Powder Technology 335 (2018) 164–170

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Powder Technology

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Effect of ethanol on the crystallization and phase transformation of

MgCO3·3H2O in a MgCl2–CO2–NH3·H2O system
Wenting Cheng a, Cuiyu Zhang a, Huaigang Cheng a, Zuliang Chen a,b, Hongqiang Liao a, Fangqin Cheng a,⁎
a
Institute of Resources and Environmental Engineering, State Environmental Protection Key Laboratory of Efficient Utilization Technology of Coal Waste Resources, Shanxi University,
Shanxi Collaborative Innovation Center of High Value-added Utilization of Coal-related Wastes, Taiyuan, Shanxi 030006, China
b
Global Centre for Environmental Remediation, University of Newcastle, Callaghan, NSW 2308, Australia

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

Article history: The effect of ethanol on the crystallization and phase transformation of MgCO3·3H2O in a MgCl2–CO2–NH3·H2O
Received 8 November 2017 system was investigated at 40 °C. The obtained crystals were characterized by X-ray diffraction and scanning
Received in revised form 29 March 2018 electron microscopy, and the phase transformation behaviors of the MgCO3·3H2O crystals were studied quanti-
Accepted 23 April 2018
tatively using an established thermal analysis method. The results showed that ethanol played a key role in
Available online 24 April 2018
inhibiting the aggregation of MgCO3·3H2O crystals because the adsorption of ethanol molecules on nuclei sur-
Keywords:
faces was preferential to that of water molecules. Active Mg2+ ions could be separated from the nuclei surfaces
Crystallization when b30% ethanol was added, preventing secondary nucleation during the crystallization of MgCO3·3H2O. As a
Ethanol result, highly dispersed and stable MgCO3·3H2O rod crystals with smooth surfaces and uniform sizes (length of
MgCO3·3H2O 25–30 μm and diameter of 2–3 μm) were successfully prepared with 30% ethanol at 40 °C. However, the rod-like
Phase transformation MgCO3·3H2O crystals started to dissolve with N40% ethanol in solution, leading to the formation of more stable,
flower-like crystals of 4MgCO3·Mg(OH)2·4H2O. The results of this study could contribute to the development of
methods for controllable crystallization of MgCO3·3H2O.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction gradually transform into another phase [9]. Therefore, it is necessary

to develop an economical and simple method for controlling the crystal-
Nesquehonite (MgCO3·3H2O), an important class of magnesium lization of MgCO3·3H2O in systems with CO2 and Mg2+ ions.
carbonate hydrate, generally exists as rod-like fine crystal and is widely Ethanol is known to affect the morphologies of crystals and influ-
used in manufacturing pharmaceuticals, cosmetics, optical devices, and ences their phase stabilities in mixed water–ethanol solutions [12–15].
chemical devices, and as a precursor for other magnesium-based Jiang et al. [14] prepared hexagonal lamellar Mg(OH)2 nanoparticles
chemicals [1–3]. Mineralization [4–6] of CO2 with Mg obtained from via a surfactant-free precipitation method using MgCl2·6H2O and
brine is considered one of the most promising methods for the prepara- NaOH as raw materials, with urea and ethanol as additives. The pre-
tion of MgCO3·3H2O owing to its relatively low cost, easy operation, and pared nanoparticles were almost hexagonal lamellas when ethanol
environmental friendliness [7–11]. Furthermore, this approach allows was added into the reaction system, indicating that ethanol can help
large-scale utilization of both CO2 and unexploited Mg resources in regulate the morphology of Mg(OH)2 nanoparticles. Aragonite (a poly-
salt lakes. Most relevant studies have focused on the mineralization pro- morph of CaCO3), which was precipitated under ambient conditions
cess of CO2 with Mg2+ ions in brine [7–11]. For instance, Ferrini et al. [7] when ethanol was added to the solution [13,16], transformed into
sequestered CO2 using a MgCl2 solution at 20 ± 2 °C in a short time vaterite (another polymorph of CaCO3) when the amount of ethanol
(~10 min), and 81.7 ± 0.7% of the sparged CO2 was captured. Wang et was varied [16–18]. The influence of ethanol on the modification and
al. [9] developed a new approach to sequester CO2 using sea/lake brines dispersion of the prepared crystals might be explained by the chemical
and NH3 in a mixed-suspension, mixed-product removal (MSMPR) and physical properties of the solution [15,17,19]. The ethanol effect on
crystallizer. Unfortunately, the above-obtained MgCO3·3H2O crystals the crystallization of MgCO3 also had been studied in some systems.
exhibit disorderly morphologies and some extent of aggregation, Chen et al. [20] had used a coupled reaction−extraction−alcohol pre-
which adversely affect their practical applications. Moreover, cipitation process to mineralize CO2 as MgCO3·3H2O directly by aban-
MgCO3·3H2O crystals do not exhibit long-term stability and will doned MgCl2. Lei et al. [21] had reported an ultrafast method for the
high-yield, scale-up synthesis of amorphous MgCO3 within 1 min
⁎ Corresponding author. through the fast diffusion of high-pressure carbon dioxide into ethanol.
E-mail address: [email protected]. (F. Cheng). They mainly focused on the effect of ethanol on the reaction rate and

