10.

492 Final Project

Reaction Intensification by Slug Flow
Date: December 11, 2002
Group Members: Joyce Chan, Christiane Gumera, Puriwana Pradipasena

Paper: The intensification of rapid reactions in multiphase systems using slug f

low in capillaries by J. R. Burns and C. Ramshaw, Lab on a Chip, 2001, Volume 1,
p 10-15.

Table of Contents:
1. Motivation 1
2. Fabrication Sequence 2
3. Experiments 2
4. Chemical Engineering Analysis 3
5. Modifications 5
6. Micro-systems vs. Macro-systems 8
7. Slug Flow vs. Parallel Flow in Micro-systems 9
Appendix A. Diffusion-Only Model vs. Model in Paper 10
Appendix B. Velocity profile in Slug 11
Appendix C. Copper(II)-Kelex Reaction 12
Appendix D. References 14

1. Motivation
The study of multiphase reactions in micro-reactors notes that greater focus has
been placed on gas-liquid reactions, with fewer studies having been done on imm
iscible liquid-liquid reactions. In each of these studies, different methods wer
e investigated for their ability to reduce the path length for diffusion, thereb
y increasing the mass transfer and the rate of reaction. The shearing motion in
slugs has long been known for being able to generate internal circulation during
slug flow even in large-scale applications.1 It is not unexpected that similar
behavior occurs in the microscale as well.
Diffusion-limited reactions are usually prone to runaway reactions and explosion
s in large-scale reactors. Thus, extrapolation calculations and numerous safety
measures are taken to prevent runaway reactions from happening. By varying certa
in parameters in slug flow, the rate of mass transfer can be controlled, and hen
ce the rate of reaction. Therefore, the performance of such high intensity react
ions can be increased while maintaining safety through use of slug flow micro-re
actors.
Another major concern of replacing a large-scale reactor by a micro-reactor, is
the throughput. It might not be economically feasible to use a micro-reactor if
the yield is orders of magnitudes lower than if a large-scale reactor was used.
One of the advantages of micro-reactors is that scale up is done by replication,
as opposed to increasing the size of process units like in the case of a large
scale process.
Reactions involving two immiscible phases are of great interest because of its w
ide applications. One of the applications is in phase transfer catalysis. A cata
lyst for an aqueous reaction may be completely soluble in organic phase, but onl
y sparingly soluble in the aqueous phase. By using the slug flow developed in t
his paper, the reactants can diffuse into the organic phase, form the product, a
nd then diffuse back to the aqueous phase again. Slug flow of two immiscible liq
uids can also be applied to solvent extraction and separation, by choosing the s
uitable solvents for the two phases.
2. Fabrication Sequence
The micro-reactor device used in this paper was made of soda-lime glass. Channel
s were cut into the device by a 380ï €ï m thick slitting saw. The depth of the chan
nels was made to approximately 380 ï m in order to match their width. Since a sli
tting saw was used to create the channels in the device, a cross-shaped intersec
tion, instead of the normal T-shaped intersection, was created, as shown in Figu
re 1. Comparisons have been made between the two kinds of intersections, and it
was found that there are not any significant differences in the flow patterns be
tween these two kinds of intersections on the slug flow. Factors such as surface
energy and channel width and depth play a much more important role than the int
ersection on the flow patterns.
Figure 1 Soda-lime device used for visualization.
A lid was attached onto the soda-lime device by diffusion bonding. Three 1.6 mm
holes were drilled into the lid for feed and exit tubing. PTFE capillary tubes w
ere then glued into the 1.6 mm holes using an epoxy. These capillary tubes had a
bore size of 300 ï m and 1.59 mm outer diameter.
Two 1 mL glass syringes were attached to the tubing using modified luer fitting.
A syringe driver was used to control the flow of reactants to the device to be
at a ratio of 1:1 for all experiments.
3. Experiments
A simple neutralization reaction between acetic acid and sodium or potassium hyd
roxide (NaOH and KOH, respectively) was used in this paper. The mechanisms of th
e two neutralization reactions are as follow:
This reaction occurs extremely rapidly, so the progress is considered to be cont
rolled by the rate of diffusion of reactants within the slugs only. Another adva
ntage of this reaction is that conventional pH indicators can be used to show th
e reaction progress, since a distinct color change from red to yellow would occu
r when the pH of the aqueous phase drops below 6.2, which indicate that all base
has reacted with acetic acid.
Distilled water, with phenol red pH indicator added, was used to produce aqueous
KOH and NaOH solutions of concentrations ranging from 0.1 to 0.4 M. The organic
phase consisted of kerosene as the basis with Sudan III (red) or V (blue) added
to facilitate visualization. Acetic acid was then dissolved in kerosene to prod
uce solutions with concentrations of 0.5 and 0.65 M.
Concentrations of KOH and NaOH in the organic phase can be considered to be negl
igible, whereas acetic acid is soluble in both aqueous and organic phases. The p
artition behavior of acetic acid was studied, and experiments had shown a strong
partitioning in favor of the aqueous phase. Therefore, the reaction is consider
ed to be occurring only in the aqueous phase, when acetic acid diffused from the
organic phase into the aqueous phase.
4. Chemical Engineering Analysis
