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Study of Esterification Reactions in a Batch Reactor:

Modeling the Industrial Synthesis of Benzoic Acid and Biodiesel

Chida Balaji Brett Levine Shirin Poustchi


chidabalaji@gmail.com levine.brett@gmail.com spoustchi@msn.com

Abstract
This experiment examines two esterification reactions: the de-esterification of
ethyl benzoate into benzoic acid and the transesterification of palm oil into biodiesel.
Through the de-esterification of ethyl benzoate, we mimicked the processes and
experimental designs that are involved in the production of API’s (active pharmaceutical
ingredients). The transesterification of palm oil allowed us to observe the production of
biodiesel on a small scale. In a 1L batch reactor at 40oC and 0.25 ethanol mole fraction,
the rate constant was experimentally found to be 0.47 M-1s-1. This value is important in
that it tells us the rate (speed) of the reaction under the given conditions and compares
favorably with the literature value of 0.51 M-1s-1 [2]. For the biodiesel reaction, we
successfully produced biodiesel in a 1L batch reactor with a percent yield of 23% at
60oC.

Introduction group to/from a molecule. Esters are a


The demand for pharmaceuticals type of molecule formed from an organic
is increasing; consequently, the need for acid and an alcohol and have the general
efficient production designs is vital to structure of R-CO-OR’. Ester molecules
the success of the pharmaceutical exist in a variety of forms, ranging from
industry. By studying the synthesis of naturally occurring esters such as
APIs, chemical engineers are striving to vegetable oils to commercially prepared
discover new ways to optimize the products such as biodiesel.
efficiency of these valuable reactions. Commercially, esters are very
Although API synthesis covers a prevalent and a valuable resource to
multitude of chemical reaction types, our many industries, especially the
research focused on one specific reaction pharmaceutical industry. Many APIs, or
type: esterification. active pharmaceutical ingredients, are
As with pharmaceuticals, the formed in esterification reactions (ex.
petroleum industry is constantly Aspirin). Without these quintessential
searching for new ways to increase their ingredients, the medical and
productivity. Additionally, these pharmaceutical industry would not be
companies are actively pursuing viable where it is today. Furthermore, it is of
and renewable alternative energy sources great importance to continue to study
as a result of the decreasing fossil fuel and understand how these esterification
reserves, which include wind power, reactions work so engineers and other
solar power, and the focus of our second professionals can continue to produce
experiment: biodiesel. products that will further benefit
Esterification reactions involve mankind.
either adding (transesterification) or Commercially, these reactions
removing (de-esterification) an ester take place in very large batch reactors.
These specially designed vessels are There were two forms of objectives set
often tailored to the reaction taking to accomplish the goals of this project:
place, and provide a closed system that the first being quantitative and the
can often easily be controlled by a second being qualitative. The
computer. These reactors also have the quantitative objectives of this research
ability to control temperature, reactant were:
concentrations, and many other things • Calculate the rate constant value,
such as pressure and pH depending on k, (ethyl benzoate reaction)
the specific reactor involved. [1] • Calculate the % yield (biodiesel
Carefully analyzing past experiments reaction)
enables chemical engineers to make The qualitative objectives were:
changes to the reactor conditions that • Carry out a model de-
would make the reactions more efficient esterification reaction using ethyl
and effective. benzoate
• Carry out a model
transesterification reaction using
palm oil (to produce biodiesel)
• Analyze the above small-scale
reactions to serve as a model for
industrial production