https://doi.org/10.1016/j.powtec.2018.04.063
0032-5910/© 2018 Elsevier B.V. All rights reserved.
 W. Cheng et al. / Powder Technology 335 (2018) 164–170 165

yield of crystal. However, the effect of ethanol on the morphology and

phase transformation of the MgCO3·3H2O is still unclear.
In this study, the effect of ethanol on the crystallization and phase
transformation of MgCO3·3H2O in a MgCl2–CO2–NH3·H2O system was
investigated by powder X-ray diffraction (XRD), scanning electron mi-

Intensity(a.u.)
croscopy (SEM), and thermogravimetric analysis (TGA). The main
aims were to determine the influence of ethanol on the crystallization
and transformation of MgCO3·3H2O, the amount of ethanol required
to modify the solid phase or morphology of MgCO3·3H2O, and the 30% ethanol
growth mechanism of MgCO3·3H2O in the presence of ethanol. The re- 20% ethanol
sults of this study can be used to determine appropriate experimental
10% ethanol
conditions for preparing MgCO3·3H2O with a stable phase and a uni-
0% ethanol
form morphology from MgCl2–CO2–NH3·H2O systems.

10 20 30 40 50 60 70 80
2. Experimental section
2 ()

2.1. Materials

MgCl2·6H2O, NH3·H2O, and ethanol were of analytical grade and 60% ethanol
CO2 had a purity of 99.9%. All chemical reagents were used without fur-
ther purification. Double distilled water (conductivity b0.1 μS·cm−1)
was employed in all experimental work (solution preparation, crystal

Intensity(a.u.)
washing, etc.).
50% ethanol

2.2. Experimental methods

The experimental apparatus used for crystallization experiments

was illustrated in Fig. 1. A standard volume (150 mL) of NH3·H2O solu-
tion (3.0 mol·L−1) was added to the reactor, and then the reactor was
40% ethanol
heated to 40 °C. Subsequently, the reactor was maintained at a constant
temperature, and the solution was stirred at 320 r·min−1. Solutions of
10 20 30 40 50 60 70 80
MgCl2·6H2O (150 mL, 0.5 mol·L−1) with different amounts of added
2 ( )
ethanol (0–60 vol% ethanol in ethanol–water mixtures) were intro-
duced into the reactor through a peristaltic pump, and CO2 was flowed
Fig. 2. XRD patterns of the crystals obtained with various amounts of ethanol: ◆:
into the reactor at a flow rate of 30 mL·min−1 for 60 min. Following MgCO3·3H2O; ○: 4MgCO3·Mg(OH)2·4H2O.
ventilation, the slurry was stirred for 2 h. Finally, the slurry was filtered,
washed, and dried at 50 °C for 12 h.

Fig. 1. Experimental apparatus for crystallization MgCO3·3H2O: (a) CO2 cylinder; (b) crystallizer; (c) gas flow meter; (d) pH meter; (e, f) stirrer; (g) thermometer; (h) peristaltic pump; (i)
circulating water bath.
166 W. Cheng et al. / Powder Technology 335 (2018) 164–170

