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Catalyzed dehydration of t-butyl alcohol

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xxx: Chemical Engineering Laboratory

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Experiment performed: xxx
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Abstract:
This lab examines the catalyzed dehydration of t-butyl alcohol (tBA) to isobutylene. This
reaction is paramount to industrial applications and the catalyst is a widely used ion exchange
resin. tBA was reacted with various concentrations of water and methylcyclohexane, an inert
diluting agent, to examine reaction rate under varying conditions. The catalyst is inhibited by the
presence of water. As such, the reaction rate sharply declines with the addition of small amounts
of water, before reducing the catalyst activity to negligible amounts. Furthermore, water is a
product of the reaction, so the reaction rate can be seen to decrease gradually over time. The
initial reaction rate peaks with pure tBA at 7.5 (mol isobutylene/mol –SO3H s). The reaction rate
declines steadily upon dilution with MCH, and very sharply upon dilution with water. Reaction
rate data is fit to a Langmuir-Hinshelwood model for reaction kinetics using non-linear
regression methods. Empirical data is compared to literature values from similar experiments.
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Table of Contents:
Introduction.............................................................................................................................Page 4

Theory.....................................................................................................................................Page 5

Experimental methods.............................................................................................................Page 6

Results.....................................................................................................................................Page 8

Discussion.............................................................................................................................Page 11

Conclusion.............................................................................................................................Page 13

Nomenclature........................................................................................................................Page 14

References.............................................................................................................................Page 15

Appendix...............................................................................................................................Page 16
a).................................................................................Sample calculations and matlab code
b).............................................................................................................................Raw data
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Introduction
Isobutylene is an important intermediate in the production of gasoline additives.
Isobutylene can be reacted with alkyl alcohols to produce valuable ethers that act as gasoline
oxygenators [7]. The production of isobutylene is accomplished via a catalyzed dehydration of t-
butyl alcohol. An ion exchange resin is used to catalyze the reaction: sulfonated poly(styrene-
divinylbenzene) [3].
The catalyst used in the experiment is inhibited by the presence of water. In order to
prepare for the experiment, the catalyst is dried in a vacuum oven to eliminate interference from
ambient moisture conditions. Water is a product of the reaction, and so the activity of the catalyst
as the reaction proceeds. Several trials of the reaction are carried out with varying initial
concentrations of water and t-butyl alcohol in order to characterize how the activity of the
catalyst depends on initial conditions. Methylcyclohexane (MCH) is used as an inert solvent to
dilute the concentration of t-butyle alcohol. A paper by Gates and Rodriguez [2] was used to
determine the concentrations to be used for each trial. The concentration of t-butyl alcohol varied
from 0-10 moles per liter. Experiments where water was added to the reaction vessel, the
concentration was primarily centered near 9 moles per liter of t-butyl alcohol. Experiments
diluted with MCH were evenly spaced from 0 to 10 moles per liter of t-butyl alcohol.
In order to determine the reaction rate given specific initial conditions, the rate of
production of isobutylene was measured incrementally throughout each experiment. The reaction
vessel was set up such that evolved isobutylene gas could escape through a graduated burette.
The product can be measured directly and plotted as a function of time.
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Theory
The reaction is assumed to be appropriately modeled by Langmuir-Hinshelwood (L-H)
kinetics. The L-H model can characterize the reaction kinetics and allows us to examine limiting
cases in terms of concentration to identify relevant parameters.
The overall governing equation:
kK A C A
rA= γ
+ k' C A
1+ K A C A +( K W C W ) Eq 1
As part of a limiting case, at high water concentration, the rate simplifies to: [2]
'
r A =k C A Eq 2
At the opposite limiting case, water acts as an inhibitor at low concentrations. The
governing equation becomes: [2]

kK A C A
rA=
1+ K A C A +( K W C W ) γ Eq 3
L-H model has the following assumptions [5]:
 The surface is perfectly flat plane and homogeneous.
 The adsorbing gas adsorbs into an immobile state.
 All reaction sites are equivalent.
 Each site can hold at most one molecule of a (mono-layer coverage only).
 There are no interactions between adsorbed molecules on adjacent sites.