Burns and Ramshaw noted that the equivalent diffusion path length was smaller th
an both slug length and slab width. To illustrate their point, sample calculati
ons are shown for the titration reaction of 0.40M NaOH with 0.65M of acetic acid
. The mass transfer coefficient was calculated from the equation
where k is the mass transfer coefficient, L is the slug length, t is observed ti
me over which the reaction takes place, and is the mole ratio of base in the a
queous phase to acid in the organic phase. The derivation can be found in the Ap
pendix A. The effective diffusion path length, to be called slab width from her
eon, is determined by solving
,
where Fo is the Fourier number, D is the diffusivity of acetone in water, and d
is the slab width into which the chemical is diffusing. Appendix Appendix A cont
ains sample calculations for the following derived equations.
Table 1 shows how the equivalent diffusive path length compares to the width cha
nnel of 380 and the slug length. The effective diffusion path is much smaller t
han channel width and slug length, an indication of improved mass transfer due t
o mixing in the slug.
Table 1. Effective diffusion length compared to channel width and slug length.
Flow Speed
mm/s Mass Transfer Coefficient (k), mm/s Slug Length
(L) mm Slab width
(d) mm % channel width % slug length
5 0.210 1.3 0.11 29.30% 8.57%
11 0.205 1.1 0.10 27.28% 9.42%
16 0.242 1 0.09 23.93% 9.09%
22 0.269 1 0.09 22.70% 8.63%
28 0.302 1 0.08 21.40% 8.13%
We also compared the time the reaction would take in the case of having only dif
fusion. The diffusion time is given by
where L and D are the slug length and diffusivity of acetone in water, respectiv
ely. From Table 2, one sees that the micro-reactor reaction time is 2-3 orders o
f magnitude smaller than with diffusion only.
Table 2. Reaction times for diffusion-only case compared to diffusion with mixi
ng in micro-reactor.
Flow Speed (mm/s) Diffusion-only time (s) Micro-reactor Time (s)
5 1363 3
11 976 2.6
16 806 2
22 806 1.8
28 806 1.6
Using the same analysis, we can observe improvements in applying the micro-react
or system to the reaction involving the extraction of copper ion in an aqueous m
edia, using Kelex within an organic solvent. We assumed that the slug length f
ormation in the copper-Kelex extraction is similar in size at the velocities tes
ted in the original micro-reactor. This reaction was also diffusion limited at
the concentrations of copper ion listed. Again, the micro-reactor system dramat
ically decreases the reaction time compared to the diffusion-only case in the la
rger scale.
Table 3. Diffusion-limited reactions at concentrations ~10^-4, [Kelex] =1.25E-4M
.
Velocity (m/s) Slug length (m) Cu2+ (M) tmacro (s) tmicro (s)
0.033 0.001 0.000257 1.80E+06 0.67
0.028 0.0011 1.80E+06 0.74
0.018 0.0012 1.80E+06 0.81
0.033 0.001 0.00011 1.80E+06 4.65
0.028 0.0011 1.80E+06 5.11
0.018 0.0012 1.80E+06 5.58
5. Modifications
Increasing the surface area of diffusion, decreasing the channel size, and incre
asing the flowrate were explored as possible improvements. By increasing the su
rface area, the reaction time in the micro-reactor can be decreased an order of
magnitude. Additionally, a decrease in the channel width will increase the reac
tion rate constant, hereby also decreasing the reaction time in the micro-reacto
r.
Based on experimental observation in the original study, only the ends o
f the slugs were determined to take part in mass transfer. The surface area per
unit slug volume, a, could be written as
,
which gives the time required for the titration at
.
However, if we are able to increase the surface area for diffusion, one can incl
ude slug surface area along the capillary walls. The surface area per unit slug
volume would then be
,
and the reaction time at
 .
When the additional surface area is taken into account, the reaction time decrea
ses by a factor of ten, as shown in Table 4 below.
Table 4. Macro vs. micro diffusion times: a) under no mixing condition b) actual
reaction time in micro-reactor c) increased surface area (S.A.). For reaction
0.65 M acetic acid with 0.40 M NaOH.
Flow Speed (mm/s) Diffusion-only
Time (s) Micro-reactor time with original S.A. (s) Micro-reactor ti
me with greater S.A. (s)
5 1363 3 0.68
11 976 2.6 0.67
16 806 2 0.55
22 806 1.8 0.50
28 806 1.6 0.44
Next we look at the effect of changing the channel width on the mass tra
nsfer coefficient. An analogy between mass and heat transfer can be used to dete
rmine the effect on the mass transfer coefficient. Approximating flow around th
e slug to be fully developed flow around a sphere with uniform surface flux, the
Nusslet number is a constant
,
where h is the convection coefficient, w is the channel width, and is the cond
uctivity. We can couple this equation with the mass transfer analogy equation:
,
where is the mass transfer coefficient and Le is the Lewis number. Using the
definition of the Lewis number and substituting it into the above equation, one
can solve for the mass transfer coefficient,
,
where A is the thermal diffusivity.
By changing the width of the channel, one can get higher mass transfer c
oefficients, as shown in Table 5. The accompanying figure (Figure 2) demonstrate
s that the greatest increase in mass transfer coefficients happens at channel wi
dths at less than 100 . Channel widths larger than 100 show smaller difference
in mass transfer coefficients at greater lengths.
Table 5 . Effect of changing the channel width on the mass transfer (MT) coeffic
ient.
Channel width (ï m) MT coefficient (m/s)
280 6.72E-04
160 1.18E-03
100 1.88E-03
80 2.35E-03
60 3.14E-03
40 4.70E-03

