought to be necessary to improve the properties of the active phase, e.g., protecting the active phase from deactivation. This paper presents preliminary results concerning mechanically mixed oxides. Its orginality resides in the fact that we started with compound oxides, which are supposed to be good or even excellent catalysts and which are frequently used in the oxidation of hydrocarbons, and investigated whether an external single oxide could modify their catalytic activity and selectivity. The external phases include antimony (IV) oxide (Sb,O,), bismuth phosphate (BiPO,) and tin (IV) oxide ( SnO,), the influence of which on the dehydration of N-ethylformamide has been explained by their role as effective donors for the production of mobile oxygen species [a]. The catalysts examined were mechanical mixtures between compound oxides and the above added phases.
EXPERIMENTAL

Catalystpreparation Compound oxides

and characterization

ZnFe,O,, Fe, ( Mo0,)3, Bi2MosO12 and BiPO, were prepared using the citrate method [ 31. The ingredients used as starting materials were Fe(N03)3*9H,0, Zn(N03)2.5H20, Bi(NO,),.5H,O, (NH,),Mo,O,,*4H,O and orthophosphoric acid. The citrate method has been proved to be successful in the preparation of the mixed oxide phases. The procedure for the preparation of Bi,Mo,O,,, for example, was as follows. An aqueous solution of Bi3+ and MO+ with a bismuth-to-molybdenum atomic ratio of 2:3 was prepared from Bi(N03)3-5Ha0 and (NH,)6M07024.4H20, a small amount of 6.5 Mnitric acid being added to the solution in order to prevent precipitation. Citric acid was then added in such a manner that the number of moles of citric acid was equal to the total number of bismuth and molybdenum ions. Evaporation of the solution thus obtained was carried out under reduced pressure in a rotary evaporator at 60 C until the liquid became viscous and at 90C until solid. An amorphous organic precursor was obtained. Decomposition of the precursor at 300 C for 16 h and finally calcination at 500C for 18 h were performed. The other compound oxides, FeSbO,, NiMoO, and CoMoO,, were prepared by coprecipitation according to procedures described previously [ 4-61.
Single oxides

Tin (IV) oxide was prepared by precipitating the tin (II) hydroxide from tin (II) chloride dihydrate followed by washing Cl- with aqueous ammonia

117

TABLE 1 Some characteristics of pure oxides Sample SbpO, BiPO, SnO, ZnFenOj FeSbO, Fe, (MOO, 11 NiMoO, CoMoO, Bi,MoBO,, Crystalline phase Orthorhombic Monoclinic Tetragonal Spine1 Tetragonal Monoclinic Monoclinic Monoclinic Monoclinic Surface area (m/g)
2.0

4.3 12.6 9.6 24.4 4.3 28.9 8.6 2.7

TABLE 2 Physico-chemical characteristics of mixtures containing St1~0:~ Sample XRD Fresh ZnFe,O,Sb,O, FeSbO,-Sb,O, Spine1 + orthorhombic Tetragonal + orthorhombic Monoclinic + orthorhombic Monoclinic + orthorhombic Used* Iden.** Iden. Iden. Iden. BET surface area (m2/g) Fresh 5.8 13.3 3.5 2.5 Used 7.0 12.3 3.1 2.1

Fe,(MoO,),-Sb,O,
Bi,Mo,,O,,-Sb,O,

*Used means after catalytic test of dehydrogenation of n-butene. **Identical.

solution, drying overnight at 100 C and finally calcining at 600 C for 8 h. Antimony (IV) oxide was prepared by the calcination of antimony (III) oxide in air at 500 C for 20 h. Crystal structures of the samples obtained were checked by X-ray diffraction (XRD ) (Siemens Kristallofex 805 diffractometer, using nickel-filtered Cu Ka radiation). The surface areas were determined gravimetrically with a Setaram MTB 10-S microbalance connected to a vacuum and gas handling system by nitrogen adsorption at 77 K. Some characteristics of these samples are reported in Table 1.
Mechanical mixture

Mechanical mixtures of pairs of oxides were prepared by dispersion of the respective powders in n-pentane for 10 min, followed by evaporation of the solvent and drying at 80 C for 20 h. No further calcination was carried out. In this study, only mixtures containing 50 wt.-% of each oxide were prepared. In

