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Article history: In this work, nano-CaCO3 particles with tunable size have been synthesized via CO2 /Ca(OH)2 precipitation
Received 24 November 2013 reaction in a microporous tube-in-tube microchannel reactor (MTMCR) with a throughput capacity up
Received in revised form 7 March 2014 to 400 L/h for CO2 and 76.14 L/h for liquid. The overall volumetric mass-transfer coefcient (KL a) of CO2
Accepted 11 March 2014
absorption into Ca(OH)2 slurry in the MTMCR has been deduced and analyzed. To control the particle
Available online 19 March 2014
size, the effect of operating conditions including initial Ca(OH)2 content, gas volumetric ow rate, liquid
volumetric ow rate, micropore size, and annular channel width was investigated. The results indicated
Keywords:
that the mass transfer in the MTMCR can be greatly enhanced in contrast with a stirred tank reactor, and
Adsorption
Mass transfer
the particle size can be well controlled by tuning the operating parameters. The nano-CaCO3 particles
Nano-CaCO3 with an average size of 28 nm and a calcite crystal structure were synthesized, indicating that this process
Microporous tube-in-tube microchannel is promising for mass production of nanoparticles.
reactor 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cep.2014.03.006
0255-2701/ 2014 Elsevier B.V. All rights reserved.
Y. Liang et al. / Chemical Engineering and Processing 79 (2014) 3439 35
excellent micromixing and mass-transfer performance with the 3.1. Synthesis process of nano-CaCO3 by reacting CO2 and
throughput capacity at L/min level [22,23]. Li et al. [24] synthesized Ca(OH)2
ultrane calcium carbonate particles by reactive precipitation of
Na2 CO3 and CaCl2 solutions in the MTMCR. The particle size can be The preparation of nano-CaCO3 by the absorption of CO2 into the
adjusted in the tube-in-tube microreactor by varying the micropore Ca(OH)2 slurry is a typical gasliquid reaction. The steps involved
size, ow rate, reactant concentration and effective length of the in this process can be expressed as [27]:
tube, etc. However, the particle size of calcium carbonate prepared Dissolution of Ca(OH)2
by the liquidliquid reaction in the MTMCR was on micrometer Ca(OH)2 (aq) Ca2+ + 2OH (1)
scale (average particle size was 0.89 m).
To obtain nano-CaCO3 , a gasliquid reaction between CO2 and CO2 absorption in water
Ca(OH)2 slurry in the MTMCR was adopted in this work. Experi- CO2 (g) + H2 O CO3 2 + 2H+ (2)
ments were carried out with different operating conditions. The
overall volumetric mass-transfer coefcient (KL a) of CO2 in the The reaction of Ca2+ and CO3 2
80 0.06
Paticle size
KLa
70 0.05
pH Meter
T
KLa (s )
Liquid Stirred Tank
50 0.03
-1
Water Bath
Flowmeter
40 0.02
30 0.01
0 2 4 6 8
Fig. 3. The effect of the Ca(OH)2 content on KL a and the mean particle size of nano-
of CO2 in gas is constant, so C* is a constant. For the fast reaction CaCO3 in the MTMCR.
between CO2 and Ca(OH)2 in the slurry, the concentration of CO2 in
liquid is far lower than C* before the end of the reaction. Therefore, M /RS
It can be deduced from Table 1 that = RCO =
Eq. (5) can be written as: CO 2 2
KL aM /KL aS = 3.9 > 1, which shows that the mass-transfer coef-
RCO2 = KL aC (6) cient in the MTMCR is much higher than that in the STR. Therefore,
According to the denition of RCO2 , it can be written as: the mass-transfer efciency in the MTMCR is enhanced, and the
nano-CaCO3 synthesis process coupling with mass transfer of CO2
nCO2 nCa2+ can be controlled via changing Ca(OH)2 content, gas and liquid ow
RCO2 = = (7)
Lt Lt rate, micropore size and annular channel width in the MTMCR.
t is the reaction time. nCO2 is the total mole number of CO2 absorbed
in the Ca(OH)2 slurry. L is the total volume of the slurry. nCa2+ is the 4. Results and discussion
total mole number of Ca2+ in the Ca(OH)2 slurry.