The rate constant, k, describes how


quickly the reaction proceeds (measured
by the change in concentration of the
reactants with respect to time). The
percent yield is a measure of how much
Figure 1: The Batch Reactor product was produced in relation to the
Above is a picture of the 1L batch reactor used in predicted yield (from stoichiometry).
both experiments. The outer layer of the reactor Although both reactions were
is a water jacket with a dedicated temperature quantitatively analyzed, our study of
probe that constantly monitors the reactor’s these reactions was mostly qualitative.
temperature.
The quantitative measures simply serve
to gauge our accuracy in comparison to
This paper analyzes two different
others who have completed similar
esterification reactions. The first, the de-
experiments. This paper does not strive
esterification of ethyl benzoate into
to find ways to maximize the efficiency of
benzoic acid, serves as a model for the
these experiments; it simply strives to
synthesis of APIs in batch reactors. The
model the nature of esterification
second, the transesterification of palm
reactions.
oil into biodiesel, offers a source of
renewable and clean alternative energy.
Background
The purpose of both experiments is to
De-esterification of Ethyl Benzoate
simply study esterification reactions,
The first reaction involved the de-
both transesterification and de-
esterification of ethyl benzoate to
esterification, and how to conduct both
benzoic acid. De-esterification reactions
experiments in a way that models their
typically involve hydrolysis, where
industrial production.
water cleaves a molecule (ethyl amount of desired product in the
benzoate) into its respective alcohol smallest amount of time.
(ethanol) and acid (benzoic acid).
Typically (and as with our experiment), The calculations for the biodiesel
these reactions take place with a basic percent yield are relatively simple when
catalyst (NaOH). compared to those for the ethyl benzoate
reaction.
The differential rate law for this
reaction is:
R = k[EB]2
Figure 2: Ethyl Benzoate Reaction [1] (Where EB represents Ethyl Benzoate)

Equation 1: Differential Rate Law


The product of this reaction,
benzoic acid, has several important uses
By taking the integral of both sides of
in consumer products. Benzoic acid is
this equation, we obtain the integrated
primarily used as a food/drink
rate law, which is what we used in the
preservative and has been shown to
experiment:
inhibit the reproduction of mold and
yeast molecules. [EB] = [EB]0
As previously mentioned, this 1+[EB]0kt
reaction serves as a model for the
synthesis of APIs in a batch reactor
Equation 2: Integrated Rate Law
similar to the one we used. In the
chemical engineering world, measures
We also know that [EB] at time t is
such as yield (how much of the product
equal to the concentration of EB at t=0
is created compared to the theoretical
minus the concentration of the acid used
yield) and speed are of great importance.
to quench it:
Pharmaceutical companies want to be
able to manufacture the APIs they need
for their medicine; however, they also [BA] = [EB]0 – [EB]
want to make the reactions as efficient as
Equation 3 (where BA represents Benzoic Acid)
possible.
The speed and yield are
By substitution, we get:
influenced by a variety of conditions,
mainly mole fraction (the relative
composition of the reactant mixture) and [EB]0 – [HCl] = [EB]0
temperature for the two reactions studied 1+[EB]0kt
in this experiment. Most esterification
Equation 4
reactions are reversible, which means
Solving for k:
that often the reactions are not complete
(the actual yield is less than the
k = [BA]
theoretical yield). This is where
[EB][EB]0t
chemical engineers use their knowledge
and experience to optimize the reactions
Equation 5
such that they yield that maximum
The results of this study offer valuable
This equation can be further simplified insight into the production of biodiesel
by: and introduce it as a valuable and
renewable alternative energy source.
k= [BA]
([EB]0 – [BA])[EB]0t Method
Both reactions, the de-
Equation 6 esterification and transesterification,
took place in a 1L glass batch reactor.
The above equations, most importantly The reactor was surrounded by a water
the integrated rate law, allow us to jacket, which allowed us to carefully
calculate a value of ‘k’. regulate the temperature throughout the
progression of both reactions. The
Note that the [EB] = [OH]c in the reactor also had a temperature probe that
original mixture. Also note that this recorded the temperature inside the
reaction is considered irreversible. reactor (a separate probe existed for the
jacket), down to a tenth of a centigrade.
Transesterification of Palm Oil Additionally, the reactor contained an
While the de-esterification of inert stirrer on the bottom side which
ethyl benzoate isn’t especially practical, spun at a rate ranging from 0-500
the second experiment certainly is. As revolutions per minute (rpm). With any
the world’s reliance on fossil fuels reaction, a well-stirred reactor is needed
increase and the supply of these energy to properly evaluate the rate constant.
sources deplete, there is an increasing For the ethyl benzoate reaction,
necessity for an alternative and we calculated the rate constant first by
renewable energy source. Biodiesel, a continuously extracting samples from
blanket term for a combustible and the reactor. The composition of the
energy rich hydrocarbon chain, is samples was then analyzed using
produced by the esterification of palm filtration. Based on previous
oil (from palm trees) in the presence of experiments conducted by others on this
methanol and a catalyst. same topic, it was determined that this
reaction was second order with respect
to ethyl benzoate [2].
To experimentally determine the
rate constant, samplings of the reactor
mixture (which contained a mixture of
ethyl benzoate, sodium hydroxide,
Figure 3: Biodiesel Reaction [6] ethanol, and benzoic acid) were taken at
The end result of the reaction is an certain intervals of time. At specified
immiscible mixture of biodiesel and times, we took a small ~10 mL sample
other waste products including excess of the reactant mixture from the
methanol and glycerin. These parts can sampling tray. Immediately after, we
be effectively separated to leave high measured exactly 5.00 mL using a
purity biodiesel. micropipette and added that to 5.00 mL
Worldwide, biodiesel interest is of cold Hydrochloric acid. This
increasing due to the looming oil crisis. important step is referred to as
quenching, which means we used the batch reactor such that they could be
HCl to effectively stop the reaction in heated to the desired temperature before
the sample that we took. As soon as the adding the final ingredient: palm oil.
HCl was added, the time was recorded. Note that NaOH was added in pellet
After agitating the sample form instead of solution form purposely
solution in a vortex, it was taken over to to prevent any water from entering the
the titrator. The titrator used 0.10N reactor. When water is present, de-
sodium hydroxide to titrate the benzoic esterification takes place via hydrolysis
acid in the sample solution that was (and forms soap), which is exactly what
formed in the reaction. we do not want to happen [1]. Once this
temperature was reached, the palm oil
was added and the reaction began.
The following day, we returned
(with the assumption that the reaction
was finished), and turned off the stirrer.
The hydrophilic and denser glycerol
migrated to the bottom of the reactor
while the less dense biodiesel rose to the
top. Using a peristaltic pump, we slowly
extracted the biodiesel layer into an
Erlenmeyer flask.
Figure 4: The Titrator

