Applied Catalysis, 14 (1985) 145-158 145

Elsevier Science Publishers B.V., Amsterdam -Printed in The Netherlands

GAS PHASE ACETOXYLATION OF 1,3-BUTADIENE OVER PALLADIUM CATALYSTS

PART 2: THE CATALYTIC PROPERTIES AND THE STRUCTURE OF Pd-Sb-V-KOAc CATALYST

Hironobu SHINOHARA
Research and Development Laboratory, Japan Synthetic Rubber Co. Ltd., Kawajiri-cho
100, Yokkaichi-shi, Mie-ken 510, Japan.

(Received 6 June 1984, accepted 25 October 1984)

ABSTRACT
The gas phase acetoxylation of 1,3-butadiene (BD) over Pd catalysts was studied.
Addition of a vanadium component to a Pd-Sb-KOAc catalyst was found to give a
remarkably improved selectivity to 1,4-diacetoxybutene-2 (about 85%), whilst keep-
ing the high activity of Pd-Sb-KOAc catalyst. The highest activity was obtained
at an Sb/Pd atomic ratio of about 0.5. Pd and Sb elements had similar concentration
profiles in the catalyst particle, and the diffraction of reduced Pd-Sb-V revealed
the formatinn of Pd3Sb. These results showed that intermetallic compounds between
Pd and Sb, Pd3Sb, were formed, as in the case of the Pd-Sb-KOAc catalyst. By
increasing the amount of a vanadium component on the catalyst, the selectivity was
remarkably improved but the activity was sharply decreased by excess loading of
V. Elemental V was distributed homoqeneouslv on the catalvst and the distribution
was quite different from that of Pd-and Sb.-The states of"Pd, Sb and V in the Pd-
Sb-V-KOAc catalvst were Pd". Sbo and V4+. which were auite different from those of
Pd and Sb (slightly positive) in the Pd-Sb-KOAc catalyst. For the acetoxylation, V
might exist around the intermetallic compound between Pd and Sb and work as a
supplier of oxygen by a redox mechanism.
For the acetoxylation of BD on the Pd-Sb-KOAc catalyst, the selectivity, the
reaction order, the durability of activity and the temperature dependence were quite
different, depending on whether the air/BD molar ratio was smaller or larger than
about 8. In the case of smaller air/BD, the surface of the catalyst might be
saturated with adsorbed BD, from the reaction order for BD (PBDO) and the select-
ivity. In the case of larger air/BD, the dependence of P D on the activity was 0.8
order, showing the low amount of BD adsorption. The dura t!. ility of the activity was
better in the conditions of higher ratio. From these observations, the lowering
of the activity might be caused by polymerization between adsorbed BD molecules.

INTRODUCTION
1,4-Diacetoxybutene-2 (1,4-DABE) can be converted into industrially useful
compounds such as 1,4-butanediol,tetrahydrofuran, etc., by suitable reactions like
hydrogenation, hydrolysis, etc., [l-3]. Recently a variety of methods has been
proposed for the production of 1,4-DABE through a reaction of 1,3-butadiene (BD),
acetic acid (AcOH) and oxygen (02) in a gas or liquid phase over catalysts com-
prising a noble metal such as Pd, Pt or Rh [4-61. For a liquid phase acetoxylation,
a Pd-Te catalyst has been reported to give a high activity and a high selectivity
[7-81, and the detail has been discussed by Takehira et al. [9]. On the other hand,
for a gas phase acetoxylation various catalysts have been researched, but satisfact-

0166-9834/85/$03.30 0 1985 Elsevier Science Publishers B.V.

146

TABLE 1
Acetoxylation of BD on various Pd-based catalysts. Catalyst: Pd 1 wt"/o,KOAc 4 wt%,
Pd:Sb:fourth component = 1:l:l (atomic ratio). Reaction conditions: 145"C,
SV 1000 h-l, BD:AcOH:air = 20:20:60 (~01%).

