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A microsystem integrated with infrared camera is developed to measure the reaction enthalpy.
The reaction enthalpy can be determined from the temperature rise of the capillary.
Two reactions including homogeneous and heterogeneous reactions are performed.
It can provide a quick, safe and non-intrusive method to obtain the temperature profiles for fast exothermic reactions.
a r t i c l e i n f o a b s t r a c t
Article history: In this paper, a microsystem integrated with infrared camera is developed to measure the reaction
Received 30 September 2015 enthalpy of fast exothermic reactions. The microsystem is composed of a micromixer and a coiled
Received in revised form 20 January 2016 capillary, which are all placed in a vacuum box to form an adiabatic environment. The fast exothermic
Accepted 22 January 2016
reactions are started in the micromixer and then the temperature profiles of the capillary are measured
Available online 4 February 2016
via the infrared transparent window by the infrared camera. The reaction enthalpy can be determined
from the temperature rise of the capillary. Two reactions which are homogeneous and heterogeneous
Keywords:
respectively are performed with this method. The results show that the data obtained are in good agree-
Microreactor
Infrared thermography
ment with the values reported in literature with the relative experimental errors less than 5%. Compared
Reaction enthalpy with the traditional calorimeter, the microsystem can provide a quick, safe and non-intrusive method to
Exothermal reaction obtain the temperature profiles of the fast exothermic reactions.
Ó 2016 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.cej.2016.01.100
1385-8947/Ó 2016 Published by Elsevier B.V.
J.S. Zhang et al. / Chemical Engineering Journal 295 (2016) 384–390 385
temperature field of a specified area. Ewinger et al. [15] used laser microreactor and the coiled capillary were both placed in the vac-
Raman spectroscopy to measure the temperature of water in uum box which was vacuumized to a value below 10 kPa during
microchannels with an accuracy of ±1.2 °C. The procedure had a the experiments. According to the reports in the literature [16],
lateral local resolution of approximately 15 lm and a depth resolu- the value below 10 kPa is enough to suppress the convective heat
tion of 25 lm. Haber et al. [16] developed a microsystem with transfer. The used infrared camera (PI400, Optris, Germany) had
infrared thermometry and the temperature profiles of the fast a resolution of 382 288 pixels with the frequency of 80 Hz. The
exothermal hydrolysis of tetraethoxysilane were measured inside measurement temperature range was 20 to 100 °C with a sensi-
a microcapillary at different flow rates. Yi et al. [17] presented tivity of 0.08 °C. The system accuracy was ±2%. An infrared window
the thermal analysis of liquid containing Al2O3 nanoparticles in a (BGIR-75, Beijing Scitlion Technology Co.) with the diameter of
microfluidic platform using an infrared camera, which allows the 75 mm was fixed on the top of the vacuum box to make the capil-
non-contact, three dimensional and high resolution capability for lary visible to the camera. The window is made of BaF2, which pro-
temperature profiling. However, there are two conditions required vides a relatively high and constant transmissivity to the infrared
for the infrared thermometry, which limit its wide applications. ray [23]. As shown in Fig. 2, the high transmittance above 90%
One is the channel must be covered with infrared transparent can be obtained for the material BaF2 in the spectral range of
materials, such as sapphire, silicon, germanium or zinc selenide 0.2–10 lm. When the wavelength is larger than 10 lm, transmit-
[18]. The other is that the system needs a careful calibration due tance is greatly decreased to a low value of 10% at 14 lm. Accord-
to the radiation losses by absorption or reflection of the IR signal. ing to Wien displacement law, it is more suitable to measure the
In this work, a microsystem, including a micromixer, a coiled temperature above 290 K (<10 lm). During our experiments, the
capillary, a vacuum box and the infrared camera was developed temperature is usually above 293 K, which means high transmit-
to measure the reaction enthalpy of fast exothermic reactions. tance above 90% can be obtained using the material BaF2. As a
The objective of this work is to provide a quick, safe and non- result, this material is quite suitable as the infrared window in
intrusive method to obtain the temperature profiles of the fast our experiments. The losses of about 10% of the radiation due to
exothermic reactions with infrared thermography. The microsys- the infrared window can lead to a slight deviation for the temper-
tem was first calibrated with a thermocouple. Two reacting sys- ature measurement, which can be corrected by calibration as
tems which are homogeneous and heterogeneous respectively described in the next section.