Solver, an Excel application,


compared the actual concentrations at
each respective time to the theoretical
concentrations as proposed by the
second order rate law. Solver used the
non-linear least squares regression test in
order to minimize the sum of the squares
of the errors to calculate ‘k’ [5].
The experiment with the biodiesel
involved simply determining the percent Figure 5: Separation of Layers
yield, which compared the actual amount (Formation of Biodiesel)
of biodiesel formed with respect to the
amount dictated by stoichiometry [1]. Next, we used a vacuum filtration
Ideally, we would have liked to study the system to filter out some of the glycerol
kinetics of the biodiesel reaction; waste products that collected in the
however, by using palm oil it is interphase of the mixture and thus were
extremely impractical and difficult. extracted into our biodiesel mixture.
Palm oil is a conglomerate of about five The product of this filtration was then
different hydrocarbons, which makes it taken to the evaporator, which further
nearly impossible to write a rate law purified the biodiesel by evaporating any
(which is needed to calculate ‘k’). methanol, glycerol, or other volatile
First, methanol and dry sodium products that were in the biodiesel
hydroxide (NaOH) were added to the solution. From here, the volume of the
biodiesel was taken and converted to a Results
mass using the density of biodiesel and De-esterification of Ethyl Benzoate
thus the yield was calculated. The concentrations of the ethyl benzoate
experiment are shown below:
The
processes we Time(min) [BA] [EB] Predicted
used in our 0.00 0 0.1 0.1
5.38 0.029 0.071 0.080
experiments
16.23 0.059 0.041 0.057
are ones that 31.97 0.052 0.048 0.040
are utilized in 44.90 0.056 0.044 0.032
a much larger 60.18 0.075 0.025 0.026
scale by 81.15 0.072 0.028 0.021
industries. 100.57 0.074 0.026 0.018
The batch Figure 7: Ethyl Benzoate Data
reactors
easily Solver minimized the difference of the
Figure 6: Evaporator allowed us to squares between the actual and
replicate the theoretical values to calculate a k value
esterification reactions that are of 0.47 M-1s-1 . Again, ‘k’ describes how
performed by large-scale industries. [1] fast the concentration of the ethyl
One of our objectives was to analyze the benzoate decreases with respect to time.
reaction mechanisms for the de-
esterification of ethyl benzoate to
benzoic acid. This was accomplished by
evaluating the second-order rate
constant, k, through analysis of the de-
esterification reaction. The rate
constant, k, is affected by temperature,
concentration of ethyl benzoate, and the
ethanol mole fraction. Through the
analysis of the reaction mechanisms of
Figure 8: EB concentration vs. time
the formation of benzoic acid we gained
information that we can apply to the
The above graph plots the concentration
production of different APIs.
of the ethyl benzoate with respect to
time. The solid line shows the expected
concentration versus time according to
the second order integrated rate law.

