University of California, Davis

Chemical Engineering and Material Science Department

ECH 155B
March 20th 2012

CATALYTIC DEHYDRATION OF
T-BUTYL ALCOHOL TO ISOBUTYLENE
Experiment performed on February 2st 2012

GROUP 9
Christopher Bailey
Michael Burgess
Alexander Nicoloff
MengjingYu
Robert Zhang

Objective
1. Study reaction mechanism of t-butyl alcohol (TBA)

dehydration reaction using sulfonated catalyst.

2. Study the water inhibition.
3. Find Langmuir model parameters that givesthe best
fit.
4. Find out how many water molecules occupy a catalyst
site.

Industrial Applications
Fuel Additives
MTBE, ETBE, isooctane

Rubber
Butyl rubber

Food Additives
Butylated hydroxytoluene

Methods to Produce Isobutylene

Steam Cracking
Fluid Catalytic Cracking
Dehydrogenation of Butane
Dehydration of T-butyl Alcohol

Previous Work
Gates and Rodriguez (1972)
Langmuir model

Heath and Gates (1971)

Effects of temperature and catalyst pore size on reaction
kinetics

Xu and Antal (1994)

Used superheated water as amedium to prove that reaction
can take place with water

THEORY

Dehydration Reaction of TBA

CH3
H3C

CH3

-SO3H

OH

CH3

t-Butyl Alcohol

Diluents:
1. Methylcyclohexane (MCH)
2. Water

C2H

+ H2O

C
CH3

Isobutylene

Literature

Figure 1. Kinetics of t-butyl alcohol dehydration catalyzed by sulfonic acid

resin at 80 C. (Gates and Rodriguez 1973)

Langmuir-Hinshelwood Model

[ +

Assume = = =1 as done by Gatesand Rodriguez.

Types of Catalytic Reaction

Heterogeneous Reaction
-When the diluent is Methylcyclohexane (MCH)
-Reaction catalyzed by the sulfonic group
Homogeneous Reaction
-When water concentration is high
-Reaction catalyzed by hydronium ions because water is
solvated by the sulfonic acid groups

Temperature Correction
Derived fr omArrhenu
is

Equation

353 =

1 1

353

EXPERIMENTAL METHOD

1. Twenty samples of catalyst

weighing around 1.5g were
dried in a vacuum oven at
120oC overnight.
2. Mixtures of t-butyl alcohol
diluted with either water or
MCH was placed in a semibatch reactor
3. After the mixture was brought
to boiling point, catalyst were
charged into the reactor.
4. Temperature, and bubble
traveling time were recorded as
reaction proceeds.
5. Catalytic site mass was
obtained through titration

Trial

TBA
TBA
volume concentration
0.5, mL
(mol/ L)

1
200
10.54
2
200
10.54
3
195
10.2765
4
190
10.013
5
185
9.7495
6
160
8.432
7
130
6.851
8
100
5.27
9
70
3.689
10
40
2.108
11*
20
1.054
12
180
9.486
13
160
8.432
14
140
7.378
15
120
6.324
16
100
5.27
17
80
4.216
18
60
3.162
19*
40
2.108
20
20
1.054
*These trials were discarded

Diluent
none
none
water
water
water
water
water
water
water
water
water
MCH
MCH
MCH
MCH
MCH
MCH
MCH
MCH
MCH

Vial
4
7
11
5
8
6
9
1
12
18
13
10
14
15
3
2
20
16

Table 1. TBA concentration in each trial and

the corresponding diluent

Vial

Catalyst Mass
(g)

Catalyst
Moles

1
2
3
4

1.472
1.508
1.488
1.452

0.009462
0.009693
0.009565
0.009333

5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Standard

1.415
1.495
1.497
1.492
1.492
1.56
1.562
1.557
1.566
1.577
1.533
1.569
1.527
1.51
1.554
1.571
1.005

0.009095
0.009610
0.009623
0.009590
0.009590
0.010027
0.010040
0.010008
0.010066
0.010137
0.009854
0.010085
0.009815
0.009706
0.009989
0.010098
0.006460

