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Dieter Bothe, Andreas Steinkemper, Hans-Joachim Warnecke

Technische Chemie und Chemische Verfahrenstechnik,

Department Chemie, Fakult at f ur Naturwissenschaften

Universit at Paderborn, Warburger Strasse 100, 33098 Paderborn, Germany

Abstract

A new mechanistic reaction scheme of the dehydration of t-butanol in

sulfuric acid is proposed which accounts for a parallel reaction path via

di-t-butylether. Based on the quasi-steady-state-approximation con-

cerning intermediates, a mathematical model is developed that incor-

porates the acidity of the solvent. Model validation is done by means

of experimental data obtained from stationary CSTR-measurements

at dierent temperatures under reaction conditions that exclude the

formation of oligomers. It is shown how numerical simulations, com-

bining this mathematical model with experimental correlations, allow

for maximization of isobutene yield in a batch reactor under avoidance

of the formation of oligomers.

1 Introduction

Isobutene is an important monomer for the manufacture of high-grade poly-

mers with special properties (high molecular weight polyisobutene and butyl

rubber). Today, one important source of isobutene is t-butanol. Besides

other heterogeneous catalytic processes, the dehydration of t-butanol (TBA)

in sulfuric acid is a common way for the production of very pure isobutene.

warnecke@tc.upb.de

1

The dehydration process has been investigated in several papers. Warnecke

et al. [1] examined the hydration of isobuten in sulfuric acid, focusing on

equilibrium measurements at room temperature conditions without account-

ing for the activity of protons. Furthermore, a single chemical reaction path

is assumed. The reaction rate constants given there are obtained by means

of empirical methods. They depend on temperature and composition of the

reacting mixture and are only valid for a small range of temperatures close to

room temperature. Especially at temperatures above 70

concentrations, oligomerization of isobutene occurs and leads to undesired

byproducts. These side reactions have been investigated in Allenbach [2]

and in Allenbach et al. [3], where rates for the oligomerization of isobutene

in the form of empirical correlations are given; cf. setion 6 below.

Both studies are based on regression methods and provide no information

about the underlying reaction mechanism. In particular, the catalytic eect

of sulfuric acid is not explicitly taken into account. To gain a better insight

into the mechanism of the isobutene formation, a mechanistic reaction model

is developed here which incorporates the inuence of the solvents acidity by

means of the Hammett acidity function.

Under quasi-steady-state-assumptions concerning intermediates, a simpli-

ed kinetic model is obtained. Fitting of the model parameters to new experi-

mental data yields parameter values which allow for better understanding of

the reaction mechanism. Combining this model with the results of Allenbach,

numerical simulations can be performed to compute reaction conditions, for

which oligomerization of isobutene is avoided and yield of isobutene is max-

imized.

2 Experimentals

The experimental set-up for the measurements of steady-state rates of isobu-

tene formation is illustrated by Figure 1. Since dilute sulfuric acid is very

corrosive, the liquid phase reaction is performed in a continuous stirred tank

reactor (CSTR) made of glass. By means of an overow, the reaction volume

is kept constant at 65 ml. The reaction temperature is controlled by an

external thermostatic unit and can be thermostated within 0.2

C. Dierent

liquid feeds are dosed with a peristaltic pump. The feed consisting of water,

TBA and sulfuric acid is prepared at low temperatures because otherwise

the heat of mixing leads to the formation of oligomers.

2

Mass ow rates into and out of the CSTR are measured. At the end of

cooler 1 (gas exit) and cooler 2 (liquid exit), gas, respectively liquid samples

are taken. Inside cooler 2 a siphon prevents gas from leaving the reactor. So

gas leaves at end of cooler 1 and liquid at end of cooler 2. For residence time

computation a colored tracer is used which is detected by a phototransistor

at cooler 2.

At steady-state condition the liquid samples are cooled down immedi-

ately by means of liquid nitrogen. Each gas sample is collected over a xed

time interval, so that the ow rate of isobutene is determined by the sam-

ples weight. It can be achieved that the liquid compounds are completely

condensed by cooler 1, hence gas samples contain isobutene exclusively.

