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Jointly published by React.Kinet.Catal.Lett.

Akadémiai Kiadó, Budapest Vol. 73, No. 1, 47-54


and Kluwer Academic Publishers, Dordrecht (2001)

RKCL3761

KINETICS OF THE OXIDATION OF tert-BUTANOL TO


METHACROLEIN ON CALCIUM IONS PROMOTED IRON-
TELLURIUM-MOLYBDENUM OXIDE CATALYST

Viacheslav Zhyznevskiy, Yevhen Fedevych and Roman Tsybukh


Lviv State Agricultural University
79020 Lviv, P. Pancha 8/123 Str., Ukraine
Tel: (0322) 39-88-31, Email: george@ktf.franko.lviv.ua

Received July 26, 2000


In revised form October 27, 2000
Accepted April 2, 2001

Abstract
In a differential reactor with a vibro-fluidized layer of catalyst, the kinetics of
partial oxidation of tert-butanol and methacrolein on calcium ions promoted Fe-
Te-Mo-O catalyst has been investigated.

Keywords: Partial oxidation, tert-butanol, methacrolein, catalyst

INTRODUCTION

Our previous studies have shown that the Fe:Te:Mo (1:0.85:1) oxide
catalyst is one of the most effective catalysts of isobutylene oxidation to
methacrolein [1], and can be used also for the oxidation of tert-butyl alcohol
(TBA). However, the yield of PHWKDFUROHLQ RQ WKLV FDWDO\VW LV QRW
F:
sufficiently high [2]. Catalytic properties of the indicated catalyst can be
improved by promoting it with ions of alkaline or alkaline-earth metals [3,4].
The highest yield is reached upon promoting this catalyst with calcium ions at a
KZ 0R UDWLR RI  8QGHU RSWLPDO FRQGLWLRQV >  . FRQWDFW WLPH
L τc)
3.3 s] and TBA concentration of 5 mol. % in air in a flow-type reactor, the yield
RI F: RQ SDVVHG DOFRKRO ZDV  7KH FDWDO\VW SURPRWHG E\ FDOFLXP LRQV
differs also by its high stability during work [5]. This paper presents the
kinetics of TBA oxidation on the above catalyst that is necessary for the
process optimization.
0133-1736/2001/US$ 12.00.
© Akadémiai Kiadó, Budapest.
All rights reserved.
48 ZHYZNEVSKIY et al.: tert-BUTANOL

EXPERIMENTAL

The analysis of reactants and reaction products was done by on-line gas
chromatography (GC). Effluent reaction mixture from the reactor with a
volume velocity of 0.56 cm3s-1 was split into two flows. The first flow was
directed to a GC column (0.4 cm x 2 m), packed with 15 % Apieson - L and
5 % PEG - 6000 on Chromaton N-AW-DMCS operated at 373 K, followed by a
flame ionization detector for the analysis of hydrocarbons. The second flow
was directed to two GC columns in series. The first was packed with Polysorb -
1 (0.4 cm x1 m) for carbon dioxide analysis and the second with molecular
sieve NaX (0.4 cmx2 m) for N2 H2   DQG DQDO\VLV RSHUDWHG DW URRP
KH
temperature and followed by a thermal conductivity detector.
7KH NLQHWLFV RI WKH R[LGDWLRQ RI 7%$ WR F: ZDV LQYHVWLJDWHG E\ SXOVH
reactions in a differential reactor with a vibro-fluidized layer of a catalyst. The
reactor consisted of a stainless steel tube (i.d. 4 mm, length 20 cm). Both ends
of the tube had silicate cotton filters. For vibro-fluidization of the catalyst an
electromagnetic source of mechanical vibrations was used, with a frequency of
50 Hz and amplitude of 2-10 mm (these parameters can be controlled). As has
been shown by preliminary studies, on switching on a vibrator, the volume of
the catalyst layer increased 2-3 times with amplitude and there were no
temperature and concentration gradients. Besides, taking into account the small
pulse volume of the reaction mixture, it can be assumed that the reaction is
carried out under the rate-control conditions (this was supported by the
invariability of rates, measured under pulse and flow reaction conditions with a
vibro-fluidized layer of a catalyst). The detailed description of apparatus
construction can be found in [6].
It is known that the iron-tellurium-molybdenum oxide catalyst considerably
changes its properties under the action of a reducing medium, and at volume
UDWLRV 
H2/ K4G8 < 4 its activity and selectivity to MA decreases [7]. Taking into
account this fact, the kinetics of TBA oxidation was studied under appropriate
oxygen excess.
7KH LQYHVWLJDWLRQV ZHUH FDUULHG RXW DW   DQG  D and contact times
of 0.6 - 3.3 s. Under these conditions TBA is completely converted into
isobutylene, which in turn undergoes further oxidation. Experimental and
calculated values for the rate of products formation under the investigated
conditions are reproducible within ± 10 % rel.