118

order to compare the results, the pure oxides were also treated in the same manner, i.e. dispersion in n-pentane. Some mixtures containing Sb,O, were characterized using XRD and BET methods. The results are reported in Table 2. It can be observed that (i) no new phase was detected during XRD measurements for either fresh or used samples and (ii) the surface areas of the mixtures are almost the simple sum of those of the pure oxides and they were not modified during the catalytic test. The Fe, (MOO, ) ,-Sb,O, system was characterized using X-ray photoelectron spectroscopy for both the fresh and used samples. No mutual contamination could be detected [ 71.
Catalytic activity measurements

The oxidative dehydrogenation of n-butene was carried out in a conventional fixed-bed reactor system. The reactor was made of a glass tube of 8 mm in diameter, into which a small tube of 4 mm in diameter was inserted to carry a thermocouple to measure the temperature of the catalytic bed. The catalyst was ground and the fractions between 500 and 800 ym were used. The catalyst was diluted with glass spheres 500 pm in diameter. The standard conditions were as follows: n-butene pressure, 76 mmHg; oxygen pressure, 152 mmHg; total pressure, atmospheric; total flow-rate, 100 ml/min; and catalyst mass, 500 mg. The products and remaining reactants were analyzed by on-line gas chromatography (Intersmat IGC 120 ML) with a column containing 17% sebaconitrile supported on Chromosorb P AW.
RESULTS

The catalytic activity results for the pure oxides and mechanical mixtures are reported in Figs. 1 and 2, respectively, showing the butadiene, CO2 yields, (Fig. 1) and butadiene selectivity (Fig. 2) at 400 and 450C. The columns at the bottom of the figures represent the absolute values for the compound oxides and those in the upper part represent the effect (or synergy) of Sb204, SnO, and BiPO, when added to these compound oxides. The synergy was calculated using the equation nY=Y*,-0.5(Y*+Y,) where YAB represents the yield or selectivity of mechanical mixture AB and YA and Ys represent the yield or selectivity of oxide A and B, respectively. From Figs. 1 and 2, it can be observed that: for pure compound oxides, ZnFe,O,, Bi,Mo,O,z and FeSbO, are moderately active and selective catalysts for the formation of butadiene whereas the activities and selectivities of the molybdates of iron, nickel and cobalt are relatively low, It should be added that

119

20Od
0

z-20-

d
(+

E
VI

loo-

902

po-40 20O-ML
BiPQ,

ZnFeP4

FeSbO4

FeZ(HGJ3

HHoO~

CoMu01,

Bi$W2

Fig. 1. Butadiene and carbon dioxide yields for compound oxides and effect of Sb204, SnO, and BiPO, ( .A Y) at 400 3C (hatched boxes) and 450 C (open boxes).

the activities of the external phases Sb204, BiP04 and SnOz (Table 3) are much lower than those of the compound oxides. Regarding the butadiene yield, Sb,O, has a positive effect on the properties a negative effect on those of FeSb04 and of ZnFe,O, and Fe,(MoO,),, Bi2M03012 and almost no effect on the nickel and cobalt molybdates. It is interesting that the addition of Sb204 inhibits the production of carbon dioxide

120

30-

O-

-4 i

ZllFeZO~

Festa

FdMoOfJj

NitllJOl+

cd-iool,

&+wlZ (AS) at

Fig. 2. Butadiene selectivity for compound oxides and effect of Sbz04, SnO, and BiPO, 400C (hatched boxes) and 450 C (open boxes).

for all of the mixed oxides investigated. It follows that the addition of Sb204 favours the butadiene selectivity with ZnFe,O,, Fe,(Mo04)s and Bi2M03012 but it has almost no influence in the other instances. The effect of SnO, is different from that of Sb,O,. It has a negative effect on the production of butadiene with all the mixed oxides except ZnFe20, at 450C. At 400 C, it increases the production of carbon dioxide with molybdate cata-