The composition of feed and outlet samples are determined from infrared

spectroscopy measurements. For this purpose the ATR-technique (attenu-

ated total reection) is employed. The ATR-crystal consists of ZrO

2

and

is resistant against strong mineralic acids. Calibration is done by means of

the chemometric PLS-method (partial least squares), where weight percents

instead of molar concentrations is used to avoid temperature dependence.

The actual concentrations are then calculated using density functions, which

are computed from density measurements at 20

C, 25

C, 30

C. It is shown

in Steinkemper [4] that these functions are also valid for the applied temper-

atures of 63

C, 68

C, 73

C.

3 Reaction Mechanism

Motivated by studies of Xu [5], whose research describes the dehydration of

t-butanol in compressed liquid water at 250

reaction mechanism illustrated in Figure 2.

According to classical organic chemistry, TBA forms a protonated al-

cohol, which dehydrates into a carbocation. Elimination of a proton then

leads to isobutene. Since the latter reaction step is very slow in strong acid

solutions, the generation of isobutene via this path alone is somewhat unplau-

sible. Therefore, we anticipate a parallel reaction path via di-t-butylether as

an intermediate. This ether is unstable in water as well as in acid solutions

and decomposes into TBA and isobutene or is hydrolyzed into two molecules

of TBA. Let us note that di-t-butylether has been synthesized and its ther-

modynamic properties are well known [6, 7]. Moreover, the intermediate c

4

is highly unstable even in strong acids. Consequently, this second pathway

3

is expected to play a role in the formation of isobutene.

Notice also that isobutene spontaneously forms a gaseous phase which

leaves the liquid bulk phase.

4 Modeling

Based on mass action kinetics, the reaction mechanism given by Figure 2

leads to the following system of ordinary dierential equations which governs

the evolution in time of the amounts of the involved species

1

V

dn

T

dt

= k

1

c

T

a

P

+ k

z

1

c

2

k

4

c

3

c

T

+ k

z

4

c

4

+k

6

c

E

+ 2k

7

c

E

c

W

, (1)

1

V

dn

H

+

dt

= k

1

c

T

a

P

+ k

z

1

c

2

+ k

z

3

c

I

a

P

+k

5

c

4

k

z

5

c

E

c

A

, (2)

1

V

dn

2

dt

= k

1

c

T

a

P

k

z

1

c

2

k

2

c

2

+ k

z

2

c

3

c

W

, (3)

1

V

dn

3

dt

= k

2

c

2

k

z

2

c

3

c

W

k

3

c

3

+ k

z

3

c

I

a

P

k

4

c

3

c

T

+ k

z

4

c

4

, (4)

1

V

dn

I

dt

= k

3

c

3

k

z

3

c

I

a

P

+ k

6

c

E

, (5)

1

V

dn

W

dt

= k

2

c

2

k

z

2

c

3

c

W

k

7

c

E

c

W

, (6)

1

V

dn

4

dt

= k

4

c

3

c

T

k

z

4

c

4

k

5

c

4

+ k

z

5

c

E

a

P

, (7)

1

V

dn

E

dt

= k

5

c

4

k

z

5

c

E

a

P

k

6

c

E

k

7

c

E

c

W

. (8)

In the system above, a

P

denotes the activity of protons and is dierent

from c

H

+. This activity depends on the degree of solvation of the protons (ei-

ther by TBA, water or both) which in turn is related to the acidity of the

medium. The latter can be described by the Hammett acidity function H

0

[8],

especially in case of strong mineralic acid solutions. For a lot of acid catalyzed

reactions a linear dependence

log

10

k = const H

0

(9)

4

is found, where k denotes the rate constant. Therefore, instead of c

H

+ the

quantity

a

P

= 10

H

0

(10)

is employed as a measure for catalytic activity of the protons.

Friedrich [9] gives several values of H

0

for the system TBA/H

2

SO

4

/H

2

O.