RESULTS AND DISCUSSION

It can be considered as proved that products of partial oxidation of


olefins form according to a step-wise scheme, though stages of reduction
ZHYZNEVSKIY et al.: tert-BUTANOL 49
50 ZHYZNEVSKIY et al.: tert-BUTANOL

and reoxidation of the catalyst can influence each other [8]. Partial TBA
oxidation involves the sequence of dehydration of alcohol to  K4G8 and further 
oxidation of the latter to MA. As the first stage is faster than the second [2],
the kinetics of TBA oxidation determines the oxidation of  K4G8. Therefore, it 
can be described by the Mars-van Krevellen mechanism applicable for the
above catalytic scheme of the process [9]:

k1MA ⋅ Ci − C 4 H 8 ⋅ k2MA ⋅ CO2


WMA = , (1)
k1MA ⋅ Ci − C 4 H 8 + k2MA ⋅ CO2

where k1 and k2 - rate constants of reduction and reoxidation stages of active


centers on a surface of a catalyst. Experimental kinetic regularities of the
process are given in Table 1.
Using experimental data presented in Table 1, k1MA and k 2MA values were
determined, by means of linearized eq. (1) (Table 2).
In the investigated temperature range k1MA > k 2MA , the limiting stage is
connected with the reoxidation of reduced centers of partial oxidation.
It is obvious that the rate constant of reoxidation will increase faster with
temperature than the reduction stage and at some temperature the latter will
become limiting. Taking into account the values of constants k1MA and k 2MA
determined at different temperatures (Table 2), eq. (1) takes the from:

3900 17400
− −
4,6 ⋅ 102 ⋅ e T
⋅ CiC 4 H 8 + 7,9 ⋅ 1010 ⋅ e T
⋅ CO2
WMA = 3900 17400
(2)
− −
(4,6 ⋅ 10 ⋅ e 2 T
+ 7,9 ⋅ 10 ⋅ e
10 T
)

Table 2

L D k1MA k2MA kCO2 kCO bCO2 ⋅103 bCO ⋅103

623 0.89 0.053 0.029 0.015 5.19 4.84


643 1.06 0.166 0.055 0.027 4.68 3.83
663 1.28 0.240 0.100 0.052 4.21 3.03
ZHYZNEVSKIY et al.: tert-BUTANOL 51

(TXDWLRQ   7DEOH   DGHTXDWHO\ GHVFULEHV WKH NLQHWLFV RI F: IRUPDWLRQ


in TBA oxidation.
The products of deep oxidation will form on centers of strong destructive
adsorption, from both LVREXW\OHQH DQG
F:  7KXV ZH DVVXPH WKDW WKH SURGXFWV
of deep oxidation will form according to the series-parallel scheme:

i − C4 H 8 MA CO2 + CO

Fig.1. Overall rate of CO2 DQG KH IRUPDWLRQ vs LVREXW\OHQH  DQG F: 
FRQFHQWUDWLRQV LQ WKH R[LGDWLRQ RI 7%$    .    .    D
7R HYDOXDWH WKH UROH RI D VHTXHQWLDO URXWH WKH R[LGDWLRQ RI F: LQ VLPLODU
FRQGLWLRQV ZDV FDUULHG RXW 7KH SORWV )LJ  RI WKH UDWHV RI KH2 and CO
52 ZHYZNEVSKIY et al.: tert-BUTANOL

formation against overall K4G8 DQG F: FRQFHQWUDWLRQ DUH SUHVHQWHG ,W FDQ EH


VHHQ WKDW LQ WKH R[LGDWLRQ RI 0$ WKH UDWHV RI &2 DQG KH2 formation are
approximately twice lower than in the oxidation of isobutylene in the presence
RI F: 7KDW VLJQLILHV WKDW F$ LV OHVV UHDFWLYH WKDQ K4G8. It is necessary also
to take into account that in the oxidation of TBA, isobutylene competes with
F: IRU DFWLYH FHQWHUV RI WKH FDWDO\WLF VXUIDFH ZKLFK UHGXFHV WKH UROH RI IXUWKHU
R[LGDWLRQ RI F: 7KH FRQVLVWHQF\ RI WKHVH FRQFOXVLRQV LV FRQILUPHG E\ GDWD
7DEOH  RQ WKH GHSHQGHQFH RI F: VHOHFWLYLW\ vs contact time, obtained in the
oxidation of TBA in a conventional flow-type reactor with a stationary layer of
the catalyst.