Figure 2 Mass transfer coefficient (m/s) vs. channel width (ï m).

As the channel length is decreased, the mass transfer coefficient increases, cau
sing a decrease in the reaction time.
Increasing the flow rate will increase the mass transfer inside the slug
s by decreasing the slug size and increasing the internal circulation. Decreasi
ng the slug size will result in decreasing the effective diffusion length. Inte
rnal circulation of the slug will also increase with increasing flow rate. The
internal circulation profile can be considered similar to that of a small sphere
in cross flow.
Application to Macroscopic Reactions
For the diffusion-limited extraction of copper with Kelex, Table 6 shows how eve
n at two different initial copper concentrations, there is a uniform decrease in
 reaction time with smaller channel widths. Figure 3 displays the same data in g
raphical form, further highlighting the effect.
Table 6 . Micro-reactor reaction times vs. decreases in channel diameter.
Adaptation to the Cu2+-Kelex system.
Velocity initial Cu 280 um 160 um 100 um 80 um 60 um 40 um
0.033 0.000257 0.50 0.28 0.18 0.14 0.11 0.07
0.028 0.55 0.31 0.19 0.16 0.12 0.08
0.018 0.59 0.34 0.21 0.17 0.13 0.08
Average 0.55 0.31 0.19 0.16 0.12 0.08
0.033 0.00011 3.43 1.96 1.22 0.98 0.73 0.49
0.028 3.77 2.15 1.35 1.08 0.81 0.54
0.018 4.11 2.35 1.47 1.17 0.88 0.59
Average 3.77 2.15 1.35 1.08 0.81 0.54
Figure 3 Diffusion time (s) vs. channel width (ï m).
The complex formation of copper with Kelex in the macro-system versus th
e micro-system also serves as a comparison. The concentration of the complex wa
s found to be 10 times greater in slugs than in macro-reaction vessel (Appendix
C).
6. Micro-systems vs. Macro-systems
The acid-base titration used in this system can be done on a macro-scale using a
buret and a beaker with a magnetic stir bar. The mixing that results from the
spinning stir bar is better that the internal circulation of the slugs because t
he mass transfer results from turbulent flow not laminar. However, the macro-sy
stem reaction usually consists of only one phase. The mass transfer time and re
action time cannot be measured on the macro-scale either because the reaction oc
curs instantaneously.
Furthermore, slug flow offers multiphase mass transfer similar to those
found in emulsions on the macro-scale. Emulsions on the macro-scale are general
ly created by either rapid stirring or high-speed spraying of one liquid into th
e other. These two methods of creating emulsions generate a lot of shear, which
could cause damage to species that are shear-sensitive. It is also more diffic
ult to control droplet size in the emulsion whereas slug size can be controlled
by varying flow rate.
Slug flow in micro-systems also provides an alternative means of liquidâ li
quid extraction besides the macro-system of counter-current cascade. The micro-
system may decrease the amount of time to perform liquid-liquid extraction since
two phases never mix because diffusion as well as internal circulation provides
the means of mass transfer. In a counter-current cascade, the two liquid phase
s have to mix and separate again before begin passed to the next stage. Usually
rapid stirring is utilized to mix the two phases in a counter-current cascade,
causing shear, which may damage products like protein.
7. Slug Flow vs. Parallel Flow in Micro-systems
Slug flow in micro-channels offers better mass transfer than typical par
allel flow. The internal circulation in the individual slugs, due to the no sli
p boundary condition on the walls and the surface tension at the water-organic i
nterface, allows for convective mass transfer in addition to diffusion. Paralle
l flow, on the other hand, only transfers mass by diffusion.
Furthermore, slug flow offers higher throughput than parallel flow. In
parallel flow, the flow rate is limited by the time required for diffusion betwe
en the parallel streams. In slug flow, the higher the flow rate in the channel
is the smaller the slug size created. A smaller slug size decreases the diffusi
on length as most of the mass transfer occurs at the ends of the slugs.