Fourth Conversion Selectivity/Z

No. component source of BD/"/, I-ABD 3,4-DABE 1,4-DABE

1 8.84 52.6 3.9 43.5

2 Na NaCl 8.37 53.5 3.9 42.6
3 M9 M9C12 8.94 51.0 3.8 45.2
4 Ca CaC12 9.08 51.6 3.5 44.9
5 B 8.87 55.5 3.9 40.6
H3B03
6 Al A1C13.6H20 8.62 34.6 8.2 57.2
7 Tl T1C13.4H20 8.80 52.2 3.9 43.9
8 Sn SnC14 9.97 45.5 4.4 50.1
9 Pb PbC12 6.29 57.8 3.4 38.8
IO P 8.94 51.9 3.9 44.2
'2'5
11 Bi BiC13 5.24 56.3 3.2 40.5
12 Se Se02 3.81 50.3 8.2 41.5
13 Te H2Te04 1.83 21.8 16.7 61.5
14 cu CuC12.2H20 7.67 52.7 4.1 43.2
15 Zn ZnCl2 8.23 52.4 3.9 43.7
5
16 Cd CdC12.T H20 5.99 47.8 7.9 44.3
17 Ce CeC13.6H20 7.73 52.6 4.1 43.3
18 Ti Tic14 8.72 51.7 4.0 44.3
19 Zr ZrClq 7.70 52.7 3.6 43.7
20 V NH4V03 6.73 8.8 6.0 85.2
21 Nb NbC15 9.89 44.4 4.5 51.1
22 Cr CrC13.6H20 11.11 47.4 4.4 48.2
23 MO ( NH41pMo05 6.16 13.7 8.1 78.6
24 Mn MnC12.4H20 12.02 43.0 4.9 52.1
25 Re Re07 8.12 52.6 4.1 43.3
26 Fe FeC13 2.43 56.9 4.9 38.2
27 co CoC12.6H20 10.67 48.6 5.2 46.2
28 Ni NiC12.6H20 10.75 44.4 5.3 50.3
29 Pt H2PtC16 5.69 60.2 3.7 36.1

or-y results have not been obtained in respect of activity, selectivity and stabil-
ity [IO-121.
The purpose of this study is to find a better catalyst for gas phase acetoxylat-
ion of BD. In previous work, the author reported that a Pd-Sb-KOAc catalyst gave
a higher activity and an improved selectivity to 1,4-DABE compared to a Pd-KOAc
 147

FIGURE 1 Dependence of the Sb/Pd and V/Pd atomic ratios in the Pd-Sb-V-KOAc
catalysts on activity and selectivities to 1,4-DABE and l-ABD for the gas phase
acetoxylation (145"C, SV 1000 h-', BO:AcOH:air = 20:20:60 (vol %)). Catalyst: Pd

1 wt%, KOAc 4 wt%. V/Pd atomic ratio:@, O;@, 0.5;0, 1 .o;*, 2.0;@. 4.0.

catalyst [13]. However, the selectivity to 1,4-DABE, a desired product, was still
not satisfactory. In this work, various catalysts were prepared and tested to
improve the low selectivity. It was found that the addition of a vanadium component
to the Pd-Sb-KOAc catalyst resulted in a dramatic increase in the selectivity [14].
Accordingly, the structure and the state of the Pd-Sb-V-KOAc catalyst were studied
by means of X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and electron

microprobe X-ray analysis (EMX). The effect of reaction variables on the aceto-
xylation was also examined. The effects of Sb and V on the catalysis were discussed
and the method for improvement of the catalytic life was proposed, based on the
results.