Table 3
Influence of contact time on K4G8 FRQYHUVLRQ DQG VHOHFWLYLW\ RI
O F: IRUPDWLRQ 6
MA) in the
oxidation of TBA. (Flow reactor, composition of the initial mixture: TBA - 5 mol. %, air - 95
mol. %)

τc, s 7  D 7  D 7  D


O  SMA (%) O  SMA (%) O  SMA (%)

0.59 38.8 90.5 56.6 92.9 66.8 88.7


1.25 78.2 91.4 89.9 94.1 95.2 95.3
1.82 86.0 93.8 94.4 94.6 97.7 94.3
3.30 92.8 94.0 98.0 94.9 99.0 94.5

Over the temperature range 633 - 693 K, with increasing τc from 0.59 to 3.3
V WKH VHOHFWLYLW\ RI F: IRUPDWLRQ GRHV QRW GHFUHDVH 7KXV ZH VXSSRVH WKDW D

sequential mechanism for the formation of products of deep oxidation under the
investigated conditions does not play an essential role. Since for the full
oxidation of isobutylene molecules adsorbed on the centers of destructive
adsorption an excess of oxygen is needed, we think that more feasible is the so-
called "shock" Rideal mechanism, the interaction between adsorbed isobutylene
and oxygen from the gas phase. In this case it is possible to describe the rate of
KH2 and CO formation by the equation [10]:

k i ⋅ bi ⋅ C i −C4 H 8 ⋅ C O2
Wi = (3)
1 + bi ⋅ C i −C4 H 8

where Wi  UDWH RI KH2 and CO formation; ki  UDWH FRQVWDQWV RI KH2 and CO


formation; b - adsorption constant of isobutylene.

ZHYZNEVSKIY et al.: tert-BUTANOL 53

Having linearized eq. (3), from the dependencies


C O2 W CO2 ,CO = f (1 C i −C ) the values of these constants at 623, 643 and
4 H8

663 K were determined. This permitted to evaluate its temperature dependence


and present eq. (3) for the rates of CO2 and CO formation in the form:

12500 2100

1,52 ⋅ 10 ⋅ e 7 T
⋅ 1,76 ⋅ 10 ⋅ e
2 T
CiC 4 H 8 ⋅ CO2
WCO 2 = 2100
(4)
1 + 1,76 ⋅ 10 ⋅ e 2 T
⋅ CiC 4 H 8

12000 4750

3,51 ⋅ 10 6 ⋅ e T
⋅ 2,35 ⋅ 10 8 ⋅ e T
⋅ C iC 4 H 8 ⋅ C O2
WCO = 4750
(5)
1 + 2,35 ⋅ 10 ⋅ e 8 T
⋅ C iC 4 H 8

The applicability of the above equations for describing the kinetics of


carbon dioxide and carbon monoxide formation is confirmed by the satisfactory
agreement of experimental and calculated values from eqs (4) and (5) (Table 1).

CONCLUSIONS

The analysis of the experimental data allows a series of qualitative


conclusions about the influence of basic parameters on the course of oxidation:
 $Q LQVLJQLILFDQW GHFUHDVH RI WKH VHOHFWLYLW\ RI F: IRUPDWLRQ LV REVHUYHG ZLWK

temperature rise from 623 to 663 K.


2. With increasing K4G8 concentration from 0.2x10-3 up to 2x10-3 mol/dm3, the
UDWH RI IRUPDWLRQ RI R[LGDWLRQ SURGXFWV LQFUHDVHV DQG WKH VHOHFWLYLW\ RI F:
formation increases essentially.
3. With increasing oxygen concentration from 8.5x10-3 up to 24x10-3 mol/dm3,
WKH UDWH RIF$ IRUPDWLRQ LQFUHDVHV E\ D IDFWRU RI  DQG WKRVH RI &2 DQG
KH2 E\ IDFWRUV RI  DQG VHOHFWLYLW\ WR F: HVVHQWLDOO\ GHFUHDVHV IURP 
up to 67 %).
54 ZHYZNEVSKIY et al.: tert-BUTANOL

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