Advanced Powder Technology xxx (2016) xxx–xxx

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Advanced Powder Technology

journal homepage: www.elsevier.com/locate/apt

Original Research Paper

Preparation of active magnesium oxide with caustic calcined magnesia

by ammonia circulation method
Xue Li ⇑, Ying Zhang, Yan Zhang, Ze Jin, Peng Chang, Yunyi Liu
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, PR China
Key Laboratory of Applied Technology for Chemical Engineering of Liaoning Province, Shenyang 110142, PR China

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

Article history: Magnesium oxide (MgO) with different morphology were prepared by calcining precursors (magnesium
Received 14 January 2016 hydroxide MH). The precursors were synthesized from industry lightly calcined powder (MgO content of
Accepted 22 March 2016 80–93%) by ammonia circulation method. The structures of MH and MgO were characterized by scanning
Available online xxxx
electron microscope and laser particle size analyzer. The crystal growth mechanism of MgO precursors
were simulated by materials studio. The experimental results showed that the MgO had the same mor-
Keywords: phology with their precursors. The adsorption of SO2

4 can significantly increase the particle size of pre-
Active magnesium oxide
cursors, and its D50 reached 2.05 lm. After adsorping Cl
, the exposure proportion of planes (0 0 1) and
Magnesium hydroxide
Mechanism
(1 0 1) was reduced, and the morphology of MH more easily grow to be uniform bulk crystal. The activity
Numerical simulations of MgO (CAA) produced with MgCl2 was 1500 85 by the citric acid method, which was higher than other
MgO produced with Mg(NO3)2 and MgSO4.
Ó 2016 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan.

1. Introduction reaction. The objective of this paper was to investigate how to pro-
duce the MgO with controlled-shape and high activity by calcining
The high active MgO as a promoters and activator has attracted different precursors method. The particle size, morphology crystal
much attention and widely used in many applications such as plas- phase, and the CAA of the synthesized MgO were characterized.
tic, rubber, and other halogen-free polymeric materials [1–12]. A
simple and low-cost fabrication method of high active MgO with
2. Experimental
specific morphological structures is still a challenge. The method
frequently used for preparing active MgO include calcining magne-
2.1. Preparation of active MgO
site, carbonating dolomite, the brine ammonium bicarbonate
method and the brine carbonization method [13–15]. However,
After the ammonia-evaporation reaction had ended, the result-
this method cannot produce the shape-controlled active MgO.
ing Mg salt solution was cooled and filtered. Mg salt was reacted
Magnesite (MgCO3) is a plentiful mineral wordwide that can be
with ammonia to produce MH precipitate and NH+4 as follows:
calcined to an inexpensive MgO product called CCM [16–20]. Com-
The samples were obtained by precipitation, at a controlled tem-
pared to the commonly used MgCl2 obtained from seawater and
perature 70–120 °C, of a Mg salt solution of concentration
brine, CCM is particularly suitable for preparing chlorine-free
1.0 mol/L by addition of NH3 used as precipitator. The precursors
MH. The direct hydration method [MgO + H2O ? Mg(OH)2] can
of different Mg salt were calcined and the resulted MgO samples
be used to prepare MH from CCM. As a result, the precursor
obtained.
(MH) was prepared by precipitation reaction which used CCM
and ammonium salt (NH4Cl, NH4NO3, (NH4)2SO4) as raw material,
ammonia gas as precipitant [21,22], and then shape-controlled 2.2. The crystal growth mechanism of MH
active MgO was prepared by precursor calcination. In addition,
the growth mechanism of MH was studied, and it focused on The numerical simulations research was using Materials Studio
how anionic groups affect the morphology of MH crystal in the to analyze the crystal growth mechanism of MH. In the process, the
Materials Studio molecular modeling was used on predicting the
crystal form of hexagonal hydroxide. By cutting the main crystal
⇑ Corresponding author. Tel.: +86 24 8938 6342; fax: +86 24 8938 3760. plane which form model predictions and using Bravais Friedel
E-mail address: ltmlx@hotmail.com (X. Li). Donnay Harkar (BFDH) models. The most important surface during

http://dx.doi.org/10.1016/j.apt.2016.03.020
0921-8831/Ó 2016 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan.