2.3. Characterization [19]. Thus, the effect of ethanol on the phase transformation behavior
of MgCO3·3H2O is primarily investigated.
XRD analyses of the crystals were performed on a Bruker D8 Ad- Fig. 2 displays the XRD patterns of the crystals obtained in the pres-
vance diffractometer using Cu Kα radiation at 40 kV and 30 mA in the ence of different amounts of ethanol. With 0–30% ethanol, the XRD pat-
2θ range of 10°–80°. SEM images were obtained using a JEOL JSM- terns of the crystals can be indexed to the standard card for pure
6701F scanning electron microscope. TGA was carried out using a MgCO3·3H2O (JCPDS 20–0669). When the amount of ethanol increases
Pyris 1 thermogravimetric analyzer in the temperature range of 100– to 40%, some diffraction peaks corresponding to 4MgCO3·Mg(OH)
800 °C at a heating rate of 20 °C·min−1 under a nitrogen atmosphere. 2·4H2O appear, indicating that the obtained crystal is a mixture of
MgCO3·3H2O and 4MgCO3·Mg(OH)2·4H2O. Further increasing the eth-
3. Results and discussion anol content to 50% results in a decrease of the MgCO3·3H2O diffraction
peaks and an increase of the 4MgCO3·Mg(OH)2·4H2O diffraction peaks.
Our previous work [22–25] showed that the operating temperature At 60% ethanol, MgCO3·3H2O disappears completely and only the peaks
has a significant effect on crystallization from solution, and of 4MgCO3·Mg(OH)2·4H2O are observed (JCPDS 25–0513).
MgCO3·3H2O crystals with large and uniform size were obtained at The above phase transformation is further investigated by TGA. The
40 °C. In addition, the solubility of CO2 in aqueous solution decreased TG curves in Fig. 3 reveal that the crystals which are obtained with 30–
[26] and the energy consumption increased at elevated temperatures. 60% ethanol exhibit entirely different behaviors. With 30% ethanol, two
Therefore, the effects of ethanol on the crystallization and phase trans- weight loss stages are observed in the TG curve, assigned to the dehy-
formation of MgCO3·3H2O were investigated at 40 °C, and no higher dration of MgCO3·3H2O and the decomposition of MgCO3 (Eqs. (1)
temperatures were examined. and (2)) [27,28]. With 60% ethanol, there are three obvious weight
loss stages in the TG curve [29,30], which can be attributed to the de-
3.1. Effect of ethanol on the phase transformation of MgCO3·3H2O in the composition of 4MgCO3·Mg(OH)2·4H2O, dehydration of Mg(OH)2,
MgCl2–CO2–NH3·H2O system and dissociation of MgCO3 (Eqs. (3)–(5)). The mass loss percentage
can be calculated by the TG curves.
Although the most common magnesium carbonate hydrate pre-
 
pared from aqueous solution under ambient conditions is MgCO3·3H2O, MgCO3
3H2 O→MgCO3 þ 3H2 O b300 ° C; 35:8%loss ð1Þ
phase transformations can occur when various conditions are changed

100 100
30 % ethanol 50 % ethanol
90 -w1
90
80 -w1 MgCO3.3H2O : 5.1 %
MgCO3.3H2O : 100 %
80
70 4MgCO3.Mg(OH)2.4H2O : 0 % 4MgCO3.Mg(OH)2.4H2O : 94.9 %
Weight (%)

Weight (%)

60 70
-w2
50 -w2 60

40
50
-w3 -w3
30
40
20
100 200 250 300 400 440 500 600 700 800 100 200 250 300 400440 500 600 700 800
o
Temperature ( C) o
Temperature ( C)

100 100
40 % ethanol 60 % ethanol
90 -w1 -w1
90
MgCO3.3H2O : 16.1 % MgCO3.3H2O : 0 %
80 80
4MgCO3.Mg(OH)2.4H2O : 83.9 % 4MgCO3.Mg(OH)2.4H2O : 100 %
Weight (%)

Weight (%)

70 70
-w2 -w2
60 60

50 50
-w3 -w3
40 40
440
100 200 250 300 400 500 600 700 800 100 200 250 300 400
440
500 600 700 800
o
Temperature ( C) Temperature ( C)
o

Fig. 3. TG curves of the crystals obtained with various amounts of ethanol.