were tested at different conditions with the method. The tempera- The reactants were delivered separately by metering pumps
ture profiles of the capillary was recorded and then the reaction (Beijing Satellite Co. Ltd.) through the steel capillaries immersed
enthalpy could be calculated from the temperature profiles along in a water bath to control the feeding temperature. Two commer-
the length of the capillary. cial temperature sensors were integrated in the capillaries to cali-
brate the temperature measurement system. The feed streams
2. Materials and methods were mixed in a T-shaped micromixer (VICI), which is made of
stainless steel with an inner diameter of 0.25 mm. A stainless steel
2.1. Chemicals coiled capillary (1.0 m) with an inner diameter of 1 mm and an
external diameter of 1.6 mm was connected directly downstream
Cyclohexanone oxime (C6H11NO, 98%) was purchased from J&K to the micromixer to perform the reaction. The inner diameter is
Scientific Ltd. (Beijing); Sulfuric acid (H2SO4, 98%) and sodium so small that the temperature profile at radial direction can be
hydroxide (NaOH, analytical grade) were acquired from Sinopharm ignored. During the experiments, the temperature profiles of the
Chemical Reagent Beijing Co. Ltd. coiled capillary at the flow direction were recorded by the infrared
camera via the infrared window. The camera was connected to the
2.2. Experimental setup computer and controlled by the software (PI Connect). To get the
variation of temperature versus time, we marked 5 measurement
The experimental setup used for measuring the temperature points every 0.2 m on the capillary. The temperature of these
profiles is shown in Fig. 1. It was composed of two pumps, a micro- points would be calibrated as described in the next section. A typ-
mixer, a coiled capillary, a vacuum box and an infrared camera. The ical temperature profile of the coiled capillary is shown in Fig. 3.
Fig. 1. The experimental setup used for measuring the temperature profiles. (a) Schematic overview, (b) the photograph.
386 J.S. Zhang et al. / Chemical Engineering Journal 295 (2016) 384–390
dT
u q Cp ¼ hloss a DT ð4Þ
dz
where u is the flow rate in the tube, about 0.3 m/s; q is the fluid
Fig. 2. Spectral transmittance of BaF2. Adapted from the Beijing Scitlion Technology density, 997 kg/m3; Cp is the specific heat capacity, 4.18 kJ/(kg K);
Co. hloss is the apparent convective heat transfer coefficient including
the three heat transfer mechanisms; a is specific exchange area
for the capillary, 4/D; D is the capillary diameter.
With the above equation, the dT/dz is determined to be 0.04 K.
Since the capillary length is only 1 m, the temperature change
due to the heat losses is only 0.04 K. As a result, the system with
the vacuum box can be considered as adiabatic when the DT is
5 K. When DT is increased to 10 K, the temperature change due
to the heat losses is still as low as 0.08 K.
The infrared signal received by the camera is influenced by
many factors [25], such as the transmissivity of infrared window
and the emissivity of measured surface, which would lead to a
deviation for the temperature measurement. Especially for the
emissivity, it depends on many factors: material, measuring angle,
geometry of the surface and so on. Therefore, the calibration is
required before accurate temperature measurement is obtained.
During the calibration, the fluids with different temperatures were
pumped into the system, the measured temperatures of every
points of the capillary were all the same with that shown in the
Fig. 3. A typical temperature profile of the coiled capillary.
thermocouple. As a result, the measured temperature with infrared
camera could be calibrated with the thermocouple. Theoretically
2.3. Calibration of the setup the resolution of 382 288 pixels can all be calibrated with the
thermocouple. But to simplify the calculation, only 5 measurement
Though the microreactor and coiled capillary are both placed in points as shown in Fig. 3 are calibrated.
the vacuum box, it is not avoided for the heat loss. Here we try to A typical calibration of the five points is shown in Fig. 4. It is
estimate the heat losses in the vacuum box from the three mech- found that there is a linear relationship between the measured
anisms of heat transfer: conduction, convection and radiation. It temperatures and the real temperature for the five points. The
is assumed that the temperature rise between the capillary and correlation coefficients R2 are all above 0.991, indicating that the
environment (DT) is 5 K. lines fit the results very well.
For the conduction heat transfer, the conduction loss (Ucond) can
be estimated using the Fourier law: 3. Results and discussion
2
DT pð1:6 103 Þ 5 3.1. Typical temperature profiles
U cond ¼ 2 S k ¼2 16
Dl 4 1:0
¼ 0:0003 W ð1Þ The classic neutralization reaction between dilute acid and base
solution is first tested as the model reaction, which is a typical fast
and exothermal reaction. In the experiments, H2SO4 solution was
where S is the sectional area of the capillary, k is the heat conduc-
used as the acid and NaOH solution was used as the lye, whose
tivity coefficient of stainless steel, about 16 W/(m K), Dl is the
flow rates were 10.6 and 8 mL min1. The concentrations of H+
capillary length.
was kept at 0.52 mol L1 while the concentration of OH was
The convective heat transfer coefficient (hconv) is estimated at
1 mol L1. Fig. 5 shows the typical temperature profiles at different
2 W/(m2 K) according to Krischers correlation [16] for convective
times during measuring process. When the reaction is not started,
heat transfer along horizontal cylinders. So the convection loss
the shape of the coiled capillary can be observed in the window.
