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Chemical Engineering and Processing 79 (2014) 3439

Contents lists available at ScienceDirect

Chemical Engineering and Processing:


Process Intensication
journal homepage: www.elsevier.com/locate/cep

Controllable preparation of nano-CaCO3 in a microporous


tube-in-tube microchannel reactor
Yan Liang a , Guangwen Chu b , Jiexin Wang a , Yan Huang a , Jianfeng Chen b ,
Baochang Sun b, , Lei Shao a,
a
State Key Laboratory of OrganicInorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
b
Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029,
China

a r t i c l e i n f o a b s t r a c t

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.

1. Introduction to the synthesis of nano-CaCO3 . The supersaturation ratio of [Ca2+ ]


and [CO3 2 ] in the interface can be expressed as:
The preparation of CaCO3 particles is currently an area of intense
scientic research due to the wide applications of CaCO3 in plastics, [Ca2+ ][CO3 2 ]
S=
paints, pigments, paper-making, etc. Nano-CaCO3 , with a particle [s.p.]
size less than 100 nm, is particularly useful for sealants compared
to common CaCO3 particles (13 m) [1,2]. Other applications where [Ca2+ ] and [CO3 2 ] are the concentrations of calcium ion and
of nano-CaCO3 in PVC, paint, rubber have also been extensively carbonate ion in the interface area respectively, and [s.p.], a con-
explored [35]. stant at a xed temperature, is the solubility product of calcium and
Gasliquid carbonation is one of the main methods to prepare carbonate ions [15]. In order to obtain a high degree of the super-
nano-CaCO3 and provides a viable route for the mass production saturation concentration of CaCO3 , high concentrations of calcium
of nano-CaCO3 [613]. The gasliquid carbonation for the prepara- ion and carbonate ion are needed. During carbonization process,
tion of nano-CaCO3 particles is a reactive precipitation process in the calcium ion amount is sufcient [16], but the mass transfer rate
which supersaturation of CaCO3 is created by the absorption of CO2 , of CO2 from the gas phase to the liquid phase is a slow process,
mixing, and chemical reaction, leading to the nucleation and crys- and the concentration of carbonate ion is determined by the mass
tal growth [14]. However, it is not easy to control the dispersion, transfer of CO2 . Therefore, fast mass transfer of CO2 is important for
mixing, and mass transfer in this process. According to the theories the synthesis of nano-CaCO3 , and the particle size can be inuenced
of crystallization kinetics, the nucleation and crystal growth can signicantly by the absorption process of CO2 .
be controlled by supersaturation of the product, which is the key Because of their specic microstructure, some reactors have
shown a short transfer time and an excellent micromixing effect
[1720]. However, most microreactors, usually at mL/min scale,
have a much smaller throughput capacity compared to conven-
Corresponding authors. Tel.: +86 10 64421706/64443134; fax: +86 10 64434784. tional reactors [21]. A high-throughput microporous tube-in-tube
E-mail addresses: sunbc@mail.buct.edu.cn (B. Sun), shaol@mail.buct.edu.cn, microchannel reactor (MTMCR) was thus developed to address
shao lei@sina.com (L. Shao). this problem. It has been demonstrated that the MTMCR has an

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

After the termination of the reaction, samples were immedi-


pH Meter
T ately taken from the CaCO3 slurry for the TEM (H-800, Hitachi,
MTMCR Japan) analysis. The average particle size and particle size distribu-
tion of CaCO3 were obtained by measuring over 200 particles in the
Liquid Tank
TEM photographs with the Image-Pro Plus 5.0 software. The CaCO3
slurry was subsequently ltered and the lter cake was dried in an
Flowmeter Water Bath oven (DZF-6020, Shanghai Yiheng Instruments Co., Ltd., Shanghai,
China) at around 353 K for 24 h to obtain the CaCO3 powder sam-
ples for XRD (XRD-6000, Shimazu, Japan, with radiation of Cu K)
analysis.
CO Flowmeter
T 3. Mass transfer-reaction mechanism in the MTMCR
Pump

The contact of CO2 and Ca(OH)2 slurry is mainly carried out in


Liquid outlet the MTMCR, so the absorption and reaction mainly takes place in
sampling point
the MTMCR. To reveal the mechanism of the absorption and reac-
Fig. 1. Experimental setup for the preparation of nano-CaCO3 in the MTMCR. tion, it is necessary to investigate the relationship between mass
transfer and reaction processes in the MTMCR.