Transesterification of Palm Oil


For the biodiesel reaction, the
main indicator was the percent yield.
According to stoichiometry, 440 grams
of biodiesel should have been produced
given the initial concentrations and
volumes. In reality, we produced 92.8
grams of biodiesel (115 mL) which
yields a density of 0.81 g/mL. The calculating the rate constant at different
actual density of biodiesel ranges from temperatures and ethanol mole fractions
0.86-0.90 g/mL. we can obtain the fastest means to carry
out the experiment. Faster processes &
92.8g biodiesel 1 mL =115 mL biodiesel better experimental designs in the
0.81 g synthesis of APIs can help make the cost
of essential drugs cheaper. Thus this
%Yield=Experimental=92.8 g = 21.1% research is applicable to pharmaceutical
Predicted 440 g companies that strive to make cheaper
drugs. The production of benzoic acid
gave us an insight into the efficient
The above calculations show the synthesis of APIs as well as the
determination of mass of the biodiesel mechanisms of a de-esterification
produced and its percent yield. Note that reaction. This area of research and work
the density of biodiesel depends on the is vital to the progress of pharmaceutical
exact composition of the triglycerides drugs and their effect on society.
used, which can not be determined Biodiesel was the chief focus of
definitively (the composition of the palm the second stage of our research.
oil is only given in percentage ranges of Biodiesel can be produced through many
the triglycerides). ways but the method we researched was
the transesterification of palm oil.
Discussion/Conclusions Through this experiment we tried to see
For the de-esterification reaction, we if biodiesel could be produced in a
obtained a rate constant of k=0.47 M-1s-1 productive way using the
at 40°C and 0.25 ethanol mole fraction. transesterification of vegetable oils. We
The rate constant was determined used 500 grams of palm oil and mixed it
through analysis of the decreasing with 450 mL of methanol and added 8.5
concentration of ethyl benzoate as the grams of NaOH pellets.
reaction progressed. The data that we Although the reaction was
gathered for the concentration of ethyl inefficient, it is the most practical
benzoate was slightly skewed from the method of producing biodiesel for
predicted values because of problems commercial use [3]. The ingredients for
with the experimental apparatus. biodiesel production are relatively
Specifically, the micropipette, which is cheap, and thus biodiesel can become a
supposed to measure exact volumes, had viable alternative to more expensive
a slight crack that was discovered upon gasoline. Biodiesel has a lot of potential
completion of the experiment. This to become the primary fuel source of not
minor fault prevented the necessary just the nation but also the world [3].
precision that we needed and thus is Additionally, biodiesel has a less of an
certainly a source of error. environmental impact than conventional
The ‘k’ value that we calculated fuel sources. Biodiesel’s applications
corroborates with the literature value are growing from just vehicular use to
(0.51 M-1s-1) at the same conditions and domestic and industrial use. Research
ethanol mole fraction [2]. This into cheap and efficient synthesis of
experiment provides a means for us to biodiesel is pivotal to the resolution of
find ways by which to make the
the world’s energy crisis [3].
production of APIs more efficient. By
On the contrary, our research This graph shows the rate constants, k,
with the biodiesel helped us identify the throughout different ethanol mole
flaws of biodiesel and biodiesel fractions (x-axis) and temperatures. As
production. Primarily, biodiesel has a a general trend, the rate constant
relatively short shelf life and poor cold decreases with increasing ethanol mole
flow properties. Although the majority fraction and increases with increasing
of it is liquid, biodiesel forms small solid temperature. Additionally, varying the
clumps at room temperatures, which ethanol mole fraction has a more
diminishes its ability to flow. Currently, pronounced effect at lower temperatures
research is being performed by chemical (it is almost negligible at relatively high
engineers to optimize the flow rate of temperatures).
biodiesel by mixing it with different Due to time constraints, we only
solvents [4]. performed one experiment with the ethyl
benzoate (0.25 mole fraction, 40oC). We
Related Work gauged our accuracy by comparing our
Phillip Moseley and Mustafa Ohag experimental rate constant to the one
published a paper in 1997 dealing Moseley and Ohag calculated for the
directly with the thermodynamic same temperature and mole fraction.
functions of the alkaline hydrolysis of For the biodiesel production
ethyl benzoate into benzoic acid. experiment, we referred to a previous
Moseley and Ohag performed the same paper published by Invensys Foxboro, an
experiment (the de-esterification of ethyl engineering firm specializing in
benzoate) we did over 70 times, with commercial automation in terms of
ethanol mole fractions ranging from 0.1- production and manufacturing systems.
0.9 and temperatures from 5-45 The paper outlines the different
centigrade at 5 degrees intervals. A ways that biodiesel is manufactured,
chart of their results is included below: providing the following useful chart
which details a generic
transesterification reaction to produce
biodiesel:

Chart 2: Biodiesel production flowchart


Figure 9: Rate constant values for
[3]
Moseley’s experiment [2]
Note that biodiesel production is a
relatively cyclic process in that many of Acknowledgements
the byproducts can be We would like to thank the following
reprocessed/recycled back into the people without whom this experiment
reaction. Consequently, this is one of would not have been able to take place.
the main reasons that biodiesel is a First, the New Jersey Governor’s School
feasible alternative energy source. Board of Overseers for allowing the
Governor’s School of Engineering and
Future Work Technology to take place. Second, we
Being that our research project covered would like to thank Rutgers University
such a current issue (especially with the and Dean Don Brown. Next, we would
biodiesel reaction), there exists myriad like to thank Blase Ur, Program
possibilities for future work. The Coordinator, for not only arranging this
world’s oil reserves will only continue to research project, but also for planning
deplete, thus exacerbating the already this entire program, which has truly been
prevalent oil crisis. Additionally, the an invaluable experience. Additionally,
world’s reliance on oil products has we thank Dr. Henrik Pedersen, Chemical
severe environmental implications. Engineering Department Chair, for his
We could implement Moseley’s everyday guidance and breadth of
design for his ethyl benzoate experiment knowledge as our primary project
into our biodiesel experiment by using advisor. We also thank Patrick Nwaoko,
different initial mole fractions and our counselor advisor for his assistance
temperatures to measure the percent throughout this entire experience. Most
yield. This experiment would show importantly, we’d like to thank the
under which conditions the production following program sponsors who
of biodiesel is most efficient. sustained this Governor’s School
As with any experiment, program in a financially difficult year:
repetition breeds more accuracy and Prudential, Morgan Stanley, Rutgers
precision. Because of time constraints, University, the John and Margaret Post
we were only able to run the ethyl Foundation, and John and Laura
benzoate and biodiesel reaction once Overdeck. We finally thank the entire
each. In the future, it would be Governor’s School staff for their
beneficial to run each experiment again friendship and guidance regarding not
at the same conditions and furthermore only this research project but also the
at different conditions. These program as a whole.
experiments would add validity to the
experiment and offer a wider scope of
analysis on both reactions.
References

[1] – Pedersen, Henrik. The Batch Reactor.


[2] – Moseley, Phillip, and Mustafa Ohag. "Thermodynamic functions of activation of
the alkaline hydrolysis of ethyl benzoate and of ethyl p-nitrobenzoate in
ethanol–water mixtures of various compositions at different temperatures."
(1997).
[3] – "Guide to Instrumentation for Biodiesel Fuel Production." Invensys Foxboro
[4] – Levine, Brett. "Batch Reactor." E-mail to Michael Boczon. 15 July 2008.
[5] – Harris, Daniel C. "Nonlinear Least-Squares Curve Fitting with Microsoft Excel
Solver." Computer Bulletin Board. 15 July 2008
<http://jchemed.chem.wisc.edu/Journal/issues/1998/jan/abs119.html>.

[6] - http://en.wikipedia.org/wiki/Image:Generic_Biodiesel_Reaction1.gif