Introduction
Conversion roasting: The spodumene concentrate is manually sent
from the concentrate silo via the bucket elevator to the
concentrate silo, and then added to the tail of the lithium
carbonate rotary kiln via the disc feeder and the screw feeder. The
tail gas preheating section high temperature gas drying
concentrate, the concentrate is crystallized and calcined at a
temperature of about 1200 ° C in the calcination section, and is
converted into β-type spodumene by α type (monoclinic system,
density 3150 kg/m3). The tetragonal system has a density of 2400
kg/m3, that is, a baking material, and the conversion rate is about
98%.Technical
Lithium carbonate production process
Baking section
Conversion roasting: The spodumene concentrate is manually sent
from the concentrate pool to the bucket elevator to the concentrate
bin, and then added to the tail of the lithium carbonate rotary
kiln via the disc feeder and the screw feeder, and preheated by the
kiln tail. Segment high-temperature gas drying concentrate, the
concentrate is crystallized and calcined at a temperature of about
1200 °C in the calcination section, and is converted into β-type
spodumene by α-type (monoclinic system, density 3150kg/m3)
(tetragonal system) The density is 2400 kg/m3, that is, the baking
material, and the conversion rate is about 98%.
Acidification roasting: After the cooling material is cooled by the
cooling section, it is discharged from the kiln head, and then
finely ground to 0.074mm in the natural cooling and ball mill to be
more than 90%, and then transported to the acidification roasting
kiln tailing bin, and then through the feeder and The screw
conveyor is added to the mixed acid machine and concentrated
sulfuric acid (93% or more) in a certain ratio (concentrated
sulfuric acid in excess of 35% of the lithium equivalent in the
baking material, about 0.21t of concentrated sulfuric acid per ton
of baking material), and then added to the acidification roasting.
In the chamber, the closed acidification roasting is carried out at
a temperature of about 250 to 300 ° C for 30 to 60 min. The β-type
spodumene in the baking is reacted with sulfuric acid, and the
hydrogen ions in the acid replace the lithium ions in the β-type
spodumene. Li2O is combined with SO42- as water-soluble Li2SO4 to
obtain acidified clinker.
Slurry leaching and washing: the clinker is cooled and slurryed to
dissolve the soluble lithium sulfate in the clinker into the liquid
phase. To reduce the corrosion of the solution to the leaching
equipment, the limestone slurry is used to neutralize the residual
acid in the clinker to adjust the pH. Adjusted to 6.5 ~ 7.0, and at
the same time remove most of the iron, aluminum and other
impurities, the leaching solution solid ratio of about 2.5,
leaching time of about 0.5h. The leaching slurry is separated by
filtration to obtain a leaching solution containing about 100 g/L
of Li 2 SO 4 (Li 2 O 27 g/L), and the filter cake is leaching slag,
and the water content is about 35%. Lithium sulfate is contained in
the leaching residue adhering liquid. In order to reduce lithium
loss, the leaching slag is washed by reverse stirring, and the
washing liquid is returned to the slurry for leaching.
Leachate purification: When the baking material is acidified and
calcined, in addition to the alkali metal can react with sulfuric
acid to produce soluble corresponding sulfate, other iron,
aluminum, calcium, magnesium and the like are also reacted with
sulfuric acid to produce the corresponding sulfate. Although some
impurities in the clinker can be removed during the leaching
process, the remaining impurities remain in the leachate and need
to be further purified to ensure product quality. The leachate
purification is carried out by alkalization decalcification method,
alkalizing the leaching solution with alkalizing agent lime milk
(containing CaO 100-150 g/L), and raising the pH to 11-12 to
hydrolyze magnesium and iron into hydroxide precipitates. Further,
a sodium carbonate solution (containing Na2CO3 300 g/L) is reacted
with calcium sulfate to produce a calcium carbonate precipitate,
thereby removing calcium in the leachate and calcium introduced by
the alkalizing agent lime milk. The alkalized calcium removal
slurry is separated by liquid solid solution, and the obtained
solution is a purification liquid. The calcium to lithium ratio is
less than 9.6×10-4, and the filter cake is calcium residue, which
is returned to the slurry for leaching.