 W. Cheng et al. / Powder Technology 335 (2018) 164–170 167

 
Table 1 4MgCO3
MgðOHÞ2
4H2 O→4MgCO3
MgðOHÞ2 þ 4H2 O b250 ° C; 14:0%loss
Quantification of the compositions of mixtures, as calculated from the TGA curves.
ð3Þ
Added ethanol (%) m0 (g) w1 (%) w2 (%) w3 (%) m1/m0 (%) m2/m0 (%)

30 10.604 34.4 32.4 3.80 100 0

40 9.514 15.4 36.8 7.30 16.1 83.9  
50 10.002 14.2 37.9 5.95 5.1 94.9 4MgCO3
MgðOHÞ2 →4MgCO3 þ MgO þ H2 O 250–440 ° C; 37:2%loss
60 9.465 14.0 37.2 6.16 0 100
ð4Þ

   
MgCO3 →MgO þ CO2 N300 ° C; 34:7%loss ð2Þ 4MgCO3 →4MgO þ 4CO2 N440 ° C; 6:16%loss ð5Þ

Fig. 4. Effect of ethanol on the morphology of crystals: (a) 0% ethanol; (b) 10% ethanol; (c) 20% ethanol; (d) 30% ethanol; (e) 40% ethanol; (f) 50% ethanol; (g) 60% ethanol.
168 W. Cheng et al. / Powder Technology 335 (2018) 164–170

Fig. 5. Schematic representation of the effect of ethanol on the crystallization.

From the above analysis of the XRD patterns and TG curves, it can be mass loss in three temperature ranges (b250 °C, 250–440 °C, and N
seen that increasing the ethanol content from 30% to 60% results in a 440 °C, respectively). The calculated results are listed in Table 1.
phase transformation of the obtained crystals from pure MgCO3·3H2O As shown in Table 1, with the ethanol content increases from 40% to
to a mixture of MgCO3·3H2O and 4MgCO3·Mg(OH)2·4H2O, and then 60%, the mass proportion of MgCO3·3H2O gradually decreases to 0,
to pure 4MgCO3·Mg(OH)2·4H2O. This finding confirms that the added whereas that of 4MgCO3·Mg(OH)2·4H2O increases to 100%. This trend
ethanol plays a key role in the transformation of crystals [15]. In order is consistent with the XRD results.
to quantitatively analyze the transformation of MgCO3·3H2O into
4MgCO3·Mg(OH)2·4H2O in the MgCl2–CO2–NH3·H2O system, the com- 3.2. Effect of ethanol on the morphology of MgCO3·3H2O in the MgCl2–CO2–
positions of the crystal mixtures were calculated by a method based on NH3·H2O system
the analysis of the TG curves (Fig. 3). The method is expressed by Eqs.
(6) and (7), as follows: It has previously been confirmed that significant changes in mor-
phology inevitably occur with phase transformations of magnesium car-
m0 ¼ m1 þ m2 ð6Þ bonate hydrate [24,25]. The effect of ethanol on the morphologies of the
obtained crystals is illustrated by the SEM images in Fig. 4.
As shown in Fig. 4(a)–(d), MgCO3·3H2O exhibits morphology of
m0 ð1−w1 −w2 −w3 Þ ¼ m1 ð1−34:4%−32:4%−3:80%Þ rod-like structures when the amount of ethanol is 0–30%. However, se-
þ m2 ð1−14:0%−37:2%−6:16%Þ ð7Þ
rious agglomeration and secondary nucleation occur without the addi-
tion of ethanol, resulting in the phenomenon of “split ends” on the
where m0 is the total mass of the sample used for TGA; m1 and m2 are crystals, and no improvement is observed with 10% ethanol. When the
the masses of MgCO3·3H2O and 4MgCO3·Mg(OH)2·4H2O in the sam- amount of ethanol increases to 20%, aggregation of the crystals is
ple, respectively; and w1, w2, and w3 represent the percentages of inhibited to some extent and consequently the amount of “split ends”

Fig. 6. Schematic representation of the effect of ethanol on the growth of MgCO3·3H2O: (a) without ethanol and (b) with 30% ethanol.
 W. Cheng et al. / Powder Technology 335 (2018) 164–170 169

is decreased. Further increasing the amount of ethanol to 30% results in Acknowledgments

MgCO3·3H2O crystals with smooth surfaces and uniform sizes. In addi-
tion, the size of MgCO3·3H2O crystals increases with the increase of the The authors gratefully acknowledge financial support from the Na-
amount of ethanol. This behavior may be attributed to the fact that the tional Nature Science Foundation of China (U1707603), Coal-based
decrease of supersaturation due to the addition of ethanol [17]. At Key Project for Science and Technology Development of Shanxi Province
higher supersaturation with 0–10% ethanol, the primary nucleation is in China (MD2014–10) and the Program for Sanjin Scholars of Shanxi
fast and many crystallites with small size are produced [31]. Hence, par- Province.
ticles cannot grow into larger ones and cluster together. On the other
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