These values turn out to be linearly correlated to the concentration c

A

of

sulfuric acid. Indeed, the relation

H

0

= c

A

+ (11)

holds with high accuracy for c

A

(made dimensionless using 1 mol/L as refer-

ence quantity) with the correlations

=1.071 0.616 exp

6.41

c

T

c

W

, (12)

=2.718 + 2.755 exp

8.69

c

T

c

W

. (13)

Due to the fact that most of the intermediate species are inaccessible to

measurements, the individual rate constants k

i

, k

z

i

in (1)-(8) cannot be ob-

tained with reasonable eort. On the other hand, the intermediate species

c

2

, c

3

, c

4

and c

E

are expected to be short-lived, hence application of quasi-

steady-state-approximation (QSSA) for these chemical species is allowed.

After application of QSSA, performed by means of a lengthy but elemen-

tary computation, it turns out that dehydration of TBA can be modeled by a

single reaction rate which formally corresponds to the acid catalysed overall

reaction

T

PSfrag replacements

k

F

k

B

I + W. (14)

The rate function of this overall reversible reaction is given by

r = k

F

a

P

c

T

+ k

B

a

P

c

I

c

W

. (15)

The structure of r is the same as if the reaction rate would follow from

mass action kinetics, but the rate constants that result from the QSSA-

procedure turn out to be rather complex functions of c

T

, c

W

and a

P

. These

5

read as

k

F

= p

1

1 + p

2

c

T

1 + p

3

c

W

+ p

4

a

P

1 + p

5

c

W

+ p

2

1 + p

3

c

W

1 + p

3

c

W

+ p

4

a

P

c

T

(16)

and

k

B

= p

6

p

5

+ p

2

p

3

c

T

1 + p

3

c

W

+ p

4

a

P

1 + p

5

c

W

+ p

2

1 + p

3

c

W

1 + p

3

c

W

+ p

4

a

P

c

T

. (17)

Here the parameters p

i

are related to the rate constants k

i

as follows.

p

1

=

k

1

k

2

k

z

1

+ k

2

, p

2

=

k

4

k

5

k

3

(k

z

4

+ k

5

)

, (18)

p

3

=

k

7

k

6

, p

4

=

k

z

4

k

z

5

k

6

(k

z

4

+ k

5

)

, (19)

p

5

=

k

z

1

k

z

2

k

3

(k

z

1

+ k

2

)

, p

6

= k

z

3

. (20)

5 Validation

Experimental validation of the kinetic model is done by means of CSTR-

measurements. In contrast to batch experiments, this allows to keep the

reaction volume constant during each measurement. Mass balances lead to

V

dc

T

dt

=

V

f

c

f

T

V c

T

V k

F

a

P

c

T

+ V k

B

a

P

c

I

c

W

, (21)

V

dc

W

dt

=

V

f

c

f

W

V c

W

+ V k

F

a

P

c

T

V k

B

a

P

c

I

c

W

, (22)

V

dc

I

dt

= V k

F

a

P

c

T

V k

B

a

P

c

I

c

W

k

L

A(c

I

c

g

I

/H

I

) , (23)

V

g

dc

g

I

dt

= k

L

A(c

I

c

g

I

/H

I

) n

out

. (24)

Under steady-state conditions, the two balances for isobutene, i.e. (23), (24)

lead to

n

out

= k

L

A(c

I

c

g

I

/H

I

) = V (k

F

a

P

c

T

k

B

a

P

c

I

c

W

) = V r. (25)

6

This can be simplied to

n

out

= V r

F

= V k

F

a

P

c

T

, (26)

since the concentration of isobutene in liquid phase is very small due to

spontaneous phase change of isobutene into a gaseous phase. Note that the

isobutene balance is most appropriate for validation, since the mass ux of

isobutene can be measured with high accuracy.

Finally, use of V =

V with residence time together with

V c

T

= n

T

=

m

T

M

T

(27)

leads to the following formulation of the isobutene balance, which is suitable

for measurement analysis and parameter estimation:

m

g

I

M

I

= n

out

=

m

T

M

T

a

P

k

F

(28)

with k

F

from (16).

We performed experiments under isothermal steady state conditions at

three dierent temperatures for various feed compositions. Evaluation of

the measurements is done by means of nonlinear t of model parameters

p

1

, . . . , p

5

in equation (16). For this purpose we utilized only experimental

data corresponding to those 13 feed compositions where reliable measure-

ments were possible at all temperatures. The feed compositions in these

measurements are shown in the following Table 1. Parameter tting shows

that not both parameters p

2

and p

5

are signicant, but only their ratio is.