Evaporation and concentration of purification liquid: The
purification liquid has low concentration of lithium sulfate and
low lithium precipitation rate. It cannot be directly used for
lithium precipitation or lithium chloride. It is necessary to
adjust the purification liquid to pH 6-6.5 with sulfuric acid
first, and evaporate and concentrate by three-effect evaporator.
The concentration of lithium sulfate in the concentrate is 200 g/L
(containing Li2O 60 g/L). The concentrated liquid is separated by
pressure filtration, and the filtrate is used to supply the liquid
to the next step, and the filter cake is returned to the slurry for
leaching.
2 Lithium carbonate production section
The completion liquid and the pure lye (containing Na2CO3 300g/L)
were added to the evaporating lithium tank to carry out evaporative
deposition of lithium (constant temperature after boiling for 2 h),
and the precipitate was precipitated due to the low solubility of
lithium carbonate, and the lithium precipitation rate was about
85%. After the lithium is precipitated, the crude lithium carbonate
(containing less than 10% of the filtrate) and the primary
lithium-plated mother liquor are separated by a centrifugal
machine.
The primary lithium liquid solution contains a large amount of
sodium sulfate and higher lithium sulfate (about 15% of the total
amount), and the pure alkali liquid (containing Na2CO3 300g/L) is
added to carry out the second lithium deposition to obtain the
second crude product and the second mother liquid, the mother
liquid. After acid neutralization and sodium hydroxide pH
adjustment, the by-product anhydrous sodium sulfate and sodium
precipitation mother liquor are separated by evaporation and
centrifugation, and anhydrous sodium sulfate is dried by air flow
and packaged to obtain by-product Yuanming powder. The sodium
mother liquor is returned to the mother liquor for one time.
The primary crude lithium carbonate and the second crude product
adhesion liquid contain impurities such as Na2SO4, and then are
stirred with purified water at about 90 ° C, and the washing liquid
is sent to the alkali, and after washing, the wet lithium carbonate
is separated by a centrifuge, and then the wet lithium carbonate is
separated. After drying by the far-infrared dryer, the magnetic
separation removes the iron debris and the like which are detached
from the dryer, and finally is crushed by the airflow and packaged
into the warehouse.
This project mainly adds battery-grade lithium carbonate production
capacity. From the perspective of the overall production process,
the battery-grade lithium carbonate and the industrial grade
lithium carbonate are basically the same, the difference is that
the process control conditions of the two sections of evaporation
and sinking lithium are different, that is, the specific gravity of
the liquid and the passing of the flame are measured by the
hydrometer when the purification liquid is concentrated by
evaporation. The photometer measures the concentration of Li2O in
the liquid to ensure that the concentration of the finished liquid
is within the process requirements. When the lithium is used, the
electromagnetic flowmeter displays the different opening degrees of
the regulating valve to control the feeding speed, and the speed of
the motor is controlled by the frequency converter to control the
stirring speed of the agitator. . The above process control
conditions are all key technologies of the company.
3 anhydrous lithium chloride sections
The completion liquid obtained in the baking section is subjected
to a metathesis reaction with the calcium chloride solution, and
after the reaction is completed, CaSO4•2H2O is separated and sent
to obtain a CaSO4 product. After separation, a dilute solution of
LiCl is obtained, and β-type active Al2O3, Na2CO3 and NaOH solution
are sequentially added to remove impurities such as SO42-, Ca2+ and
Mg2+ in the dilute solution of LiCl, and then the concentration of
LiCl is increased to 400-500 g/L by evaporation and concentration.
Cooling filtration was carried out, and solid NaCl was separated to
obtain a concentrated solution of LiCl. The LiCl concentrated
solution is transported to the refining tank and the company's
self-produced refined preparation (the company's patented
technology, inorganic components, containing no toxic and harmful
heavy metals) is substituted with Na+ to control the Na+/LiCl ratio
in the solution end point solution to be less than 30 ppm. After
separation, a LiCl completion liquid is obtained, and finally, the
finished liquid is spray-dried to obtain a uniform anhydrous
lithium chloride product.