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

MTMCR was deduced to investigate the effect of CO2 mass-transfer Ca 2+


+ CO3 2
CaCO3 (s) (3)
coefcient on the particle size of CaCO3 .
When CO2 is excessive, reactions (1)(3) can be combined as:
Ca(OH)2 (aq) + CO2 (g) CaCO3 (s) + H2 O (4)
2. Materials and methods
It was reported that a high degree of supersaturation, uniform
Ca(OH)2 (A.R. grade) was purchased from Beijing Reagent Co., spatial concentration distribution, and identical growth time for
China. Deionized water was produced by a water purication sys- all crystals are the main inuencing factors for the preparation
tem (RO-DI plus, Hitech, China). CO2 gas with a purity of 99.9% was of nano-CaCO3 [28]. The uniform spatial concentration distribu-
purchased from Beijing Tianyoushun Gas Co., Ltd., China. tion and identical growth time can be achieved by the excellent
Schematic diagram of the experimental setup is illustrated in micromixing in the MTMCR. In addition, the ow pattern in the
Fig. 1. There are two main parts in the microreactor: the inner MTMCR can be assumed to be a plug ow [29]. Thus the residence
tube and outer tube. A detailed description of the structure of the time distribution and dispersion number of the uid are negligible.
MTMCR can be found in literatures [25,26]. The micropores are Such a well-micromixed plug ow reactor is regarded as a suitable
distributed around the wall at one end of the inner tube (micro- apparatus for the preparation of nanoparticles with narrow size
pore zone: porosity of 46%; length of 1 cm). The inner tubes with distribution [28].
pore sizes of 5 m, 10 m, 20 m, 40 m, 80 m, 100 m were The preparation process of nano-CaCO3 includes the absorp-
employed in this study. The width of the mixing channel (the dis- tion of CO2 into the Ca(OH)2 slurry and the precipitation reaction
tance between the inner and outer tubes) can be changed from between CO2 and Ca(OH)2 . The reaction (3) is so fast that a high
0.5 mm to 1.5 mm. degree of supersaturation of CaCO3 can be achieved in the local
In the MTMCR, CO2 was forced to ow from the inner tube sites in the reactor. And it can be assumed that the absorbed CO2 is
through the micropores into the annular channel to contact with totally consumed by the reaction (3) before the end point of the
the Ca(OH)2 slurry from the outer tube. The initial content of reaction. Therefore, the degree of supersaturation of CaCO3 can
Ca(OH)2 was 1.08 mol/L, and the initial pH of the Ca(OH)2 slurry be controlled by the absorption rate of CO2 . In other words, the
was 13.31. The Ca(OH)2 slurry was circulated between the MTMCR absorptionreaction process is controlled by the mass transfer of
and a liquid tank, and the reaction was terminated when the pH CO2 into Ca(OH)2 slurry in the MTMCR.
of the slurry reached 7 (the yield of calcium carbonate could reach The average reaction rate is equal to average absorption rate of
nearly 98%). CO2 in terms of the mass conservation in this process, and it can be
As shown in Fig. 1, the MTMCR, liquid tank and connecting expressed as:
pipeline were placed in a water bath, which was used to control
RCO2 = KL a(C C) (5)
the reaction temperature, and the temperature uctuation of the
water bath was less than 2 K. The temperature of the resulting slurry RCO2 is the average reaction rate of Eq. (4). KL a(C* C) is the average
in the liquid tank was also monitored by the pH meter and found absorption rate of CO2 . C* is the equilibrium dissolved CO2 con-
almost the same as the temperature of the water bath. centration. C is the dissolved CO2 concentration. The concentration
36 Y. Liang et al. / Chemical Engineering and Processing 79 (2014) 3439

80 0.06

Paticle size
KLa
70 0.05
pH Meter
T

Paticle size (nm)


60 0.04

KLa (s )
Liquid Stirred Tank
50 0.03

-1
Water Bath
Flowmeter
40 0.02

30 0.01
0 2 4 6 8

Ca(OH)2 content (%)


Fig. 2. Experimental setup for the preparation of nano-CaCO3 in the STR.