This leads to arbitrarily large values for p

2

and p

5

, hence the tting algo-

rithm is not convergent. Note that large values for p

2

and p

5

are reasonable,

since both parameters contain the factor 1/k

3

, and the reaction step with

rate constant k

3

characterizes the nonpreferred reaction path, i.e. k

3

takes

small values [10]. To overcome this defect, we x p

2

at a suciently large

value and use the ratio p

5

= p

5

/p

2

as a new parameter. This corresponds to

the following simplied relation for k

F

.

k

F

=

p

1

c

T

1 + p

3

c

W

+ p

4

a

P

p

5

c

W

+

1 + p

3

c

W

1 + p

3

c

W

+ p

4

a

P

c

T

. (29)

7

no. c

f

A

[mol/L] c

f

W

[mol/L] c

f

T

[mol/L]

1 31.3 15.6 53.1

2 30.9 15.2 53.9

3 29.8 15.6 54.5

4 29.0 29.0 41.9

5 30.2 34.2 35.6

6 30.7 20.4 48.9

7 35.4 23.6 41.0

8 25.5 12.2 62.3

9 26.6 7.9 65.5

10 24.8 7.9 67.3

11 33.8 28.1 38.1

12 30.4 4.6 65.0

13 19.4 2.7 77.9

Table 1: Feedcompositions

The results of the parameter estimation is shown in Table 2, while the qual-

ity of tting the model predictions to the measurements is illustrated by

Figures 3, 4 and 5. Unfortunately, due to the restricted number of these

quite elaborate experiments, a specication of statistical quantities is not

reasonable here. Nevertheless, the gures show a sucient agreement.

63

C 68

73

p

1

[ - ] 0.0071 0.0074 0.0345

p

3

[L/mol] 0.7821 0.2684 0.2182

p

4

[ - ] 0.6633 2.1985 10.6578

p

5

[ - ] 7.5169 2.5244 1.7657

Table 2: Parameter

The values of the obtained model parameters are dicult to interpret on

the basis of individual reaction constants, since each term is a combination

of several rate constants. For this reason the activation energies cannot

be calculated. Still, the model parameters show a monotonic dependence

on temperature. The model shows that formation of isobutene due to the

decomposition process of the ether is relevant and its contribution increases

8

with temperature.

6 Simulation of the dehydration of t-butanol

in a batch reactor

At a rst glance, the kinetic model developed above seems unapplicable for

the real process since the formation of oligomers has been omitted. But

production of oligomers has to be avoided anyhow, hence a combination

of our model with the production rates of oligomers, obtained empirically

by Allenbach [2] can be used for process optimization in the regime where

formation of oligomers is negligible.

We illustrate this approach in case of batch simulations. Since the batch

volume V changes signicantly during the reaction, we have to formulate the

balance equations in terms of the total amounts of molar masses instead of

concentrations. Together with (15) this leads to the system

dn

T

dt

=k

F

(a

P

,

n

T

V

,

n

W

V

) a

P

n

T

, n

T

(0) = n

0

T

dn

W

dt

= k

F

(a

P

,

n

T

V

,

n

W

V

) a

P

n

T

, n

W

(0) = n

0

W

dn

I

dt

= k

F

(a

P

,

n

T

V

,

n

W

V

) a

P

n

T

, n

I

(0) = n

0

I

(30)

with k

F

(a

P

, c

T

, c

W

) from (16), where a

P

is computed according to (10) - (13).