EXPERIMENTAL
Catalysts
The catalysts were prepared according to the previous report [133. PdC12 and
SbC13 together with the fourth component (see Table I), if necessary, were support-
ed on the silica-alumina previously sintered at 1200C. The carrier was dried in
a N2 stream at 200C and then reduced by H2 at 200C for 2 h and at 400C for 2 h,
successively. Potassium acetate (KOAC) was then supported on the carrier.
The concentrations of Pd and KOAc in the catalyst were 1.0% and 4.0% by weight,
respectively, and the atomic ratio of Pd/Sb/the fourth component was normally l/l/l.
148

I 500 cps

340 335 545 540 535

DInding Energy (eV 1 Binding Energy (ev )

FIGURE 2 XPS of Pd3d5,2 and Pd3d3,2 on various catalysts reduced by hydrogen at

200C for 2 h and at 400C for 2 h successively. 1, Pd-KOAc catalyst; 2, Pd-Sb-
KOAc catalyst (Sb/Pd atomic ratio = 0.5/l); Pd-V-KOAc catalyst (V/Pd atomic ratio =
l/l); Pd-Sb-V-KOAc catalyst (Pd/Sb/V atomic ratio = l/0.5/1).

FIGURE 3 XPS of Sb3d3,2 on various catalysts reduced by hydrogen at 200C for 2 h

and at 400C for 2 h successively. 1, Sb-KOAc catalyst; 2, Pd-Sb-KOAc catalyst
(Sb/Pd atomic ratio = 0.5/l); Pd-Sb-V-KOAc catalyst (Pd/Sb/V atomic ratio = l/O.

5/l).

Apparatus and reaction

10 ml of the prepared catalyst was packed in a reaction tube [13]. A gaseous
mixture comprising BD, AcOH, O2 and N2 was introduced into the tube at a flow rate
of 10 1 h-l. The reaction temperature was normally 145C. The products were collect-
ed for 1.5 h commencing at 1 h after the reactants were introduced. The analysis
of the products was performed by a gas-chromatograph.

Analysis of catalysts
XPS was measured by a du Pont ESCA 650B using MgKcl, radiation. All binding
energy values were referred to C IS (285 eV). The distribution of Pd, Sb and V
elements on the carrier were examined by a Shimazu EMX-SM7, using PdLa,. SbLcl, and
 149

V 2PQ

..L
I I I I I I I I

520 515 0 2 L 6
Binding Energy (eV )
Oxidized State of V Compound

FIGURE 4 XPS of V2~3,~ on various catalysts reduced by hydrogen at 200C for 2h

and at 400C for 2 h successively. 1, Pd-V-KOAc catalyst (Pd/V atomic ratio = l/l);
Pd-Sb-V-KOAc catalyst (Pd/Sb/V atomic ratio = l/0.5/1).

FIGURE 5 XPS of V2~3,~ on various vanadium compounds.

lines. The diffraction measurements were carried out by Shimazu XD-3A using
VLCLl
radiation [13].
CuKcll

RESULTS
The improvement of the selectivity to 1,4-DABE
For the gas phase acetoxylation of BD, the Pd-Sb-KOAc catalyst gave a very high
activity but the selectivity (at most 50%) to 1,4-DABE, a desired product, was not
high enough [13]. In order to improve the selectivity, the effect of addition of
the fourth component on the catalytic properties was examined.
Table 1 lists the results. The catalysts with V or MO as the fourth component
gave a dramatically improved selectivity to 1,4-DABE, although the STY (space time
yield) was slightly lowered. Thus, the selectivity reached 85.2% with the Pd-Sb-V-
KOAc catalyst compared to 43.5% with the Pd-Sb-KOAc catalyst. The fourth components,
which gave a slightly improved selectivity (at most 607:) were Al, Sn, Te, Nb, Mn
and Ni, Nb, Cr, Mn, Co and Ni slightly improved the activity.

Pd-Sb-V-KOAc catalyst
The influence of the Pd/Sb/V atomic ratio on the catalytic activity. In order to
examine the effect of Sb and V on the catalytic activity, some Pd-Sb-V-KOAc
catalysts with varying composition were prepared and tested.
The results are shown in Figure 1. For the Pd-Sb-V-KOAc catalyst (Pd 1 wt"c,
150

T
surface center
1

FIGURE 6 EMX of Pd, Sb and V on the Pd-Sb-V-KOAc catalyst particle (Pd/Sb/V =

l/0.5/1).

Pd,Sb
Pd,Sb
I

FIGURE 7 X-ray diffraction patterns of the powder obtained by reducing Pd-Sb-V

(Pd/Sb/V = l/l/l).

