minerals
Article
Optimization of a Rare Earth and Aluminum Leaching Process
from Weathered Crust Elution-Deposited Rare Earth Ore with
Surfactant CTAB
Xiaoyan Wu 1, *, Jian Feng 2, *, Fang Zhou 1 , Chufan Liu 1 and Ruan Chi 1
Citation: Wu, X.; Feng, J.; Zhou, F.;
Liu, C.; Chi, R. Optimization of a Rare
Earth and Aluminum Leaching
Process from Weathered Crust
Elution-Deposited Rare Earth Ore
with Surfactant CTAB. Minerals 2024,
14, 321. https://doi.org/10.3390/
min14030321
Academic Editor: Kenneth N. Han
Received: 27 February 2024
Revised: 15 March 2024
Accepted: 17 March 2024
Published: 20 March 2024
Copyright: © 2024 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Minerals 2024, 14, 321. https://doi.org/10.3390/min14030321
1 Key Laboratory of Green Chemical Process of Ministry of Education, School of Xingfa Mining Engineering,
Wuhan Institute of Technology, Wuhan 430073, China
2 School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China
* Correspondence: 16092803@wit.edu.cn (X.W.); fengjian5658@csu.edu.cn (J.F.)
Abstract: Ammonium sulfate is typically employed as a leaching agent in the in situ leaching of
weathered crust elution-deposited rare earth ore. However, it is associated with challenges such as
low efficiency in mass transfer for rare earth (RE) leaching, high usage of the leaching agent, and
prolonged leaching duration. To address the issues mentioned above, the surfactant cetyltrimethyl
ammonium bromide (CTAB) was compounded with 2% ammonium sulfate to form a leaching agent
in this paper. The effects of CTAB concentration, temperature, pH, and leaching agent flow rate on
the rare earth (RE) and aluminum (Al) leaching mass transfer process from RE ore were investigated
using chromatographic plate theory. The results revealed that CTAB addition improved the RE
mass transfer process while moderately inhibiting the Al mass transfer efficiency. Increasing the
temperature and pH of the leaching solution led to higher theoretical plate numbers for RE and Al
leaching, lowered theoretical plate height (HETP), and enhanced leaching mass transfer efficiency.
However, under high temperature and alkaline conditions, the mass transfer efficiency begins to
decrease, indicating that high temperature and alkaline conditions are not conducive to the synergistic
enhancement of RE and Al leaching by CTAB. Considering that clay minerals have good pH buffering
properties, adjusting the pH of the leaching solution during rare earth ore leaching operations was
deemed unnecessary. The optimal mass transfer conditions for leaching RE and Al were identified as
2% ammonium sulfate concentration, 0.00103 mol/L CTAB concentration, pH range of 5.2–5.5 for the
leaching solution, 0.6 mL/min leaching solution flow rate, and room temperature. The rare earth
leaching mass transfer effect could be enhanced during summer operations.
Keywords: weathered crust elution-deposited rare earth ore; surfactant CTAB; rare earth; leaching;
mass transfer
1. Introduction
Rare earth elements (REEs) are composed of scandium (Sc), yttrium (Y), and 15 lan-
thanide elements [1,2]. Rare earths are widely used in the metallurgical industry, lumi-
nescent materials, agriculture, and other fields because of their unique 4f -layer electronic
structure and good optical, electrical, and magnetic properties [3,4]. Medium and heavy
rare earths are more competitive in the market compared to light rare earths due to their
scarcity in raw materials and wider utilization.
Rich in medium and heavy rare earths, weathered crust elution-deposited rare earth
ore is primarily found in seven southern provinces of China [5,6]. Medium and heavy rare
earth reserves make up over 80% of the global rare earth reserves and are valuable mineral
resources in China [7–9]. Weathering-type rare earth ore is formed by weathering RE-
containing granites or volcanic rocks for many years and clay minerals make up 40%–70% of
its composition. REEs primarily bond to clay minerals through either hydration or hydroxyl
hydration cations and it is difficult to enrich and recover rare earths by conventional
https://www.mdpi.com/journal/minerals
Minerals 2024, 14, 321 2 of 18

physical methods. The scientific and technological workers have carried out long-term
research and practice on RE ore, developed a method of extracting rare earths from clay
minerals by ion exchange using electrolyte aqueous solution, and gradually developed
three generation processes for leaching rare earths [10,11].
Currently, the third-generation rare earth leaching process being widely used is the
in situ leaching process. This process involves injecting the leaching solution into the ore
injection well, allowing it to diffuse into the ore body through seepage. Then, the RE
ions adsorbed on the clay minerals are exchanged and leached from top to bottom [12].
When ammonium salt is utilized as the leaching agent [13,14], the ion exchange reaction
equation is represented in Formula (1). The advantage of the in situ leaching process is that
it no longer requires “mountain moving”, thereby protecting the mountain, improving the
utilization rate of RE resources, and achieving efficient rare earth recovery [15,16].