Please cite this article in press as: X. Li et al., Preparation of active magnesium oxide with caustic calcined magnesia by ammonia circulation method,
Advanced Powder Technology (2016), http://dx.doi.org/10.1016/j.apt.2016.03.020
2 X. Li et al. / Advanced Powder Technology xxx (2016) xxx–xxx

Table 1
D50 of MH by different Mg salt solution.

Samples of Fig. 1 Sample (a) Sample (b) Sample (c)

Mg salt solution MgCl2 Mg(NO3)2 MgSO4
D50 (lm) 0.68 2.6 20.08

(a) MgCl2 (b) Mg(NO3)2 (c) MgSO4

Fig. 1. SEM micrographs of MH by different Mg salt solution.

Table 2a
D50 of MH by adding different cationic.

Samples None NH4Cl KCl BaCl2 CaCl2

D50 (lm) 0.68 0.71 0.79 0.69 0.61

Table 2b
D50 of MH by adding different anionic.

Samples None MgAc2 Mg(NO3)2 MgSO4 C2H2O4

D50 (lm) 0.68 0.58 0.82 2.05 2.84

Table 3
The MH crystal surface area and total energy of different crystal plane.

hkl dhkl Surface area Esurf (Total)/Kcal/moL

(0 0 1) 4.766 51.297
2.2932
(1 0 0) 8.163 29.949
1.4102
(1 0 1) 4.115 59.400
1.6869
(1 1 0) 3.745 65.273
1.2277
(1 0 2) 2.287 106.87
1.8156
(1 0 3) 1.559 156.77
1.8347
(1 1 1) 2.944 83.018
1.2346
(2 0 1) 3.100 78.862
1.4862

(001) (100) (101) (110)

(102) (103) (111) (201)

Fig. 2. The growth habit and directions of each slab model of MH single crystal cell by BFDH method.

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 X. Li et al. / Advanced Powder Technology xxx (2016) xxx–xxx 3

growth processes was illustrated. The vacuum slab model of each

plane (0 0 1), (1 0 0), (1 1 0), (1 0 1), (1 0 2), (1 0 3), (1 1 1) and (2 0 1)
of MH unit cell was simulated. On this basis, the nature of the
plane (0 0 1) and (1 0 1) of clean MH was simulated with the use
of CASTEP software. Finally, the influence of Cl2
and SO2
4 on the
plane MH (0 0 1) and (1 0 1) was simulated.

2.3. Characterization

The morphology and element analysis of the MH and MgO

products were examined by scanning electron microcopy at accel-
Fig. 3. The ideal growth morphology of MH. eration voltage of 10 kV (SEM, a LEO, 1530 VP system, with an
energy dispersive spectroscopy detector, EDS) and X-ray diffrac-

12 16

14
10
12
8
10

6 8

6
4
4
2
2

0 0
-40 -20 0 20 -40 -20 0 20
Energy/eV Energy/eV
(a) PDOS of (001) (b) PDOS of (101)

12
6 12 6
3 3
10
6XP
6XP 10

8
8

6
B
B

4
4

2 2

0 0
-40 -20 0 20 -40 -20 0 20
Energy/eV Energy/eV
(c) PDOS of (001) (d) PDOS of (101)

90 70
6
6 3
80
3 60 6XP
70 6XP
50
60

50 40
B
B

40 30

30
20
20
10
10

0 0
-50 -40 -30 -20 -10 0 10 20 -50 -40 -30 -20 -10 0 10
Energy/eV Energy/eV
(e) PDOS of (001) (f) PDOS of (101)

Fig. 4. The partial density of states (PDOS) of the plane (0 0 1) and (1 0 1) after MH adsorping different ions (a) none, (b) none, (c) Cl
, (d) Cl
, (e) SO


4 , (f) SO4 .

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4 X. Li et al. / Advanced Powder Technology xxx (2016) xxx–xxx

tion (XRD, a Bruker D8Advance diffractometer, with CuKa radia-

tion), respectively. The size distribution of MH and MgO were char-
acterized by laser particle size analyzer (BT-9300H, Dandong Baite
Products Co., Ltd., China). The precursors of the crystal structure
were analyzed by Materials Studio molecular modeling software.
The concentrations of soluble Mg2+ were analyzed by EDTA
titration.