KOAc 4 wt%), the activity increased with increasing the Sb/Pd atomic ratio to 0.4
but reduced sharply over 0.5, being highest at 0.4 - 0.5 of the Sb/Pd atomic ratio.
This tendency was independent of the V/Pd atomic ratio. The selectivity to 1,4-
DABE increased and that to I-acetoxy-1,3-butadiene (I-ABD) decreased with increas-
ing Sb/Pd atomic ratio. Similar results were observed with the catalyst which con-
tained no vanadium [13].
On the other hand, the activity decreased and the selectivity to 1,4-DABE
increased sharply with increasing V/Pd atomic ratio.
 151

Pd 111

FIGURE 8 X-ray diffraction patterns of the powder obtained by reducing Pd-V

(Pd/V = l/l).

Ti Ch
Ti 02

TiOz

*,L
TiO2

TiOo
t

35 40 45 50
Zb

FIGURE 9 X-ray diffraction patterns of catalyst. 1, Pd-Sb-V catalyst supported

on TiO2 reduced by H2 at 200C for 2 h and at 400C for 2 h successively (Pd 3 wt%,
Pd:Sb:V = 1:0.5:1); 2, only Ti02 catalyst.

XPS of Pd, Sb and V. The states of Pd, Sb and V in the Pd-Sb-V-KOAc catalysts
(Pd:Sb:V = 1:0.5:1) were examined by an XPS method. The spectra of Pd, Sb and V are
shown, respectively, in Figures 2, 3 and 4.
As shown in Figure 2, the binding energies of Pd3d5,2 and Pd3d3,2 in the Pd-Sb-
V-KOAc catalyst were 335.8 and 341.1 eV, corresponding to Pd" [15]. These values
were the same as thosein the Pd-KOAc and the Pd-V-KOAc catalysts but different
from those (336.3 and 341.6 eV) in the Pd-Sb-KOAc catalyst. As Figure 3 indicates,
the binding energy of Sb3d3,2 in the Pd-Sb-V-KOAc catalyst was 538.3 eV, being
the same as that in the Sb-KOAc catalyst but different from that (539.3 eV) in
the Pd-Sb-KOAc catalyst. The state of Sb in the Pd-Sb-V-KOAc catalyst was estimated
to be Sb" C161. The binding energy (517.2 eV) of V~P~,~ in the Pd-Sb-V-KOAc
152

FIGURE 10 The dependence of the molar ratio of reactants on the catalytic activity.

145"C, SV 1000 h-'. Partial pressures of AcOH are given in this Figure by per cent.

(Figure 4) corresponded to V4+, which was estimated from the binding energies of

various vanadium compounds (Figure 5). The ionic state was the same as that in the

Pd-V-KOAc catalyst.
From these resultsthe states of Pd, Sb and V in the Pd-Sb-V-KOAc catalyst were
4+
determined to be Pd', Sb" and V , respectively.
The distributions of Pd, Sb and V. The distributions of Pd, Sb and V elements

on the Pd-Sb-V-KOAc catalyst particle (Pd:Sb:V = 1:0.5:1) were examined by an EMX

method.
Figure 6 shows the EMX spectra of Pd, Sb and V by a line analysis from the

surface to the center of the catalyst. Pd and Sb were distributed heterogeneously.

However, it is worthy of note that the detail of concentration profiles of the two
components was quite similar to each other. On the other hand, V was distributed
rather homogeneously on the catalyst particle. The concentration profile of V was
independent of that of Pd and Sb.
X-ray diffraction. X-ray diffraction patterns of black powders obtained by

reducing the mixture of PdC12, SbC13 and NH4V03 (Pd:Sb:V = 1:1:1) and the mixture
of PdC12 and NH4V03 (Pd:V = 1:1) using sodium borohydride are shown, respectively,
in Figures 7 and 8. The lattice spacings and the relative intensity ratio of
every peak in Figure 7 indicate the formation of Pd3Sb [17], as in the case of that
of PdC12 and SbC13 [13]. No peak due to Pd metal was observed. On the other hand,
the pattern of the powder of PdC12 and NH4V03 (Figure 8) was identical to that of