(Uconv) can be estimated as follows:
The reason is that the emissivity of steel and air are different
though their real temperatures are the same. When the two fluids
U conv ¼ hconv aout DT ¼ 2 p 1:6 103 1 5
are pumped into the system and the reaction is started. With the
¼ 0:05 W ð2Þ time going on, the tube becomes much brighter from the outside
to inside along the capillary. This indicates that the capillary is
where aout is the surface area of the capillary. gradually heat up with the fluids in it. When the time is about
J.S. Zhang et al. / Chemical Engineering Journal 295 (2016) 384–390 387
Fig. 5. The typical temperature profiles at different times during measuring process.
9 s, the process is in a steady state. From the temperature profiles, NaOH solution was used as the lye, whose flow rates were 10.6
we can get the temperature rise at different measurement points and 8 mL min1. The concentrations of H+ were kept at 0.43, 0.52
and then the reaction enthalpy can be calculated. and 0.64 mol L1 while the concentration of OH was 1 mol L1.
Excessive OH was used in the measurement, so the molar reaction
3.2. Measuring the reaction enthalpy of homogeneous reaction enthalpy could be calculated based on the feed rate of H+ as
follows:
The classic neutralization reaction between dilute acid and base
C p mDT
solution is still used as the model for the homogeneous reaction. DH m ¼ ð5Þ
nHþ
During the experiments, H2SO4 solution was used as the acid and
388 J.S. Zhang et al. / Chemical Engineering Journal 295 (2016) 384–390
where DHm is the molar reaction enthalpy; Cp is the specific heat Table 1
capacity; m is the mass flow rate of the reacted solution; DT is The results for the neutralization reaction.a
the temperature rise of the reacted solution; nH+ is the molar feed C+H Measurement DT Reaction enthalpy Relative
rate of H+. (mol L1) points (°C) (kJ mol1) error (%)
During the experiments, the NaOH solution was first pumped 0.43 1 3.34 57.1 0.5
into the system and then the acid solution was pumped into the 0.43 2 3.46 59.2 3.1
system. Meanwhile, the plots of temperature versus time at the 0.43 3 3.27 55.9 2.6
0.43 4 3.2 54.7 4.7
five measurement points were recorded by the software as shown
0.43 5 3.44 58.8 2.5
in Fig. 6. The temperatures are all at about 24 °C with the time 0.43 Average of 1–5 3.34 57.1 0.5
below about 10 s. But there is an obvious vibration for all the plots. 0.52 Average of 1–5 4.14 58.1 1.2
To reduce the error, the average value for a certain time range is 0.64 Average of 1–5 5.11 58.8 2.5
adapted. When the acid solution is pumped into the system, the a
The relative error ¼ jmeasuredactual
valueactual valuej
100%.
value
temperatures at the five points are increased greatly and the order
is the same with that in the flowing direction. After about 15 s, the
temperatures are all turned into a steady state. The temperature 3.3. Measuring the reaction enthalpy of heterogeneous reaction
rise at each point can be obtained. As the solutions used in
the experiments are all diluted, the specific heat capacity used is Besides the homogeneous reaction, there are tremendous
the same with that of water at 25 °C, 4.18 J/(g °C). The calculated heterogeneous reactions in the chemical process. It is also very
results are all listed in Table 1. important to test the performance of this method for heteroge-
As shown in Table 1, the temperature rises for the five points neous reaction. The rearrangement of cyclohexanone oxime
are nearly the same with the H+ concentration of 0.43 mol L1. This (COX) in oleum is an important step to produce caprolactam, the
indicates that the reaction has been finished at the first point. The monomer for nylon-6 [6]. In our previous work, COX is usually dis-
results demonstrate the excellent mixing performance of the solved in octane, an inert organic solvent [7,27]. During the reac-
micromixer. From the temperature rise, we obtain the reaction tion, the oxime will transfer from octane to the oleum and starts
enthalpy at each point. The molar neutralization enthalpy of dilute the reaction. Here oleum is replaced by sulfuric acid (98%). As a
acid and base solutions is 57.3 kJ mol1 in literature [26]. We can result, only the quick protonation of COX in sulfuric acid happens
find that the results are quite close to the literature value and the within the residence time of about 5 s. The rearrangement would
relative errors are all below 5%. When the H+ concentrations not happen within such a short time at the absence of SO3 [28].
are increased to 0.52 and 0.64 mol L1, the obtained results also As a result, the protonation of COX is a good heterogeneous model
agree with the literature value [26] very well. reaction to test the system. The protonation is shown as follows:
Fig. 6. The plots of temperature versus time at the five measurement points with the different H+ concentrations.
J.S. Zhang et al. / Chemical Engineering Journal 295 (2016) 384–390 389
Fig. 7. The plots of temperature versus time at the five measurement points with the different flow rates.
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