3. Results and discussion

3.1. Preparation of precursors

3.1.1. Effect of different solution

As shown in Table 1, MH was synthesized by different Mg salt
solution at 75 °C.
Compared with magnesium sulfate and magnesium nitrate, the
particle size of MH products using magnesium chloride as a mag-
nesium source was significantly smaller (0.68 lm). It can reach
20 lm with magnesium sulfate as magnesium source. The MH
using magnesium sulfate as a magnesium source can make parti-
cles easier to agglomerate, resulting in the increase of particle size.
It can be clearly seen in Fig. 1(a) that the MH produced with
MgCl2 exhibited well dispersed quadrilateral massive morphology.
The MH produced with Mg(NO3)2 exhibited well dispersed hexag-
onal nanoplates morphology and the MH produced with MgSO4
exhibited flower spherical morphology. Since the interaction
between anion and surface charge of MH through electrostatic
force, the anions like Cl
, NO
2

3 and SO4 can be regarded as a sur-
face modified agent. By the action of these modified agents, the
nucleation and growth of crystals was affected, thus the crystals
growth habit was changed and different morphologies of MH par-
ticles were got.
3.1.2. Effect of ions
As shown in Tables 2a and 2b, MH was synthesized by adding
different ions in MgCl2 solution at 75 °C.
It can be clearly seen in Table 2a that the particle size increased
insignificantly by adding different cation. Table 2b displays the dif-
ferent anionic can significantly increase the particle size. Adding
MgSO4 or C2H2O4 can significantly increase the particle size, and
its D50 reached 2–3 lm.
MH is polar crystal with a polar axis and both ends of pole have
different interface structure. Surface of positive electrode is Mg2+,
surface of cathode is OH
. Adding different ions in solvent could
adjustable the grain boundary surface and solvent interactions to
control the relative growth rate of crystal, and then control growth
habit of crystal. In the process of crystal growth, anion adsorption
on the crystal surface through electrostatic interaction. This will
impact nucleation and growth of crystal and change the growth
habit of crystal and get different morphology of samples.
Fig. 6. XRD patterns of MgO prepared from different magnesium salt: produced
with (a) MgCl2, (b) Mg(NO3)2, (c) MgSO4.
3.2. Growth Mechanism of precursors
3.2.1. BFDH method analyses of MH
Possible growth faces and growth habit of each slab model for
MH single crystal cell were calculated by BFDH method. Fig. 2
shows the growth habit sketch of each slab model and the relative
orientations of growth crystal planes. The vacuum slab model of
plane (0 0 1) tended to be grow hexagonal massive crystals. Plane
(1 0 0), (1 0 1), (1 0 3) and (2 0 1) tended to be grow hexagonal
prisms crystals in vertical direction. Plane (1 1 0) tended to be
inclined top cuboid crystal. Plane (1 0 2) tended to be vertical
cuboid crystal and plane (1 1 1) tended to be inclined top hexagonal
massive crystals. Through the calculation of each surface of dis-
tance, the ideal growth morphology of MH was as shown in
Fig. 3. As can be seen, the plane (0 0 1) was the main growth crystal
plane, the other planes were not the main growth crystal plane, as
the plane (1 1 0), (1 0 0) and (0 1 0).
3.2.2. Crystal plane analyses
Table 3 show that the total energy ratio on the surface was ETot
(0 0 1) < ETot (1 0 3) < ETot (1 0 2) < ETot (1 0 1) < ETot (2 0 1) < ETot
(1 0 0) < ETot (1 1 1) < ETot (1 1 0). The plane (0 0 1) eventually became
main crystal due to the low surface energy resulting in the slow
growth rate and easily reserved in the process of growth. Repre-
sented by (1 1 0) crystal plane of the side faces had the strong
polarity, which had the high surface energy resulting in the fast
growth rate and in a unstable state. Compared with plane (0 0 1),
the other side planes like (1 1 0) were easy to be disappeared due

(a) produced with MgCl2 (b) produced with Mg(NO3)2 (c) produced with MgSO4
Fig. 5. SEM micrographs of MgO prepared from different Mg salt.