PdCQ [13,18].
Furthermore, the X-ray diffraction pattern of the Pd-Sb-V catalyst, prepared by
supporting PdC12, SbC13 and NH4V03 (Pd 3 wt%, Pd:Sb:V = 1:0.5:1) on Ti02 (CS-700-
 153

oh
0.1 0.5 IO 50 10 50
AIRIBD molar rat10

FIGURE 11 The dependence of the molar ratio of reactants on the selectivity to

1,4-DABE. 145"C, SV 1000 h-l. Partial pressures of AcOH are indicated in this

Figure by per cent.

24 from Sakai Chemical Co., Ltd.,) and reduced by H2 as preparing the catalyst,

is shown in Figure 9. There are two strong peaks (20 = 39.3 and 41.0) discounting
the peaks due to Ti02. These peaks correspond to the strong peaks of Pd3Sb [I71
shown in Figure 7.
From these results it is concluded that the only intermetallic compound between

Pd and Sb such as Pd3Sb was formed in the Pd-Sb-V-KOAc catalyst as well as the
Pd-Sb-KOAc catalyst [13].

The dependence of reaction conditions on the catalytic behavior

The molar ratio of reactants on the activity and selectivity. The catalytic
properties of the Pd-Sb-V-KOAc catalyst (Pd:Sb:V = 1:0.5:1) were examined by react-
ing BD, AcOH and 02 under various conditions.
Figure IO shows the dependence of the molar ratio of reactants on the catalytic
activity (SV 1000 h-', 145C). The increase in air/BD ratio from 0.1 to 8 resulted
in an increase in the STY, which decreased for values over 8. This tendency was
independent of the partial pressure of AcOH. The STY increased with increase in
the partial pressure of AcOH from 0.1 to 0.4, but over 0.4 it decreased. The hiph-
-1 h-1
est STY was 1.35 mol l-catalyst around the molar ratio of BD:AcOH:air = 6:40:
54 under the conditions of a space velocity (SV) of 1000 h-' at 145C.
The dependence of the partial pressure of BD, AcUH and O2 (PBD, PAcOH and Po2)
on the formation rate for 1,4-DABE was determined over the range of PAcOH from
0.1 to 0.4. The formation rate for 1,4-DABE was proportional to PBDo*o, PAcOH1*'
1.0
and PO2 in the air/BD ratio smaller than 8. In the air/BD ratio larger than 8,
0.8 0.9 1.0
it was proportional to PBD and PO2 .
'AcOH
Figure 11 gives the dependence of the partial pressure of reactants on the
selectivity to 1,4-DABE. As the air/BD molar ratio increased from 0.1 to 40, the
value of the selectivity to 1,4-DABE gradually increased. An increase in the partial
154

120 160 200 120 160 200

Temperature (C )
Temperature (C )

FIGURE 12 The effect of the reaction temperature on activity and selectivity

over the Pd-Sb-V-KOAc catalyst (Pd/Sb/V = l/0.5/1). SV 1000 h-l, BD:AcOH:air = 20:

20:60 (vol %).

FIGURE 13 The effect of the reaction temperature on activity and selectivity over
the Pd-Sb-V-KOAc catalyst (Pd/Sb/V = l/0.5/1). SV 1000 h-l, BD:AcOH:air = 5:20:75

(vol %).

pressure of AcOH from 0.1 to 0.4 resulted in higher selectivity.