The value of KL a can be obtained by Eqs. (5) and (6). 4.1. Effect of Ca(OH)2 content
RCO2 RCO2
KL a = = (8) Fig. 3 exhibits the effect of Ca(OH)2 content on the KL a of CO2 and
C C C the size of nano-CaCO3 particles. The total volume of slurry, liquid
The intensication of reaction in the MTMCR caused by the volumetric ow rate, CO2 volumetric ow rate, temperature, size of
enhancement of mass transfer can be expressed as a coefcient micropore and size of annular microchannel were 0.2 L, 19.18 L/h,
of . 100 L/h, 298 K, 10 m and 0.5 mm, respectively.
M
It can be seen from Fig. 3 that the KL a of CO2 increased from
RCO KL aM
= 2
= (9) 0.018 to 0.051 s1 with the increase of Ca(OH)2 content from 0.7%
S
RCO KL aS to 8%. The absorption of CO2 into aqueous solution is a liquid lm
2
controlled process and the mass-transfer resistance of this process
M is the average reaction rate in the MTMCR, RS
RCO is the average
2 CO 2
is mainly in the liquid phase. The reaction of CO2 with Ca(OH)2
reaction rate in the STR. KL aM is the KL a in the MTMCR. KL aS is the in slurry and the excellent micromixing in the MTMCR lead to the
KL a in the STR. decrease of the mass-transfer resistance. In addition, the forma-
tion of CaCO3 precipitation reduces the CO2 concentration in water
3.2. Comparison between MTMCR and STR and boosts the driving force for CO2 mass transfer. Therefore, the
increase of Ca(OH)2 content results in the increase of the KL a.
To investigate the difference of mass-transfer efciency It is also observed from Fig. 3 that the particle size of CaCO3
between the MTMCR and the STR, the experiment was carried out increased from 38 to 75 nm with the increase of Ca(OH)2 content
under the same operating conditions in an STR with a high stir- from 0.7% to 8%. As mentioned above, the increase of Ca(OH)2 con-
ring speed of 1300 rpm. The schematic diagram of the comparison tent is benecial to the mass transfer of CO2 from gas phase to liquid
experiment is shown in Fig. 2. The RCO2 and KL a in the two reactors phase. The increase of CO2 concentration in the slurry enhances the
are shown in Table 1. reaction between CO2 and Ca(OH)2 to generate a larger amount of
primary nuclei of CaCO3 . However, the increase of Ca(OH)2 con-
tent will increase the reaction time, leading to the growth and
Table 1
Comparison of KL a between MTMCR and STR.
coalescence of the primary nuclei and thus a larger particle size.
90 0.06 45
0.0450
Paticle size Paticle size
75 KLa 40 KLa
0.05
0.0425
60
35
KLa s
0.0400
KLa (s )
0.04
-1
45
-1
30
0.0375
0.03
30
25 0.0350
15 0.02 0 20 40 60 80 100
0 100 200 300 400 500
micropore size (m)
Gas flow rate (L/h)
Fig. 6. The effect of the micropore size on KL a and the mean particle size of nano-
Fig. 4. The effect of the gas volumetric ow rate of CO2 on KL a and the mean particle CaCO3 in the MTMCR.
size of nano-CaCO3 in the MTMCR.
40
KLa 0.026
Fig. 6 shows that the KL a decreased from 0.044 to 0.036 s1
KLa (s )
45 0.060
Paticle size
40 KLa 0.055
Paticle size (nm)
35 0.050
KLa (s )
30 0.045
-1
25 0.040
20 0.035
0.50 0.75 1.00 1.25 1.50
Annular channel width (mm)
Fig. 7. The effect of the annular channel width on KL a and the mean particle size of
nano-CaCO3 in the MTMCR.
Fig. 9. The TEM image of the as-prepared nano-CaCO3 .
100
4.5. Effect of annular channel width
800 CaCO3 agrees with that of the calcite crystal structure in the JCPDS
(Joint Committee on Powder Diffraction Standards) database, indi-
cating that the nano-CaCO3 has a calcite structure.
600
Fig. 9 is the TEM image of the nano-CaCO3 . It shows that such
nano-CaCO3 has a particle size of about 28 nm and a cubic morphol-
400
ogy. As-prepared CaCO3 also exhibits a narrow size distribution
ranging mainly from 15 to 40 nm as can be seen from Fig. 10.
200
0
5. Conclusions
0 20 40 60 80 100
2 (degree) This work presents the preparation of CaCO3 nanoparticles by
the absorption of CO2 into Ca(OH)2 slurry in the MTMCR. The
Fig. 8. The XRD pattern of the as-prepared nano-CaCO3 . KL a of this process was deduced to investigate the mass-transfer
Y. Liang et al. / Chemical Engineering and Processing 79 (2014) 3439 39
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