Table 2. Catalyst mass and the corresponding

moles

RESULTS and DISSCUSSION

Determination of Initial Reaction Rates

Trial 8: TBA diluted with 100 ml MCH
0.02

Reaction Rate (mol isobutylene/ mol catalyst*s)

0.018
0.016
0.014
0.012
0.01

y = -9E-06x + 0.0185

0.008
0.006
0.004
0.002
0
0

100

200

300

400

500
600
Reaction Time (s)

700

Hence, the initial rate of reaction for this trial is 0.0185

800

900

1000

Initial Reaction Rates vs. Alcohol

Concentration
Reaction Rate (mol isobutylene/ mol catalyst*s)

0.03

0.025

0.02

0.015

0.01

0.005

0
0

Alcohol Concentration (mol/ L)

Methylcyclohexane

Water

10

12

Data Fitted to Langmuir-Hinshelwood Kinetics

Initial Reaction Rate vs. Alcohol Concentration:

With Experimentally Deter mined Rate Equation
Reaction Rate (mol isobutylene/ mol catalyst*s)

0.03

0.025

0.02

0.015

0.01

0.005

0
0

TBA Concentration (mol/ L)

Methylcyclohexane

Water

10

12

Homogenous vs. Heterogeneous Catalysis

Resin structure in
anhydrousmedium

Resin structure in
aqueousmedium
Tejero, Cunill & Iborra, 1986

Homogeneous Mechanism
CH3
H3C

OH

CH3

Rapid,
Reversible
CH3
H3C

H
O
+

CH3

O
H

CH3

CH3
H

H3C

O+

H3C

C+

H
CH3

Slow,
Rate
Determining

CH3

+ H2O

CH3

C+

Rapid,
Reversible

CH3
H2C

C
CH3

CH3

Heterogeneous Catalysis Mechanism

Reaction occurs viatwo separate mechanisms, first order and fourth order
1st Order

4th Order

Gates, Wisnouskas, Heath, 1971

Scale-Up
Any dehydration catalyst can be
used
Azeotrope forming agent
Xylenes
Toluene
Benzene
Paraxylene preferred
3 to 60 wt% H20 in feed
stream
FeedTBA after dehydrator - 20
For pureTBA feed 120

(Levine R, inventor, 1979)

Sources of Error
Major:
Flow meter ( 0.05mL)
Thermocouple ( 1C)
Recording in time ( 1sec)
Minor:
Catalyst mass ( 0.001g)
Buret reading during titration ( 0.05mL)

CONCLUSION
Kinetics fit to the Langmuir-Hinshelwood model gives:

.
R=
+ . + 4.

+ . 4

Water as a byproduct and additive has a dramatic effect on

reaction rate
Pseudo-first order occurs when
mixtures

<7M for TBA-Water

Reference

B. C. Gates andWilliam Rodriguez, J. Catal. 31 (1973) 27

ECH 155B reactor Lab Handout, UC Davis Chemical Engineering and Material
Sciences
Tejero, J., F. Cunill, and M. Iborra. "Molecular Mechanisms of MTBE Synthesis on
a Sulphonic Acid Ion Exchange Resin."Journal of Molecular Catalysis42 (1987): 25768. Web.
Gates, B. C., J. S. Wisnouskas, and H. W. Heath. "The Dehydration of T-Butyl
Alcohol Catalyzed by Sulfonic Acid Resin."Journal of Catalysis24 (1972): 320-27.
Web.
Levine, Ralph. Continuous Process for Dehydration of Tertiary Butyl Alcohol.
Cities Service Company, assignee. Patent 4155945. 22 May 1979. Print.
Brown, William Henry. Organic Chemistry. Belmont, CA: Brooks/ Cole Cengage
Learning, 2009. Print.
Levine R, inventor, 1979 May 22. Continuous process for dehydration of tertiary
butyl alcohol

Questions?