Appendix A. Diffusion-Only Model vs. Model in Paper

Diffusion-only:
Mass balance around a differential layer in a slab can be summarized as follows:
 ,
in which is the molar flux (in mole/m2-s), A is the area through which diffusi
on occurs, and C (in M) is the local concentration at location x and time t.
Since the A, is constant in a slab, the term can be eliminated in the above equa
tion. Dividing the equation by gives:
.
Fickâ s Law relates the flux to the local concentration by the following relation:
By incorporating Fickâ s Law into the partial differential equation above, the diff
usion equation in a slab can be obtained:
In the case of the reaction described in the paper, the boundary condition is ,
and the initial concentration is 0 everywhere.
For each value of C/C0 at a specified location, x, a Fourier number can be found
from the graph above, extracted from the paper by Burns and Ramshaw. From the F
ourier number, the diffusion time can be calculated, since Fourier number is def
ined as follows:
Model in paper:
The model for diffusion described by Burns and Ramshaw is as follows:
where is the concentration difference of acetic acid between the organic and a
queous phases. Since it was assumed that acetic acid reacts once it comes into c
ontact with the aqueous phase, it is reasonable to assume that . Therefore, the
above differential equation reduces to
, or
which is a first-order linear differential equation, which can be integrated to
obtain the following results:

in which A is an arbitrary constant that can be found from the boundary conditio
n given. In this case, A was found to be , where C0 is the initial concentratio
n of acetic acid in the organic phase. Simplifying the results, we get:
Letting , the diffusion time can be expressed as
as seen in Section 5.
Appendix B. Velocity profile in Slug
1

Calculations were done with and .

Table 3 Internal circulation velocity of slugs.
Velocity, m/s Slug Length, m Vï ±, m/s Vr, m/s
0.033 0.0010 0.00533 -0.00800
0.028 0.0011 0.00453 -0.00679
0.018 0.0012 0.00291 -0.00433
Sample Calculations

Appendix C. Copper(II)-Kelex Reaction

Concentration of Copper-Kelex complex in Heptane:
3
where co, Keq, and the diffusion coefficients are given below.
4
Diffusion coefficient (m2/s) Value
 5
Reaction performed at pH = 3
6
Calculations at t = 3000s are shown in Table 4.
Table 4 Comparison of complex concentration in organic phase.
Velocity, m/s [Cu2+]0, M horg(slug), m horg (macro), m C(t)slug, M
C(t)macro, M
0.033 0.000257 0.00050 0.005 5.47E-5 5.47E-6
0.033 0.000110 0.00050 0.005 2.87E-5 2.87E-6
0.028 0.000257 0.00055 0.005 4.98E-5 5.47E-6
0.028 0.000110 0.00055 0.005 2.61E-5 2.87E-6
0.018 0.000257 0.00060 0.005 4.56E-5 5.47E-6
0.018 0.000110 0.00060 0.005 2.39E-5 2.87E-6
Sample Calculations:

Appendix D. References
1. J. R. Burns and C. Ramshaw. The intensification of rapid reactions in mu
ltiphase systems using slug flow in capillaries by, Lab on a Chip, 1, 10-15 (200
1)
2. Gregâ s Homework
3. McCulloch, Jennifer K., Jilska M. Perera, Enda D Kelly, Lee R. White, Ge
offrey W. Stevens, and Franz Grieser. A Kinetic Study of Copper Ion Extraction
by Kelex 100 at a Heptane-Water Interface. Journal of Colloid and Interface Sci
ence 184, 406-413(1996)
4. Data obtained from: McCulloch, Jennifer K., et al. A Kinetic Study of C
opper Ion Extraction by Kelex 100 at a Heptane-Water Interface. Journal of Coll
oid and Interface Science 184, 406-413(1996); McCulloch, Jennifer M. et al. Di
rect Spectroscopic Measurement and Theoretical Modeling of the Diffusion of a Si
ngle Species in a Two-Phase Unstirred System. Journal of Colloid and Interface
Science 184, 399-405 (1996); and www.knovel.com
5. Data obtained from: McCulloch, Jennifer K., et al. A Kinetic Study of C
opper Ion Extraction by Kelex 100 at a Heptane-Water Interface. Journal of Coll
oid and Interface Science 184, 406-413(1996)
6. Data obtained from: McCulloch, Jennifer K., et al. A Kinetic Study of C
opper Ion Extraction by Kelex 100 at a Heptane-Water Interface. Journal of Coll
oid and Interface Science 184, 406-413(1996)