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to the planes with a fast growth rate and more easy to be superim- conducive to the MH crystals ultimately growing into hexagonal
pose by new planes. In addition, the morphology of MH can more plate crystals.
easily grow to be hexagonal flake crystal.
3.3. Characterization of active MgO

3.2.3. Effect of adsorping different ions 3.3.1. SEM analyses of MgO

Fig. 4 exhibit that the DOS distribution form of MH clean surface
(0 0 1) and (1 0 1) without any ions was very similar. After Cl
was
adsorpted, the DOS distribution of planes (0 0 1) and (1 0 1) were
significantly different. Due to the adsorption of Cl
, it can make
ionic bond with a weak covalent between H and Cl, O and Cl, which
increased the H–Cl, O–Cl bond of planes (0 0 1) and (1 0 1). After
adsorption, the average bond population of O–Mg bond of planes
(0 0 1) and (1 0 1) was down from clean surface. It can improve
the exposure proportion of planes (0 0 1) and (1 0 1), wherein the
reduction of plane (0 0 1) was larger. So the exposure proportion
of it was higher than plane (1 0 1), which was more conducive to
the MH crystals ultimately growing into hexagonal plate crystals.
After the adsorption of SO2
4 , the DOS distribution of planes
(0 0 1) and (1 0 1) were also significantly different. The average
bond population of O–Mg bond of planes (0 0 1) and (1 0 1) was
risen from clean surface after adsorption. It can reduce the expo-
sure proportion of planes (0 0 1) and (1 0 1), wherein the increase
of plane (0 0 1) was larger. So the exposure proportion was lower
than plane (1 0 1) and the growth was inhibited, which was not
Compared with Figs. 1 and 5, we found that the morphology of
MgO produced with different magnesium salt kept the same mor-
phology with its precursor. With different precursors the size of
MgO was increased from 1.10 to 2.45 lm. It can be clearly seen
in Figs. 1(a) and 5(a) that the morphology of precursor produced
with MgCl2 and MgO were all bulk, which had uniform particle
size. Figs. 1(b) and 5(b) show that the morphology of precursor
produced with Mg(NO3)2 and MgO were all nanoplates. Figs. 1
(c) and 5(c) show that the morphology of precursor produced with
MgSO4 and MgO were all flower spherical, which had large particle
size and serious particles agglomeration. It shows that the shape-
controlled active MgO can be prepared by the specific morphology
precursor.
3.3.2. XRD analyses of MgO
As shown in Fig. 6, MgO was prepared by using different mag-
nesium salt. All diffraction peaks of each sample could be indexed
as MgO with lattice constants (NO. 78-0403). No peaks from other
phases can be observed.

Fig. 7. Effects of (a) calcinations temperature, (b) calcinations time, (c) heating rate on the active of the MgO products.

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3.3.3. Activity analyses of MgO
The activity of MgO was determined by the citric acid method.
Lowed CAA means the high activity. The influences of the calcina-
tions temperature, the calcinations time, and the heating rate were
investigated. From Fig. 7(a), it can be seen that, as the calcinations
temperature increased, the CAA went down first and then increased,
possibly because a high reaction temperature made parti-
cles agglomeration. In this work, 600 °C was used as the calcinations
temperature. At this time, the active of MgO was the maximum, and
the active of MgO of order was: bulk > flake > flower spherical. From
Fig. 7(b) and (c), it also can be seen that, as calcinations time and
heating rate increased, the CAA also went down first and then
increased, and the active of MgO of order was: bulk > flake > flower
spherical. Thus, 10 °C/min and 2 h was used as the constant
temperature and the heating rate.
On the basis of these results in Fig. 7, the activity of MgO pro-
duced with MgCl2 was exceeded by the activity produced with
Mg(NO3)2 and MgSO4. Therefore, using MgCl2 as the material for
preparing MgO had more activity.
4. Conclusions
A process using light calcined powder to prepare shape-
controlled and high active MH has been developed. The results
showed that the precursors produced with MgCl2 had the small
particle size and its morphology was uniform bulk. The adsorption
of SO2

4 significantly increased the exposure proportion of planes
(0 0 1) and (1 0 1), and its growth was inhibited. The precursors
with different Mg salt had the same morphology with the MgO.
In addition, the MgO produced with MgCl2 and Mg(NO3)2 had the
highest activity, the CAA was respectively 1500 85 and 1700 75.
Acknowledgments
Financial support from the Program for Liaoning Innovative
Research Team in University (LNIRT; Project LT2013010) and the
Education Administration of Liaoning Province (Project
L2012143) is gratefully acknowledged.
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