[Al4 (Si4 O)10 (OH)8 ]m ·nRE3+ (s) + 3nNH4 + (aq) ⇄ [Al4 (Si4 O10 )(OH)8 ]m ·3nNH4 + (s) + nRE3+ (aq) (1)

Due to the different genesis of the deposits, the weathered crust elution-deposited
rare earth ore bodies formed have different properties and the rare earth ores in some areas
are characterized by thick weathered layers and poor permeability. This characteristic will
reduce the effective seepage rate and RE mass transfer efficiency of the in situ leaching
process, which will affect the utilization rate and revenue of RE resources. Therefore,
exploring the seepage and mass transfer behavior of RE ore is crucial for advancing the rare
earth industry, solving the seepage and mass transfer problems of the RE leaching process,
and optimizing the in situ leaching process.
At present, ammonium salts are mainly utilized as leaching agents for extracting
REEs, with ammonium sulfate being the most commonly applied in industry. Li et al. [17]
also found that as the cation concentration of the leaching agent increased from 0 to 5%,
there was a gradual decrease in the permeability coefficient of the leaching solution. This
phenomenon occurs because as the concentration of cations in the solution increases, more
rare earth ions are displaced, resulting in an accumulation of negative charges on the surface
of mineral particles. This leads to the formation of a thicker water film and enhances the
fluid retention effect. In addition to ammonium salts, rare earth workers have also studied
the effects of magnesium and calcium salts on the seepage process. Liang et al. [18] found
that magnesium sulfate and calcium chloride, as leaching solutions, can strongly compress
the double layer of weathered crust elution-deposited rare earth ore particles after entering
the ore body. This helps to prevent the migration of fine particles during leaching, decrease
the likelihood of pore blockage, and enhance the permeability of the ore body.
Leaching aids have the characteristics of low usage and low environmental harm. In
the rare earth leaching process, adding a certain amount of leaching aids to the leaching
solution can improve the infiltration and RE mass transfer process and improve the effective
infiltration rate and RE mass transfer efficiency. Tang et al. [19] found that the use of
sesbania gum as a leaching aid in the leaching process of low-grade RE ore could greatly
enhance the RE leaching rate. As an emulsifier, thickener, and stabilizer in food processing,
sesbania gum is able to strengthen the penetration performance of the leaching solution
and improve the RE leaching rate. Tian et al. [20] modified this by adding carboxymethyl
to sesbania gum to reduce the composite agent viscosity and enhance the hydrophilicity
and permeability of the composite agent. Compared with sesbania gum, modified sesbania
glue has stronger leaching aid performance. Feng et al. [21] found that the equilibrium
time of ammonium formate as a leaching aid compound with ammonium sulfate was 5.3 h
shorter than that of ammonium sulfate.
A surfactant is a substance that can make the interfacial state of a solution system
change significantly by adding a small amount. The solution has fixed hydrophilic and
lipophilic groups that can be oriented in a specific direction on its surface. Surfactants
have an amphiphilic molecular structure, featuring hydrophilic groups at one end and
hydrophobic groups at the other end. Wu et al. [22] used surfactants as a percolation aid in
Minerals 2024, 14, 321 3 of 18