Reaction temperature. The effect of reaction temperature on the activity and
selectivity was examined. Figures 12 and 13 were obtained, respectively, for the
molar ratio of BD:AcOH:air = 20:20:60 (air/BD = 3) and 5:20:75 (air/BD = 15)

with 1000 h-' of SV at 145C. The temperature dependences are quite different in
the two cases, probably reflecting the dependence of kinetics on air/BD ratio.
In the case of the smaller air/BD (Figure IZ), by raising the reaction tempera-
ture from 130C to 2OO"C, (I) the activity did not change, (2) the selectivity
to 3,4-diacetoxybutene-1 (3,4-DABE) decreased and that to I-ABD and CO2 slightly
increased, and (3) that to 1,4-DABE did not consequently vary (about 78%). On the
other hand, in the case of greater air/BD (Figure 13), by raising the reaction
temperature from 120C to 2OO"C, (I) the activity gradually increased, (2) the
selectivity to 3,4-DABE decreased and that to I-ABD and CO2 slighly increased and
(3) that to 1,4-DABE did not consequently vary (about 85%). The apparent activation
energies were estimated at 0.0 kcal mol -' (air/BD = 3) and at 6.6 kcal mol -' (air/

BD = 15), respectively.
The durability of the activity. Figure 14 gives the dependence of the molar
ratio of reactants on the durability of the activity. The durability was defined
as the ratio of the STY at running time of 5 h to 2 h (A5/A2 x 100). With increas-
ing air/BD ratio, the durability was gradually improved. Over an air/BD ratio of
about 8, the original activity did not change over 5 h. The difference in the
 155

I I a ,..I I I
0.1 05 IO 5.0 IO 50
AlRiBD ( molar ratm 1

FIGURE 14 The dependence of the molar ratio of reactants on the durability of

the activity. Catalyst: Pd-Sb-V-KOAc catalyst (Pd/Sb/V = l/0.5/1). Reaction condit-
ions; SV 1000 h-l, 145C. Partial pressure of AcOH:@, 20%,0, 402.

partial pressure of AcOH between 0.2 and 0.4 gave little difference in the durabil-
ity.

DISCUSSION
The feature of the Pd-Sb-V-KOAc catalyst
It was reported in previous work [I31 that the Pd-Sb-KOAc catalyst gave a much
higher activity and an improved selectivity compared to the Pd-KOAc catalyst. But
the selectivity to 1,4-DABE was at most 507:. On the other hand, the Pd-V-KOAc
catalyst did not improve the activity and the selectivity (at most 15%) of the
Pd-KOAc catalyst.
The remarkable fact found in this study was that the Pd-Sb-V-KOAc catalyst
(Pd:Sb:V = 1:1:1) gave improved selectivity to 1,4-DABE (85%), almost keeping the
high activity of the Pd-Sb-KOAc catalyst. It was worthy of note that the addition
of V to the Pd-Sb-KOAc catalyst gave a remarkable effect, though the addition to
the Pd-KOAc catalyst gave no effect, indicating that the catalysis of the Pd-Sb-
KOAc catalyst was quite different from that of the Pd-KOAc catalyst.
Accordingly, it was concluded that the excellent catalytic properties of the
Pd-Sb-V-KOAc catalyst were not obtained till the three components of Pd, Sb and V
were combined. And this catalyst, Pd-Sb-V-KOAc, was thought to be a practically
useful catalyst for the gas phase acetoxylation of BD.

The role of Sb
In the Pb-Sb-V-KOAc catalyst, the concentration profiles of Pd and Sb elements
were quite similar as seen in EMX spectra. However, the distribution of elemental
V was quite different from that of the above two elements. Furthermore, with
increasing Sb/Pd atomic ratio to about 0.5, the activity and selectivity increased.
156

But passing a Sb/Pd ratio of 0.5 the activity was abruptly depressed and the
selectivity reached a nearly constant value.
X-ray diffraction study showed that the black powder obtained by reducing PdC12,
SbC13 and NH4V03 with sodium borohydride contained an intermetallic compound,
Pd3Sb. No crystalline compound containing V could be found, and in the Pd-Sb-V
catalyst prepared by reducing with H2, there were two strong peaks of X-ray
diffraction based on Pd3Sb.
These results were quite similar to those for the Pd-Sb-KOAc catalyst as
described in the previous study [13]. Therefore, it is concluded that the inter-
metallic compounds, Pd3Sb were formed between Pd and Sb in the Pd-Sb-V-KOAc cata-
lyst and the intermetallic compounds were supposed to be active species as in the
case of the Pd-Sb-KOAc catalyst.