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.

Items MTMCR STR


4.2. Effect of gas volumetric ow rate of CO2
Temperature, K 298 298
Pressure, atm 1 1
Ca(OH)2 concentration, % (w/w) 7.4 7.4
Fig. 4 shows the effect of CO2 volumetric ow rate on the KL a
Gas ow rate, L/h 100 100 and mean particle size of nano-CaCO3 . The total volume of slurry,
Liquid volume, mL 200 200 Ca(OH)2 content, temperature, liquid volumetric ow rate, size of
RCO2 , 102 mol L1 s1 0.18 0.046 micropore and size of annular microchannel were 0.2 L, 7.4%, 291 K,
KL a, 102 s1 5.47 1.40
38.17 L/h, 10 m and 0.5 mm, respectively.
Y. Liang et al. / Chemical Engineering and Processing 79 (2014) 3439 37

90 0.06 45

0.0450
Paticle size Paticle size
75 KLa 40 KLa
0.05
0.0425

Paticle size (nm)


Paticle size (nm)

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.

It is observed from Fig. 4 that the KL a increased from 0.029 to


0.055 s1 with the increase of CO2 volumetric ow rate from 60 to size of micropore and size of annular microchannel were 0.25 L,
400 L/h. The increase of CO2 volumetric ow rate boosts the turbu- 7.4%, 291 K, 300 L/h, 10 m and 0.5 mm, respectively.
lence and the renewal rate of gasliquid interface and decreases the Fig. 5 shows that the increase of the liquid ow rate from 11.59
gas-side mass-transfer resistance, which leads to the enhancement to 73.14 L/h led to the increase of the KL a from 0.022 to 0.029 s1 .
of the gasliquid mass transfer. In addition, a higher gas volumet- The possible reason for this phenomenon was that a higher liq-
ric ow rate leads to a higher CO2 concentration in the liquid, and uid ow rate gives rise to a greater liquid-side mass transfer, as a
consequently facilitates the reaction between CO2 and Ca(OH)2 , result of more liquid spreading over the surface of the packing. The
resulting in an increase of the mass-transfer driving force, which is absorbed CO2 can quickly convert to CaCO3 , which decreases the
also favorable for the increase of KL a. CO2 concentration in the slurry and increases the absorption driv-
Fig. 4 also shows that the particle size of nano-CaCO3 decreased ing force, resulting in the increase of mass transfer efciency. Also,
from 81 to 31 nm with the increase of CO2 volumetric ow rate increasing liquid ow rate enhances the turbulence of the slurry
from 60 to 400 L/h. The increase of CO2 volumetric ow rate results in the MTMCR and the corresponding reduction of mass transfer
in the increase of KL a, leading to the increase of CO2 concentration resistance, thereby leading to the increase of KL a.
in the slurry and the rise of the reaction rate, which gives rise to a Fig. 5 also shows that the particle size of CaCO3 decreased from
larger amount of smaller primary nuclei of CaCO3 . In addition, the 50 to 25 nm with the increase of liquid ow rate from 11.59 to
increase of KL a decreases the reaction time and the crystal growth 73.14 L/h. The increase of liquid volumetric ow rate results in the
time, causing a smaller particle size of CaCO3 . increase of KL a, which increases the mass transfer between CO2
and liquid, resulting in the increase of CaCO3 nucleation rate. In
4.3. Effect of liquid volumetric ow rate addition, the increase of mass transfer decreases reaction time and
crystal growth time. All of these result in the decrease of the mean
Fig. 5 shows the effect of the liquid volumetric ow rate on particle size of CaCO3 .
the KL a and mean particle size of nano-CaCO3 . The total volume
of slurry, Ca(OH)2 content, temperature, gas volumetric ow rate,

