P10-3

t-butyl alcohol (TBA) is an important octane enhancer that is used to replace lead
additives in gasoline [Ind. Eng. Chem. Res., 27, 2224 (1988)]. t-butyl alcohol was
produced by the liquid-phase hydration (W) of isobutene (I) over an Amberlyst-15
catalyst. The system is normally a multiphase mixture of hydrocarbon, water and solid
catalysts. However, the use of cosolvents or excess TBA can achieve reasonable
miscibility.
The reaction mechanism is believed to be

S TBA S TBA
S S TBA S I S W
S W S W
S I S I
+
+ +
+
+


Determine a rate law assuming:
(a) the surface reaction is rate- limiting
(b) The adsorption of isobutene is limiting
(c) The reaction follows Eley-Rideal kinetics

S TBA W S I +

and that the surface reaction is limiting
(d) Isobutene (I) and water (W) are adsorbed on different sites

2 2
1 1
S W S W
S I S I
+
+


TBA is not on the surface and the surface reaction is rate limiting.

1
]
1

+ +

) 1 )( 1 (
] / [
' ' :
I I W W
C TBA W I
I TBA
C K C K
K C C C k
r r Ans

(e) What generalization can you make by comparing rate laws derived in parts (a)
through (d)?
The process flow sheet for the commercial production of TBA is shown in Figure
P10-3.
(f) What can you learn from this problem and the process flow sheet?

SOLUTION

(a) If the surface reaction is rate limiting the reaction rate can be given by

,
_

sr
S TBAS
IS WS sr S TBAS sr IS WS sr TBA
K
C C
C C k C C k C C k r

Since the other reactions are fast and reversible we may assume that they are at
equilibrium. Thus the concentrations of the adsorbed species are given by:

S TBA TBA TBAS
S W W WS
S I I IS
C C K C
C C K C
C C K C

Substituting these into the rate expression gives

,
_

,
_

sr
TBA TBA
I I W W S sr
sr
S S TBA TBA
S I I S W W sr TBA
K
C K
C K C K C k
K
C C C K
C C K C C K k r
2


We now need an expression for C
s
. If C
ST
is the total number of active sites on
the catalyst surface we get

TBAS WS IS S ST
C C C C C + + +

Using the expressions for the absorbed species concentrations from above gives

S TBA TBA S W W S I I S ST
C C K C C K C C K C C + + +

Solving this for C
S
gives

( )
TBA TBA W W I I
ST
S
C K C K C K
C
C
+ + +

1


Substituting this into the rate expression gives

( )
2
2
1
TBA TBA W W I I
sr
TBA TBA
I I W W ST sr
TBA
C K C K C K
K
C K
C K C K C k
r
+ + +

,
_

After some rearranging this gives

( )
2
1
'
TBA TBA W W I I
TBA
I W I W sr
TBA
C K C K C K
K
C
C C K K k
r
+ + +

,
_

(b) If the adsorption of isobutene is limiting the reaction rate expression becomes

,
_

I
IS
S I aI IS aI S I aI I TBA
K
C
C C k C k C C k r r

The expressions for the concentration of WS and TBAS remain as before. Since
the surface reaction is now fast and reversible we can assume that it is at
equilibrium to get

WS IS
S TBAS
sr
C C
C C
K

Rearrange this to get

W W sr
S TBA TBA
S W W sr
S S TBA TBA
WS sr
S TBAS
IS
C K K
C C K
C C K K
C C C K
C K
C C
C

Substitute this expression into the rate expression to get

,
_

,
_

W W sr I
TBA TBA
I S aI
W W sr I
S TBA TBA
S I aI TBA
C K K K
C K
C C k
C K K K
C C K
C C k r

Again we need an expression for C
S
. Proceeding as in part (a) we get

S TBA TBA S W W
W W sr
S TBA TBA
S
TBAS WS IS S ST
C C K C C K
C K K
C C K
C
C C C C C
+ + +
+ + +


Solving for C
S
gives

TBA TBA W W
W W sr
TBA TBA
ST
S
C K C K
C K K
C K
C
C
+ + +

1


Substituting this into the rate expression gives (after slight rearrangements)

,
_

+ + +

,
_

TBA TBA W W
W W sr
TBA TBA
W
TBA
I aI
TBA
C K C K
C K K
C K
C K
C
C k
r
1
'


(c) If the system follows Eley-Rideal kinetics the mechanism looks like

S TBA S TBA
S TBA W S I
S W S W
S I S I
+
+
+
+


If the surface reaction is still rate limiting then the reaction rate expression is
given by

W IS sr W TBA
C C k r r

Since the adsorption of A is fast and reversible we can write for C
IS


S I I IS
C C K C

We will still need an expression for C
S.
Since the surface reaction is controlling
all adsorption reactions are at equilibrium. This was the same situation as in part
(a) so we will obtain the same expression for C
S
. Combining these expressions
with the rate expression gives

( )
( )
TBA TBA W W I I
W I I sr
TBA
TBA TBA W W I I
W I ST I sr
W S I I sr TBA
C K C K C K
C C K k
r
C K C K C K
C C C K k
C C C K k r
+ + +

+ + +

1
'
1


(d) For this part the mechanism is given by

2 1 1 2
2 2
1 1
S S TBA S I S W
S W S W
S I S I
+ + +
+
+


The rate expression is now given by

,
_

sr
S S TBA
WS IS sr S S TBA sr WS IS sr TBA
K
C C C
C C k C C C k C C k r
2 1
2 1 2 1 2 1


We now need to find expressions for both C
IS1
and C
WS2
. These will be done in
exactly the same manner as before using C
S1T
and C
S2T
to represent the total
concentration of sites of types 1 and 2, respectively. Thus we get

1 1 1
IS S T S
C C C +

Since the surface reaction is limiting all adsorbed specie concentrations are at
equilibrium so we get

1 1
S I I IS
C C K C

Substituting this into the expression above and solving for C
S1
gives

( )
I I
T S
S
C K
C
C
+

1
1
1


Doing the same thing for C
S2
yields

( )
W W
T S
S
C K
C
C
+

1
2
2


Combine all of these with the rate expression to get

( ) ( ) ( ) ( )

,
_

+ +

+ +

,
_

W W
T S
I I
T S
sr
TBA
W W
T S
I I
T S
W W I I sr
sr
S S TBA
S W W S I I sr TBA
C K
C
C K
C
K
C
C K
C
C K
C
C K C K k
K
C C C
C C K C C K k r
1 1 1 1
2 1 2 1
2 1
2 1


After some rearranging this gives

( )( ) ( )( )
W W I I
W I sr
TBA
W I W I sr
W W I I
sr
TBA
W I W I sr
TBA
C K C K
K K K
C
C C K K k
C K C K
K
C
C C K K k
r
+ +

,
_

+ +

,
_

1 1
'
1 1
'


(e) The rate laws change depending upon the rate- limiting step. The changes that
occur are primarily in the denominator (adsorption group) and in the kinetic
constant.
(f) The C
8
stream at the end indicates that there are other reactions going on inside
the reactor. In the first tower the C
4
s are separated. The bottoms from that tower
go on to separate TBA and water. TBA has a lower boiling point than water. So
it seems likely that the bottoms from the tower marked AC contains mainly
water (little to no TBA or isobutene). Thus it seems that the process is trying to
keep water concentrations high and isobutene and TBA low. Having this pattern
of concentrations would help increase the rate in both (b) and (d). Thus it would
seem likely that one of these two is the actual mechanism.