Simultaneously, the amount n

Ol

of oligomers is calculated by solving the

initial value problem

dn

Ol

dt

= V r

Ol

(

n

T

V

,

n

W

V

; T, c

0

T

, c

0

A

), n

Ol

(0) = 0, (31)

where r

Ol

(c

T

, c

A

; T, c

0

T

, c

0

A

) is the rate of formation of oligomers at tempera-

ture T and for initial composition c

0

T

, c

0

A

due to Allenbach [2]. To keep the

paper self-contained, this correlation is reproduced here. It reads as follows,

where temperature, time and molar concentrations are made dimensionless

using K, min and

mol

L

as reference dimensions, for T, t and c, respectively.

r

Ol

= k(T) (c

0

T

, c

0

A

)(c

T

, c

A

) (32)

with

log k(T) = 25.81

6539

T

, (33)

9

log (c

0

T

, c

0

A

) = 12.6(0.414c

0

T

1) log c

0

A

38.5 log c

0

T

, (34)

(c

T

, c

A

) = c

2

T

c

7

A

. (35)

Let us note in passing that this experimental correlation is based on the

molar acid concentration c

A

instead of an acidity function. This makes the

large exponent in the last equation plausible.

Since the batch volume V is not constant, we use conservation of sulfuric

acid, i.e.

V

0

c

0

A

= V (t)c

A

(t), (36)

for solving (30) and (31). Here c

A

(t) is determined from the relation

c

A

=

1000(c

T

, c

W

, T) 74c

T

18c

W

98

(37)

with the experimentally obtained correlation (see [4])

(c

T

, c

W

, T) = 2.55 + a

1

(T 293.15)

+(0.163 a

2

(T 293.15)) c

T

(38)

+(0.028 a

3

(T 293.15)) c

W

.

In (38), all concentrations are dimensionless with 1 mol/L as reference quan-

tity and the parameter values are

a

1

= 1.84 10

4

, a

2

= 3.02 10

4

, a

3

= 4.45 10

5

.

Altogether, given n

T

, n

W

as well as T and c

0

A

, the batch volume V is implic-

itly determined by the relation

V

0

c

0

A

V

=

1000(

n

T

V

,

n

W

V

, T) 74

n

T

V

18

n

W

V

98

. (39)

Knowing the molar masses hence allows for computing the corresponding con-

centration. The ratio between production of oligomers and that of isobutene

is then given by

n

Ol

(t)

n

I

(t)

=

V

0

c

0

A

n

I

(t)

t

0

r

Ol

(c

T

(s), c

A

(s); T, c

0

T

, c

0

A

)

c

A

(s)

ds. (40)

10

Now we proceed as follows. The numerical calculation is continued until

either

n

Ol

(t)

n

I

(t)

= q

crit

at a rst t = t

crit

or (41)

1

c

T

(t)

c

0

T

> U

at a rst t = t

, (42)

i.e. until a critical fraction of oligomers (say q

crit

= 0.01) or the desired

conversion, say U

t

proc

= min{t

crit

, t

} (43)

and the associated conversion

U(c

0

T

, c

0

A

) = 1

V (t) c

T

(t

proc

)

V (0) c

0

T

. (44)

Hence U(c

0

T

, c

0

A

) denotes the conversion which is reachable with suciently

small production of oligomers. This is shown in Figure 6, where the plateau

region corresponds to those initial conditions for which our model is valid

because formation of oligomers is negligible. Recall that the rate function

(15) is based on experiments without formation of oligomers.

For optimization of the dehydration process we dene a performance by

means of

P(c

0

T

, c

0

A

) =

0 if t

proc

= t

crit

U(c

0

T

, c

0

A

)

t

proc

if t

proc

< t

crit

, (45)

where the performance is dened to be zero if production of oligomers is not

negligible. The process performance is shown in Figure 7, which illustrates

the existence of an optimal initial composition at approximately (c

0

A

= 3.8

mol/L, c

0

T

= 8.0 mol/L, c

0

W

= 3.32 mol/L) within realizable range of initial

concentrations.

The optimal composition corresponds to about 5% of water and is only

achievable by mixing almost concentrated sulfuric acid with TBA. In practice

one has to be careful concerning release of mixing enthalpies, since this can

lead to oligomerization. The peaks that can be noticed in Figure 7 are due

to numerical instabilities and hence articial.

11

The dynamical behavior during the dehydration process is illustrated by

Figures 8-11, where the initial composition is chosen as

c

0

T

= 8 mol/L, c

0

A

= 3.8 mol/L, c

0

W

= 3.32 mol/L (c

0

I

= c

0

Ol

= 0 mol/L).

