Critical analysis of the article:

Efficient continuous production of ionic liquids in a loop reactor

Experimental and theoretical studies for the example of 1-ethyl-
3-methylimidazolium ethyl sulphate

Universidad de Antioquia
Departamento de Ingeniera Qumica

Resumen.

El anlisis crtico en los estudios realizados alrededor del mundo junta los conceptos de varias
disciplinas cientficas con el objetivo de realizar investigaciones complementarias y dar ventajas
del conocimiento obtenido a cualquier persona que est trabajando en el mismo campo cientfico o
que tenga un inters en el tema. El artculo efficient continuous production of ionic liquids in a
loop reactor-Experimental and theoretical studies for the example of 1-ethyl-3-methylimidazolium
ethyl sulphate muestral que tan importante es tener todos los conceptos relacionados a los
reactores y los parmetros de cintica de reaccin claros, para poder disear y optimizar procesos
existentes o desarrollar nuevos procesos lo cual va a hacer una contribucin a la industria y a la
sociedad.

Abstract.

The critical analysis on the studies being made around the world brings together different scientific
disciplines with the objective to make complementary research and give the advantage to make use
of the knowledge obtained while writing an article, to anyone working on the same scientific field
or is interested in the topics discussed in the study. The article efficient continuous production of
ionic liquids in a loop reactor-Experimental and theoretical studies for the example of 1-ethyl-3-
methylimidazolium ethyl sulphate shows how important is to have all the concepts related to the
reactor and kinetics reaction parameters clear, and be able to design and optimize current
processes or developed a new process that is going to make a contribution to the industry and the
society.

Key words: ionic liquids,


Introduction

[1] Ionic liquids are growing great interest in
the scientific community for their unique
properties, such as: negligible low vapor
pressure, thermal stability and catalytic
activity among others; for all this reasons is
of great importance to developed processes
that can yield the growing demand and being
economically available to the industry, so
they can be incorporate them to processes
and make them highly profitable.
Continuous processes involving ionic liquids
synthesis have being published for the last
five years but they involved the use of
microreactors or other high manufacturing
cost equipment, that even with optimum
conditions the production rate is very
limited, due to the high release during the
reaction a temperature control is essential
prevent discoloration or thermal
decomposition.
In previous work, theoretically, has been
shown that the use of a loop reactor with
product recycle could be an alternative
option to the production of 1-ethyl-3-
methylimidazolium ethyl sulphate and other
ILs (ionic liquids) with a higher production
rate that the conventional methods.
Analysis
a. Identify the problem that the article is
trying to solve.

The article is trying to develop a process for
the synthesis of 1-ethyl-3-
methylimidazolium ethyl sulphate and others
ILs with a higher production rate than the
known processes.

b. Establish the objectives of the article.

Use a loop reactor with product recycles
to be able to synthetize 1-ethyl-3-
methylimidazolium ethyl sulphate.

Get the kinetics reaction parameters for
the synthesis of 1-ethyl-3-
methylimidazolium ethyl sulphate.

Optimize the parameters involved in a
loop reactor, such as the recycle ratio.

Simulate the process to get the
temperature profiles along the reactor.

Increases the production rate of 1-ethyl-
3-methylimidazolium ethyl sulphate
synthesis using a loop reactor with
product recycle.

c. Describe with details the procedure that
the article follows to reach the propose
objectives.

i) Considerations of a loop reactor for fast
exothermic reactions (figure 1):

Increase of the recycle ratio (R) leads to
a lower adiabatic temperature rise, hence
for a value of R, the inlet temperature
can be adjusted.
Recycle decrease the reactants
concentration, which decrease the
reaction rate.
The loop reactor is much less expensive
than other continuous reactors.

ii) Determination of the design equations:

For the reaction rate, Eq. 1, was presumed a
first order reaction respect to both reactants.

For an isothermal tubular reactor and
equimolar ratio of the reactants A and B, the
conversion for a given residences time is:

Also for the initial reactant concentration at
the reactor entrance is given by:

The mean temperature (assuming 100%
conversion is given by:

Figure 1. Process flowsheet of the adiabatic tubular flow reactor


For a constant flow rate of fresh feed using
Eq. 3 y 4 the volume reactor relative to the
volume without recycle can be related to the
recycle with Eq (5).

(5)

)(

iv). Experimental set up and procedure.

A loop reactor was built based on
simulations previously made, the reactor
possess an inner tube diameter of 21mm and
length of 600mm, sampling valve was
installed at the reactor outlet.

The reaction rate constant was determined
by nuclear magnetic resonance (NMR),
assuming a first order reaction with respect
both reactants, experimental data was fitted
to the rate equation to get the rate constants.

v). Modeling.

The equations for mass and energy balance
for steady state, Eq. 6 and 7, were solved
simultaneously using Presto Kinetics.

(7)
vi). Results analysis.

With the results from the experimental data
and the simulation made, it was determined
the optimal operational conditions for the
loop reactor

d. Are all the objectives propose in the
article fulfill? Explain, identify and
describe the figures, tables and/or
sketches which are used to verify the
fulfillment of the objectives.

Graphing Eq. 5 for values of the activation
energy of 60, 80 and 100 kJ/mol, it was
found out form figure 2, an optimum
minimum at around 2 , it can be seen that
the rising of the mean temperature have a
great influence on the fast decreasing
behavior at the beginning of the curves.

Figure 2. Requiered reactor volume relative to
the volume without recycle to reach 99%
conversion.


With NMR technics it was possible to make
measurement of the concentration at different
times to be able to get the kinetics rate constants
at a given temperature, the data obtained is
shown in figure 3, these data was fitted by
numerical means and it was calculated
k(0C)=1.37x10
-7
m
3
mol
-1
s
-1
.