4.4. Effect of the size of micropore of the inner tube


0.030

Fig. 6 displays the effect of the micropore size on KL a and the


50
average size of CaCO3 nanoparticles. The total volume of slurry,
0.028
content of Ca(OH)2 , temperature, gas volumetric ow rate, liquid
volumetric ow rate and size of annular microchannel were 0.2 L,
Paticle size
7.4%, 291 K, 100 L/h, 19.18 L/h, 0.5 mm, respectively.
Paticle size (nm)

40
KLa 0.026
Fig. 6 shows that the KL a decreased from 0.044 to 0.036 s1
KLa (s )

with the increase of micropore size from 5 to 100 m. The bubble


0.024 size of gas phase as dispersed phase in the slurry is mainly deter-
-1

mined by the micropore size. The smaller micropore size leads to


30 the smaller and more gas bubbles and the increase of turbulence,
0.022 surface area and renewal rate of the gasliquid interface, resulting
in the increase of mass-transfer coefcient.
It can also be seen from Fig. 6 that the mean particle size
20 0.020 increased from 27 to 40 nm with an increase of the micropore
0 20 40 60 80
size from 5 to 100 m. With the increase of the micropore size,
Liquid flow rate (L/h) the mass transfer, micromixing effects and primary nuclei num-
ber decreases, whereas the reaction time and crystal growth time
Fig. 5. The effect of the liquid volumetric ow rate on KL a and the mean particle
size of nano-CaCO3 in the MTMCR. increase, resulting in a larger particle size of nano-CaCO3 .
38 Y. Liang et al. / Chemical Engineering and Processing 79 (2014) 3439

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

Fig. 7 shows that the annular channel width is another impor- 80


tant parameter for the preparation of the nano-CaCO3 particles in
the MTMCR. The total volume of slurry, Ca(OH)2 content, temper-
ature, gas volumetric ow rate, liquid volumetric ow rate and 60
size of micropore were 0.2 L, 7.4%, 298 K, 100 L/h, 19.18 L/h, 5 m,
respectively.
%

It is observed from Fig. 7 that the KL a decreased from 0.055 to 40


0.040 s1 with the increase of annular channel width from 0.5 to
1.5 mm. The decrease of annular channel width leads to the increase
of liquid and gas ow rates in the channel as well as the enhance- 20
ment of the turbulence of CO2 and the slurry in the MTMCR. Also,
the thinner liquid lm and the enhancement of gas dispersion in
liquid result in the subsequent intensication of gasliquid mass 0
transfer process. 15 20 25 30 35 40 45 50 55 60
It can also be seen from Fig. 7 that the mean particle size
Particle size (nm)
increased from 25 to 41 nm with the increase of annular chan-
nel width from 0.5 to 1.5 mm. The increase of the annular channel Fig. 10. Particle size distribution of the as-prepared nano-CaCO3 .
width causes a decrease in KL a, which means decreased mass trans-
fer and micromixing effects and increased reaction time and crystal
growth time, leading to a larger particle size of CaCO3 . 4.6. XRD and TEM analyses

The XRD and TEM analyses were performed on CaCO3 sam-


ple prepared at a temperature of 298 K, Ca(OH)2 content of 7.4%,
1400 gas volumetric ow rate of 100 L/h, liquid volumetric ow rate
of 57.16 L/h, slurry volume of 250 mL, which were determined as
1200 the optimum operation conditions in this study by considering the
CaCO3 quality, cost, easiness and stability of the operation.
1000 The XRD pattern of the as-prepared nano-CaCO3 is shown in
Fig. 8. It is found that the XRD pattern of the as-prepared nano-
intensity (cps)

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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