Isobutylene is assumed to be an ideal gas. The molar volume can be computed from the
ideal gas law. The reaction rate is converted from measured values of volumetric flow rate, this
gives the reaction rate as:
PQ
rA=
RTmCat s Eq 4
The reaction rates must be normalized to some temperature to be compared and analyzed
effectively. The temperature dependence of the rate constant is described by the Arrhenius
equation, with a given activation energy of 18 kJ*mol-1 [1]:
E 1 1
k=Fref exp [− ( − )]
R T T ref Eq 5
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Experimental Methods:
In preparation for the experiment, 20 samples of the
commercial catalyst were prepared the day before. Each sample was
weighed and placed into a vacuum oven, see Fig. 1, to remove as
much water as possible from the samples. At the start of each trial,
the samples were removed from the oven and quickly weight and
added to the reaction vessel. This is done with speed to prevent
moisture from the air from diffusing into the dry catalyst.
Two reaction vessels are set up within a fume hood. Each
reaction vessel is comprised of a heater, a round-bottomed flask, a
condenser, and a burette; see Fig. 2. The condenser allows for any tBA, MCH and water to boil
and completely condense back into the reaction vessel. Any
Fig. 1: vacuum oven
isobutylene evolved can escape the reaction vessel, as its boiling
point is much higher than the reagents. For each trial, the reagents
are heated until reflux is achieved before the catalyst is added to the
reaction vessel. As gaseous isobutylene is produced, it flows through
the condenser and through the burette. A soap bubble was placed
over the opening, allowing us to measure the volumetric flow rate of
isobutylene. The flow rate and temperature were measured on
regular intervals throughout each trial.
Sixteen trials were run in total; the various concentrations can
be seen in Table 1. All trials took place within a fume hood to
prevent inhalation of volatile gases. Before each trial, the flasks are
cleaned and primed with acetone, to remove impurities and water from the vessel. For each trial
the total volume of all the reagents is 200mL. The relevant volumes of tBA, MCH, and water are
added to the round-bottom flask. A magnetic stir bar was used to
Fig. 2: Reaction vessel
keep the reagents homogeneous in the flask.
In order to perform the analysis, an equivalent number of active sites per gram of catalyst
was needed. We performed a titration experiment to determine the number of –SO3H groups. 1
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gram of the catalyst is placed into an Erlenmeyer flask with 200mL of standard 0.1-N NaOH in
5% wt NaCl solution [3]. The solution is allowed to sit overnight. The supernatant fluid is
decanted off and back-titrated with standard 0.1M HCl. This allows us to express reaction rates
in terms of (mol of isobutylene produced)/(mol of catalyst -SO3H groups of catalyst · s).

Table 1: Solution Concentrations

Tria tBA (mL) H20 (mL) MCH tBA Concentration

l (mL) (mol/L)

1 200 0 0 10

2 172 0 28 8.6

3 150 0 50 7.5

4 130 0 70 6.5

5 115 0 85 5.75

6 95 0 105 4.75

7 75 0 125 3.75

8 55 0 145 2.75

9 15 0 185 0.75

10 190 10 0 9.5

11 185 15 0 9.25

12 180 20 0 9

13 175 25 0 8.75

14 170 30 0 8.5

15 165 35 0 8.25
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Results:
Reaction rate data was fit to the
equation[1]:
kK A C A
rA= γ
+ k' C A
1+ K A C A +( K W C W )

Using non-linear regression methods

Table 1: Regression parameters

Gamma k KtBA Kw k’
1 8±8 2±9 1.9±0.6 0.17±0.02
2 15±4.9 0.10±0.46 0.07±.04
3 17±4 0.083±0.03 0.0845±0.02

For the trial with an initially pure

concentration of tBA, the reaction rate can be seen
as a function of time in Fig. 3. There is noise in
the data,Initial
however, the reaction
reaction rates canrate can be seen
be plotted as a to
decrease of
function steadily over time. As
the concentration of the concentration
tBA. From this,
of water
we increases
can gather in the vessel,
information aboutthe
thereaction
reactionrate
decreases.
kinetics for the experiment. Fig 4. shows the initial reaction rates as a function of tBA
concentration only for trials with MCH mixtures. Fig 5. Shows initial rates for trials with water
mixtures. Reaction rate data is taken from each trial and extrapolated to find the initial rate. The
tBA concentration represents the initial conditions within the reaction vessel. All reaction rates
are normalized to 80˚C using the method outlined in the Honkela et al. paper.
Fig 3. Rxn rate vs. time
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Reaction rate as a function of tBA concentration for MCH mixtures. The data shows
good agreement with examples in the Gates and Rodriguez paper [2]. The reaction rate increases
steadily as the tBA concentration increases.

Fig 4. Reaction rate vs. time: MCH mixture

Reaction rate as a function of tBA

concentration for water mixtures. The
reaction rate decreases sharply as the
concentration of water increases. Once the
water has reached a saturated
concentration, around CtBA=9, the reaction
rate declines steadily in a near linear
fashion. This also shows good agreement
with the Gates and Rodriguez paper [2].