The role of V
In the Pd-Sb-V-KOAc catalyst, elemental V was distributed rather homogeneously
and the concentration profile of V was quite different from those of Pd and Sb as
seen in EMX spectra. The selectivity to 1,4-DABE was greatly improved by the
addition of a small amount of V to the Pd-Sb-KOAc catalyst and gradually improved
by increasing the amount of V. On the other hand, the activity decreased by
increasing the amount of V, which probably caused the decrease in the activity
due to a covering of the active species such as Pd3Sb.
Pd and Sb on the Pd-Sb-KOAc catalyst were in the slightly positive states
(Pd+' and Sb+ls2 ) [133. On the other hand, the states of Pd, Sb and V on the
Pd-Sb-V-KOAc catalyst were Pd', Sb" and V4+. It might be thought that V had an

important effect on the states of Pd and Sb.

V compounds are well known as the catalysts for oxidation such as the synthesis
of maleic anhydride from benzene [I91 and from butene [203, and the synthesis of
ohthalic anhydride from o-xylene [21] etc., Mars and van Kreven proposed a redox
mechanism, oxidation-reduction cycle, that V205 oxidized benzene and consequently
reduced V 0 was oxidized by gaseous oxygen [19]. Simard also proposed the redox
2 5
mechanism of V205 Z 3'vo 5 ,3 + 4 O2 [Zl]. For the oxidation of n-butene it was
proposed that the oxidation proceeded by oxidation-reduction cycle of V5+ = V4+,
based on the relation between the oxidized state of V ion and its activity 1201.
The gas phase acetoxylation of BD is a kind of oxidation using oxygen. Accordirg-
ly for the acetoxylation, the oxidation ability of V compound on the Pd-Sb-V-KOAc
catalyst may play an important role. Thus, the V component exists in the close

vicinity of intermetallic compounds (Pd3Sb, being the active species) and controls
the oxidized states of Pd and Sb, and affects the catalysis by an activation of O2
such as a redox mechanism, (the cycle where oxygen is supplied to reaction by V

compound and the reduced V compound is oxidized by 02).

 157

The influence of the reaction conditions on the catalytic properties

It was observed that the selectivity, the temperature dependence on the activity,
the durability of the activity and the partial pressure dependence on the reaction
velocity were quite different, depending on whether the air/ED molar ratio is
smaller or larger than 8. These facts imply that the reaction mechanism is differ-
ent in each of the two cases.
Under the reaction conditions of high BD ratio, the dependence of partial
pressure of BD on the activity was zero order, indicating that the surface of the
catalyst was saturated with adsorbed BD. On the other hand,
in the case of air/BD
0.8
molar ratio greater than 8, the reaction rate was proportional to PBD . This fact
shows that the concentration of BD adsorbed on the catalyst was low in this case.
For the acetoxylation of BD, 1,4-DABE is formed from 1 molecule of BD and 2
molecules of AcOH. And the saturation of the surface with BD may result in the
decrease in adsorbed AcOH. Accordingly, the selectivity to I-ABD, formed from 1
molecule of BD and 1 molecule of AcOH, was thought to be rather increased, at the
expense of the selectivity to 1,4-DABE.
Also, the difference in the amount of adsorbed BD might be related to the
durability of the activity. BD is well known as a monomer for polymerization. When
the concentration of adsorbed BD was high, the polymerization between BD molecules
adsorbed on the catalyst might proceed on the catalyst surface. The polymer formed
in this way might cover active species for the acetoxylation of BD. This might
correspond to the lowering of the durability of the activity in high partial
pressure of BD (air/BD molar ratio < 8).

ACKNOWLEDGEMENTS
The author is grateful to Prof. T. Ono (Tokyo Institute of Technology) for his
valuable discussions, to Dr. K. Ninomiya, Dr. T. Kotani and Mr. Y. Yoshida (Japan
Synthetic Rubber Co. Ltd.,) for their directions and to colleagues in the laborat-
ory for their help for these experiments.

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