Preparation and precipitation experiments

The schematic diagram of the integrated process is depicted in Fig. 1. The

main steps in the process are production of MgAlCO 3-LDHs (Mg recovery),
boron extraction (boron removal), acidification (residual CO32– removal),
evaporation and precipitation. The precipitation step includes removal of
SO42 − and production of lithium carbonate.

Fig. 1. Flowsheet for the co-preparation of LDHs and lithium carbonate.

2.3.1. Production of MgAlCO3-LDHs

MgAlCO3-LDHs were produced from the brine by double-drop method. Briefly, deionized
water and AlCl3·6H2O salt were added to brine A, and then both of the resultant mixture and
solution A were simultaneously added dropwise into a round-bottom flask at a rate that
allowed reaction mixture pH to be maintained at 10. Because brine A is saturated with
bischofite (413.12 g·L− 1 MgCl2), water was added to ensure AlCl3·6H2O solid easily dissolved
into brine A. The mass ratio of water to brine A ranged from 0.5 to 2.0, and solution A was a
mixed base solution of sodium carbonate and sodium hydroxide. Precipitation was carried out
at 40 °C and the slurry was aged at 80 °C in a water bath for 24 h. The precipitate was then
filtered, thoroughly washed with water, and dried at 80 °C for 24 h.

2.3.2. Removal of boron, CO32 −, and SO42 −

After the recovery of Mg, an adsorption method with LSC-800 resin (He et al., 2011) was
used to remove boron element from the residual brine. Boron removal consisted of three
stages: (1) LSC-800 resin treatment, (2) boron adsorption and elution, and (3) resin
regeneration. First, LSC-800 resin was steeped in water for 6 h, treated with a 4% NaOH
solution, and then washed with deionized water until the washing solution pH was
approximately 7.0. Then, boron adsorption was initialized with a flow rate of 5.9 mL/min and
ended when the mass boron concentration in the effluent was 0.05 times higher than in the
feed. After boron adsorption, the resin was eluted with 0.5 mol/L HCl solution in the form
of boric acid. Finally, the LSC-800 resin was regenerated with the 4% NaOH solution for
recycle purpose. The rate of boron removal is given by:
R=c0·ρ0·m0−c1·ρ1·m1/c0·ρ0·m0×100%
where c0 (g/L), ρ0 (g/mL), and m0 (g) are boron concentration, density, and mass of brine prior
to boron removal; and c1 (g/L), ρ1 (g/mL), and m1 (g) are boron concentration, density, and
mass of brine after boron removal, respectively.
In order to remove residual CO32– ion, the brine after boron removal was acidified using
12 mol/L HCl and discharging in the form of CO2 until the solution pH was below 4.0.
After boron and CO32– removal, the residual brine was primarily composed of Na+, K+, Li+,
Cl−, and SO42 −. The Li+ concentration was about 1.0 g/L. Evaporation had to be performed to
concentrate lithium. When the brine was evaporated closed to saturation of lithium salts
(around 10 g/L Li+) based on the metastable phase diagram of the Na+, K+, Li+/Cl+, SO42 −//H2O
system (Liu et al., 2014), a barium chloride solution was added to the brine to precipitate
SO42 −. The mole ratio of Ba2 +/SO42 − remained 1.0.

2.3.3. Precipitation of lithium carbonate

After the removal of Mg2 +, borate, CO32– and SO42 − ions, the residual brine was enriched in
lithium and primarily composed of Na–K–Li–Cl. This brine was further concentrated via
evaporation (11–30 g/L Li+) and used for production of lithium carbonate through
precipitation. The lithium-rich brine was precipitated at 90 °C with a 30% sodium carbonate
solution. The molar ratio of CO32 −/2Li+ ranged from 0.9 to 1.3. After aging for 0.5 h, the
precipitate was filtered, thoroughly washed well with water, and dried at 90 °C for 24 h.
Finally, the lithium carbonate product was obtained and characterized.