A titration was performed to

Fig 5: Reaction rate vs time: water mixture
determine the number of active sites per
gram of catalyst.
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This conversion allowed us to express calculated reaction rate values in terms of (moles of
isobutylene per mol active site per second).
S=0.00503 ± 2e-4 (mol –SO3H/gcat)
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Discussion:
Sixteen trials were run in total; each with varying initial concentrations. The water was
used to examine how the presence of water affects the catalyst activity. MCH is an inert solvent
that was used to reduce the concentration of tBA to examine how concentration affected the
reaction rate and catalyst activity. The literature results in a paper by Gates and Rodriguez were
used as a comparison for emperical results. Their experimental methods clostly aligned with
those of our experiment, and could be compared directly.
The reaction rate fit equations are based off of Langmuir-Hinselwood kinetics. Limiting
cases are used to determine several of the parameters for the model; non-linear regression
techniques are used to determine the remaining parameters. For instance, at near pure
concentrations of tBA, the adsorption of water can be considered negligible, and the reaction rate
equation simplifies substantially, easing the calculation of a reaction rate constant. The limiting
cases are a good approximation of the actual reaction kinetics that greatly simplify the
calculations.
Upon examination of the reaction rate data, we can see that the presence of water, even in
small amounts, greatly reduces the activity of the catalyst. For commercial processes, such as
methyl-t-butyl ether (MTBE) production, precautions must be taken to control the amount of
water in the system. If a high yield is desired, proper preparation and operating conditions must
be met to control the reaction rate. Additionally, the system must be monitored to detect
abnormalities in the reaction rate, which could indicate the precense of water, or other inhibitors.
From Fig. 3-5, we can see that there is a great deal of noise in the reaction rate data. The
operating conditions within the lab are a hugh factor to limiting our accuracy. The experiment
was conducted under a time constraint with limited resources. Reaction vessels had to be
dismantled, cleaned, primed, and refilled before every trial. Each trial was run for approximately
30 minutes; with data recorded every 1-2 minutes. Reaction rate data was recorded via a soap-
bubble flow meter. The accuracy limitations of the equipment used had the potential to
contribute significant error to the results.
Built-in functions in MATLAB were used to perform the non-linear regression to fit the
reaction rate data. These functions output very large errors, on the order of ~50-100% of the
calculated parameter. This indicates that the complexity of the system limits the accuracy of the
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fit. This is further evidence that limiting cases must be applied to reduce the complexity of the
equations and increase accuracy for all calculations.
Error for the calculated reaction rate data is approximately ±0.024%. This indicates that
reaction rate measurements were consistence and precise. Given this small error, and the close
correlation between calculated data and the literature results, we can conclude that the data
collected is accurate and gives a good representation of the reaction kinetics for this system.
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Conclusion:
The commercial ion exchange resin used gives us insight into the application for these
reactions in industry. The catalyst has the potential to greatly increase the reaction rate and yield
the desired isobutylene with high purity. The presence or absence of water has a very drastic
affect on the system, it allows us to examine limiting cases with the reaction kinetics. After the
tBA concentration falls below 8M in water mixtures, the activity of the catalyst is negligible and
the reaction rate emulates power-law type kinetics. In MCH mixtures, the reaction rate can be
modeled to Langmuir-Hinshelwood type kinetics, which were used in the non-linear fit to
identify relevant parameters. MCH was used as a diluting agent to examine the reaction rates’
dependence on concentration of tBA. The initial reaction rate can be seen to decrease fairly
steadily with a decrease in concentration. This allowed us to identify the significance of
adsorption and the specific kinetics, and fit the data to a model equation.
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Nomenclature:
CA = tBA Concentration (mol/L)
CW = H2O Concentration (mol/L)
k = reaction rate constant [mol/(mol of catalyst – SO3H groups)]
k’ = pseudo, 1st order reaction rate constant [L/mol of catalyst –SO 3H groups) s] for water
mixtures
KA = adsorption constant for tBA (L/mol)
KW = adsorption constant for water (L/mol)
mcat = mass of catalyst
MCH = Methylcyclohexane
MTBE = methyl-t-butyl ether
rA = reaction rate [mol/mol of catalyst – SO3H groups) s]
s = Conversion factor [mol of catalyst –SO3H groups/g of catalyst]
tBA = t-butyl alcohol
Tref = reference temperature
γ = power in empirical rate equation, integer values of 1, 2, and 3
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References:
[1]. Honkela,*, M., Ouni, T., & Krause, A. (2004). Thermodynamics and Kinetics of the
Dehydration of tert-Butyl Alcohol. KINETICS, CATALYSIS, AND REACTION
ENGINEERING,43(15), 4060-4065.
[2]. Gates, B. (1973). General and specific acid catalysis in sulfonic acid resin. Journal of
Catalysis, 31, 27-31.
[3] “Kinetica of catalytic dehydration of t-butyl alcohol in a semi-batch reactor” UC Davis, Dept
of CHMS, winter, 2015, web.
[4]. Kumar, K., Porkodi, K., & Rocha, F. (2007). Langmuir–Hinshelwood kinetics – A
theoretical study. Catalysis Communications, 82(9), 82-84.
[5]. Masel, Richard (1996). Principles of Adsorption and Reaction on Solid Surfaces. Wiley
Interscience. p. 240. ISBN 0-471-30392-5.
[6]. Metzner, A.B., Lashmet, P.K., and Em-Reich, J.E., “Actes du deuxieme Congres
International de Catalyse,” pp. 735-47, Ed. Technip, Paris, 1965.
[7] "Tert-Butanol | C4H10O - PubChem." Tert-Butanol | C4H10O - PubChem. N.p., n.d. Web.
02 Mar. 2015. <http://pubchem.ncbi.nlm.nih.gov/compound/6386?from=summary>.