Figure 3. Concentration of 1-methylimidazole vs
reaction time at 0C

As it was mention before the temperature control
is very important to prevent discoloration or
thermal decomposition, to have a first
approximation of the temperature profile
inside the reactor it was simulated the
solution of Eq. 6 and 7 using the data in
table 1, as it can be seen from figure 4 the
temperature rises as increase the position on
the reactor, which was expected due to the
highly exothermic reaction.

Table 1. Model parameters for the simulation.




Figure 4. Temperature profile in the loop
reactor vs normalized length.

Figure 5 shows the Arrhenius diagram
fittings for different references and the
measurements made by NMR, the values
obtained by NMR are in good agreement to
the ones reported in the literature.



Figure 5. Arrhenius diagram of [EMIM]
[EtSO
4
] synthesis.

Figure 6 shows experimental results and
simulation profile of the temperature vs
position in the reactor, if an overall heat
transfer coefficient of 4 W m
2
K was used to
consider the deviation from the ideal
adiabatic behavior made a better agreement
with the experimental data, in table 3 are
given the conversions of diethyl sulphate
(DES) at different reaction conditions


Figure 6. Comparison of experimental data and
simulation.

Table 2. Measured and calculated conversion of
DES.



e. What subsequent studies will you
propose to the authors?

I think a good subsequent study will be
involving potential packing materials for the
loop reactor to increase production rate
and/or optimize some others parameters.

Experimental data to obtain kinetics rate
constants of ILs, because there is just few
information about this substances.

The use of a semi-batch reactor to control
the temperature reaction and compare the
conversion under various conditions with the
obtained in the article.

f. What other articles besides the
referenced by the authors, have reported
on similar topics? Include a summary of
two articles, point out the similarity and
differences of the selected articles with
the analyzed article.

1. Scalable synthesis of ionic liquids:
comparison of performances of
microstructured and stirred batch reactors
[2].

In this article are comparing the performance
of reactors commercially used to synthetize
ILs, The reaction performs better in MSR for
shorter duration time and lower temperature,
but because of the better
conversion/selectivity of the Hex/MSR in
comparison with the batch reactor, the
quantity of organic solvents required for
purification of IL is strongly minimized and
the process of synthesis significantly
improved as shown in figures Figures 7 and
8.

Figure 7. Conversion rate at different
temperatures vs reaction duration


Figure 8. Conversion rate at different
temperatures vs residence time


2. Brnsted imidazolium ionic liquids:
Synthesis and comparison of their catalytic
activities as pre-catalyst for biodiesel
production through two stage process

In this article the use of ILs as catalyst in the
production of biodiesel is being test it, and
evaluated as potential catalyst at industrial
level and they come to the conclusion that
besides, their high stability, easy product
isolation and environmentally friendly, the
properties of the produced biodiesel revealed
that Brnsted acidic ILs have potential as
catalysts in the production of biodiesel.

Both articles relate with the one being
analyzed with the study of ILs as potential
materials, and as a consequence the need to
create processes with ILs are being
developed, and one important equipment in
the process us the reactor, thus the
understanding on reactor designing and all
the parameters involved is a key component
to select the most fitted equipment for each
developed process.



g. What aspects related to the chemical
reaction engineering class did you
identify in the article? Explain, Identify
the chapters or specific subjects.

Subjects used to model the loop reactor.

* Mole balances, reaction rate (session 1)
* Conversion (session 2)
* Reaction rate constant, reaction order
(session 4)
* Isothermic reactor design (session 7)
* Tubular reactors, piping pressure drop
(session 8)
* Session 11 y 12 were necessaries to find
the value of the rate constant
* Energy balance (session 19)
*Continuous flow reactor no isothhermic
(session 20)
*residence time (session 23)

Exercise

Using the data given in the article find the
conversion that could be achieve using a
CSTR and a PFR reactors with the same
volume used for the loop reactor (assuming
isothermal reaction)

Initial conditions:

The volume of the loop reactor is

The reaction is given by



CSTR

Using the function fzero from MatLab the
the conversion was calculated, giving a
value of:



PFR

Conclusions

The analysis of articles helps us to
comprehend subjects previously learned
from a practical point of view.

It is very important to make sure that the
objectives and results made in article are
consistent with the problem that the article is
trying to solve.

The understanding of the modeling and
assumptions made in articles helps us to get
a better idea of the correct assumptions that
can be applied for an specific process, thus
the design or the simulation of the process is
a close representation of the reality.

The information contained in articles is very
valuable and is very important to do a
complete research through all the available
databases when realizing a project to have
all the information about the subject and see
if the study has not been done yet.
References

[1] Willmes S., Jess A. Efficient continuous
production of ionic liquids in a loop reactor
Experimental and theoretical studies for the
example of 1-ethyl-3-methylimidazolium
ethyl sulphate. Chem. Eng. J. 222,198-208
(2013)

[2] Hicham Iken, Frdric Guillen, Hlne
Chaumat, Marie-Rose Mazires, Jean-
Christophe Plaquevent, Thodore Tzedakis,
Scalable synthesis of ionic liquids:
comparison of performances of
microstructured and stirred batch reactors,
Tetrahedron Letters, Volume 53, Issue 27, 4
July 2012, Pages 3474-3477, ISSN 0040-
4039, 10.1016/j.tetlet.2012.04.119.

[3] Y.A. Elsheikh, Zakaria Man, M.A.
Bustam, Suzana Yusup, C.D. Wilfred,
Brnsted imidazolium ionic liquids:
Synthesis and comparison of their catalytic
activities as pre-catalyst for biodiesel
production through two stage process,
Energy Conversion and Management,
Volume 52, Issue 2, February 2011, Pages
804-809, ISSN 0196-8904,
10.1016/j.enconman.2010.08.005.