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RKCL3761
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.
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.
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]:
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
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
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. %)
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
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
CONCLUSIONS
REFERENCES
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