For this feed composition and for a batch volume of 1L, say, the total amount

of oligomers, produced until a conversion of 95% is reached, is about 0.04

mol. Hence the ratio n

Ol

/n

I

is below 0.5% (cf. Figures 8,9). Observe also that

the acidity attains a gentle maximum at approx. 200 min (see Figure 10).

This agrees with the changes in volume and in water concentration. Indeed,

the fast decrease of the batch volume (cf. Figure 11) leads to an increase of

the acid concentration in the initial phase, followed by a decrease in the long

run due to dilution by increasing amounts of water.

7 Conclusions

The dehydration of t-butanol (TBA) in sulfuric acid is a common way for the

production of very pure isobutene. The demands concerning the quality are

high, in particular for the synthesis of polymers with high molecular weight.

Depending on composition of the acid phase, cleavage of TBA is problematic

since it leads to dierent yields of isobutene. Especially at temperatures

above 70

isobutene occurs.

This work investigates the optimization of the dehydration process with

respect to isobutene yield under avoidance of the formation of oligomers.

For this purpose a mechanistic reaction model is developed which incorpo-

rates the inuence of the solvents acidity by means of the Hammett acid-

ity function. The reaction scheme includes the postulated intermediates t-

butyloxoniumion, trimethylcarboniumion, di-t-butylether (DTBE) and the

protonated form of the ether.

Determination of the model parameters is based on measurements under

steady-state conditions in a continuous stirred tank reactor (CSTR). To study

temperature dependence, experiments are performed at 63

C, 68

C and 73

C.

Under quasi-steady-state-assumptions concerning intermediates, a sim-

plied kinetic model is obtained via QSSA. Coupling of the resulting kinetic

equations to CSTR balance equations leads to the complete mathematical

model. Fitting of the remaining model parameters to experimental data

yields parameter values which allow for better understanding of the reaction

12

mechanism. In particular, the formation of isobutene via decomposition of

DTBE is conrmed by the values of the tted model parameters.

Combining this model with the results of Allenbach, numerical simula-

tions are done to compute reaction conditions, for which oligomerization of

isobutene is avoided and yield of isobutene is maximized.

13

Nomenclature

A interfacial area [m

2

]

H

0

Hammett acidity function

H

I

Henry coecient

K equilibrium constant

M molar mass [g]

P performance

T temperature [K]

U conversion

V reaction volume [L]

V volumetric ux [L min

1

]

a activity

c concentration [mol L

1

]

c

2

concentration of t-butyloxonium ion [mol L

1

]

c

3

concentration of t-butylcation [mol L

1

]

c

4

concentration of protonated di-t-butylether [mol L

1

]

k reaction rate constant [(L mol

1

)

m1

min

1

] for m-th order

k

L

mass transfer coecient

m mass [g]

m mass ow [g s

1

]

n molar amount of species [mol L

1

]

n mol ow [mol s

1

]

p, p

parameter

q mol ratio

r reaction rate

s integration variable

t time [min]

Greek symbols:

tting parameter of Hammett function [L mol

1

]

tting parameter of Hammett function [ - ]

, correlation function

density [kg L

1

]

residence time [min]

14

Subscripts:

0 initial value

A sulfuric acid

B reverse reaction

E di-t-butylether (DTBE)

F forward reaction

I isobutene

T t-butanol

W water

Ol oligomers

crit critical

out outlet

proc process

innity

Superscripts:

0 initial value

f feed

g gas phase

z reverse reaction

Abbreviations:

CSTR continuous stirred tank reactor

DIB diisobuten (2,4,4-trimethyl-penten-1 and 2,4,4-trimethyl-penten-2)

DTBE di-t-butylether

TBA t-butylalcohol

ATR attenuated total reection

References

[1] H.-J. Warnecke, J. Pr uss, B. Bienek, R. G. Presenti, Modeling isobutene

extraction from mixed C

4

-streams, Chem. Eng. Sci. 47, 533-541 (1992).

[2] U. Allenbach, Untersuchung der schwefelsauer katalysierten Bildung von

Oligomeren des Isobutens, PhD-Dissertation, Berlin (1978).

[3] U. Allenbach, B. Wichtendahl, W.-D. Deckwer, Makrokinetik und Se-

lektivitat der Bildung von Oligomeren des Isobutens, Erd ol+Kohle 31,

353-355 (1978).