121 TABLE 3 Catalytic activity and selectivity for Sb,O,, BiPO, and Sn02 Sample 400C Yield ( % ) Sb,O, BiPO, SnO? 0.08 2.78 13.40 Selectivity (% ) 0.59 7.51 37.33 450C Yield(%) 0.72 12.84 20.28 Selectivity (% ) 4.12 23.76 31.44

lysts but inhibits it at 450C for all the catalysts investigated. Regarding butadiene selectivity, SnO, has a negative effect with most of the mixed oxides, except ZnFe,O, and CoMoO, at 450 C. The addition of BiPO, favours butadiene formation and its selectivity for ZnFe,O,, Fe,(MoO,), and NiMoO,, which is not the case for FeSbO, and Bi,Mo,O,,. Like Sb,O, it inhibits the formation of carbon dioxide in all instances and the inhibiting effect increases with increasing reaction temperature.
DISCUSSION

Several processes may take place when two oxide phases are mixed together, for instance the formation of a new phase or the contamination of one oxide by the other. Therefore, the explanation for the results with multi-phase catalysts may vary from one system to another, depending on which phenomenon appears between phases. The preliminary characterization results presented here do not allow for further interpretation until further characterization results are obtained. However, it would still be useful to discuss some points based on the results obtained. It is generally accepted that the oxidative dehydrogenation of n-butene operates via a redox mechanism, namely that the catalyst is reduced by the reactant and reoxidized by the gaseous oxygen. Therefore, a good catalyst must be capable of being reduced and reoxidized easily, a criterion usually best satisfied by mixed oxides. The presence of gaseous oxygen is necessary to maintain the catalyst in an active and selective (not deactivated) form. However, it may be expected that, in certain instances during reaction the catalyst may be deactivated owing either to the reduction (e.g., the reduction rate of the catalyst is more rapid than that of reoxidation) or to the deposition of carbonaceous products, and the supply of oxygen species coming from other phases may improve the activity and, more particularly, the selectivity of the catalyst. This may be the reason for the positive effect of Sbz04, BiPO, and SnO, on ZnFe,O, and of Sb204 and BiP04 on Fez (Moo,),. The detailed investigations of the ZnFe,O,-

122

Sb204 system showed clearly that at 450 oC pure ZnFe,O, was deactivated during reaction owing to its phase segregation to ZnO whereas this segregation did not take place when Sb,O, was present [ 81. This result indicates that oxygen species emitted by Sb,O, can stabilize the ZnFe20, phase. Another series of results demonstrating the influence of oxygen concentration on the synergistic effect for ZnFe,O,, Fe2(Mo04)3 with Sb,O, and BiP04 confirms the above interpretation [ 731. An interesting observation is that the influence of SnO, changes substantially from 400 to 450 C. For instance, SnOz increases the production of carbon dioxide at 400C whereas at 450 C it inhibits it for molybdate catalysts. This may be related to the change in the nature of the oxygen species adsorbed on SnO, at these two temperatures. It has been shown that the main oxygen species adsorbed on SnOa at 400C are electrophilic and are suitable for carbon dioxide production, and that when the temperature increases, these species are converted to nucleophilic O*- suitable for selective oxidation [ 9,101. It could be expected that most of the oxygen species adsorbed on SnO, are nucleophilic at 450C. Some of the above systems, such as NiMoO,-Sb,O, and FeSbO*-Sb204, have been investigated in the selective oxidation of isobutene to methacrolein [ 111, where a synergy was observed, contrary to the present results. Although both reactions are considered to operate via the same mechanism for the first step of the reaction, i.e., abstraction of a-hydrogen, the oxidation of isobutene would require the insertion of lattice oxygen in the main product and hence the reoxidation of the catalyst would be more substantial in this instance. It may be that this difference will explain the contradictory results obtained with these reactions. In conclusion, these preliminary results show that the activity and/or selectivity of compound oxides, similarly to those of single oxides, can benefit from contact with Sb204, BiP04 and sometimes Sn02. As regards the remote control mechanism, the results suggest that the active centres on these compound oxides can be modified owing to the action of spillover oxygen.
ACKNOWLEDGEMENT

The financial support of FNRS (Belgium ) accorded to F.Y. Qiu for his stay in Louvain-la-Neuve is gratefully acknowledged.

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