15

[4] A. Steinkemper Modellierung der Dehydratisierung von t-Butanol

unter Vermeidung der Oligomerenbildung, PhD-Dissertation, Paderborn

(2001).

[5] X. Xu and M. J. Antal, Kinetics and Mechanism of Isobutene Forma-

tion form t-Butanol in Hot Liquid Water, AIChE Journal 40, 1524-1534

(1994).

[6] E. J. Smutny and A. Bondi, Di-t-Butyl Ether: Strain Energy and Phys-

ical Properties , J. Phys. Chem. 65, 546-550 (1961).

[7] J. O. Fenwick, Thermodynamic Properties of Organic Oxygen Com-

pounds: Enthalpies of Formation of Eight Ethers, J. Chem. Thermo-

dynamics 7, 1943-1947 (1975).

[8] Hammett, L. P.: Physical organic chemistry : reaction rates, equilibria,

and mechanisms. (2

nd

ed.), McGraw-Hill 1970.

[9] A. Friedrich, H.-J. Warnecke, H. Langemann Die Hammettsche Acidi-

t atsfunktion von Schwefels aure in Wasser-t-Butanol L osungen, Z. Phys.

Chemie 265, 11-16 (1984).

[10] E. Velo, L. Puigjaner Inhibition by Product in the Liquid-Phase Hy-

dration of Isobutene to tert.-Butyl Alcohol: Kinetics and Equilibrium

Studies, Ind. Eng. Chem. Res. 27, 2224-2231 (1988).

16

0.00g 0.00g

PSfrag replacements

balances

measure unit

PC

pump

cooler 2

cool traps

cooler 1

T

exible connection

reactor

magnetic stirrer

Figure 1: Experimental set-up

+

+

+

+

PSfrag replacements

k

1

+H

+

H

+

k

z

1

+H

+

k

z

3

k

3

H

+

k

2

H

2

O

+H

2

O

k

z

2

k

7

+H

2

O

+H

+

k

z

5

k

5

H

+

O

O

O

O

H

OH

OH

OH

OH

OH

2

+

+

c

T

c

2

c

3

c

I

c

4

c

E

k

4

k

z

4

k

6

2

Figure 2: Postulated reaction mechanism of the dehydration of t-butanol

17

PSfrag replacements

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

0.0

1.0

2.0

3.0

4.0

5.0

n

I

[

1

0

4

m

o

l

/

s

]

No. of Experiments

Model

Samples

Figure 3: Fit for 63

C

PSfrag replacements

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

n

I

[

1

0

4

m

o

l

/

s

]

No. of Experiments

Modell

Samples

Figure 4: Fit for 68

C

18

PSfrag replacements

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

n

I

[

1

0

4

m

o

l

/

s

]

No. of Experiments

Modell

Samples

Figure 5: Fit for 73

C

19

3.5

4

4.5

5

c

A

@molLD

4

5

6

7

8

c

T

@molLD

0.4

0.6

0.8

1

Conversion

3.5

4

4.5

5

c

A

@molLD

Figure 6: Simulation of conversion depending on c

0

T

und c

0

A

3.5

4

4.5

5

c

A

@molLD

4

5

6

7

8

c

T

@molLD

0

0.02

0.04

0.06

0.08

Performance

3.5

4

4.5

5

c

A

@molLD

Figure 7: Simulation of process performance depending on c

0

T

und c

0

A

20

0 200 400 600 800 1000

t @minD

0

2

4

6

8

n

I

@

m

o

l

D

Figure 8: Simulated molar mass of isobutene

0 200 400 600 800 1000

t @minD

0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

n

O

l

@

m

o

l

D

Figure 9: Simulated molar mass of oligomers

21

0 200 400 600 800 1000

t@minD

0

20000

40000

60000

80000

100000

a

H

H

2

S

O

4

L

@

m

o

l

L

D

Figure 10: Evolution of acidity

0 200 400 600 800 1000

t @minD

0.2

0.4

0.6

0.8

1

V

s

V

0

@

D

Figure 11: Simulated change in relative acid volume

22

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