the uranium heap leaching process, which improved the soluble leach permeability and the
uranium leaching efficiency. Fang et al. [23] added surfactants in the bioleaching of arsenic-
containing gold concentrates, which improved the arsenic leaching rate. Ai et al. [24]
employed surfactants during the copper ore leaching process and observed that the inclu-
sion of surfactants not only improved the permeability in column leaching significantly but
also enhanced the copper leaching rate by 8.4%. Chen et al. [25] used cationic surfactant
CTAB to assist in the leaching of manganese from low-grade rhodochrosite and the results
showed that surfactant CTAB was beneficial for improving the manganese leaching rate
and that the leaching rate could reach 99.07%. Liu et al. [26] used anionic surfactant SDS
to promote the leaching of potassium in phosphorus and potassium-associated minerals.
The addition of SDS would produce adsorption in ore cracks, allowing the acid-leaching
solution to penetrate the interior of the mine and undergo chemical reactions inside the
mine, thereby enhancing the potassium leaching rate. Thus, the utilization of cationic and
anionic surfactants to assist in leaching has achieved good reinforcement effects in the
leaching process.
Through preliminary exploration, it was found that surfactant CTAB had a better effect
on RE leaching. Thus, the effect of CTAB and ammonium sulfate compounding on the
leaching mass transfer process of RE and Al under different conditions was investigated.
By analyzing the outflow curve of RE and Al and calculating with the chromatographic
plate theory, the influence law of complex leaching of RE and Al with CTAB and (NH4 )2 SO4
under different conditions was obtained to enhance the leaching process by minimizing
the use of leaching agent, improving its percolation rate, and reducing the leaching time.
It provides a theoretical basis for the development of high-efficiency leaching agents and
technologies for weathered crust elution-deposited rare earth ore and offers valuable
insights for research on enhancing mass transfer through surfactant compound processes.

2. Materials and Methods

2.1. Materials
The weathered crust elution-deposited rare earth ore samples used in this study were
from Jiangxi province, China. The mineral composition of the rare earth ore sample is shown
in Table 1. Ammonium sulfate ((NH4 )2 SO4 ), cetyltrimethyl ammonium bromide (CTAB),
ascorbic acid, sulfosalicylic acid, xylenol orange, ethylenediaminetetraacetic acid disodium,
zinc oxide, hexamethylenetetramine, hydrochloric acid, and ammonium hydroxide were
purchased from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China, with analytical
grade. A standard solution of zinc was purchased from the National Center of Analysis
and Testing for Nonferrous Metals and Electronic Materials.

Table 1. Mineral composition.

Mineral Types Quatz Metahalloysite Kaolinite Muscovite Dolomite Mica Microcline

Composition ratio/% 26.7 5.9 18.7 14.0 2.0 22.8 9.9

2.2. Column Leaching Experiment

A total of 250 g of dried RE ore sample was slowly and evenly packed into a glass
column with a diameter of 45.0 mm. Several pieces of filter paper were placed on the surface
of the ore sample. The glass column was then fixed to the iron frame and placed vertically.
The peristaltic pump was used to send a certain amount of CTAB and 2% ammonium
sulfate compound leaching liquid to the top of the glass column at a uniform speed. Then,
a measuring cylinder was used to collect the leachate from the bottom of the glass column.
The schematic diagram of the experimental apparatus is shown in Figure 1. When the
leachate flowed out, the time was started, the leachate was collected at regular intervals,
and the volume of the leachate was measured and analyzed for the content of rare earths
and aluminum.
Minerals 2024, 14, x FOR PEER REVIEW 4 of 18

Minerals 2024, 14, 321 intervals, and the volume of the leachate was measured and analyzed for the content
4 of 18 of
rare earths and aluminum.

Figure1.1.Schematic
Figure Schematicdiagram
diagramofofthe experimental
the apparatus.
experimental apparatus.

2.3. Analytical Methods

2.3. Analytical Methods
The content of RE in the leachate was determined by EDTA titration [21]. The appro-
The content of RE in the leachate was determined by EDTA titration [21]. The appro-
priate amount of rare earth leachate was accurately transferred into the conical flask by
pipette.amount
priate Then, 25ofmLrareof earth leachate
deionized was
water, 0.1accurately
g of ascorbictransferred
acid, and 2into
mL the conical flask by
of sulfosalicylic
pipette. Then, 25 mL of deionized water, 0.1 g of ascorbic acid,
acid solution were added to the sample in turn. Ascorbic acid and sulfosalicylic and 2 mL of sulfosalicylic
acid are
acid solution
mainly used towere
maskadded
impurity to ions
the sample in turn.
such as iron Ascorbic acid
and aluminum. and sulfosalicylic
Hydrochloric acid are
acid (volume
mainly
ratio 1:1)used to mask (volume
or ammonia impurityratioions1:1)
such
was asused
iron to
and aluminum.
adjust Hydrochloric
the pH value acid (vol-
of the solution
ume
to ratio then
5.0–5.5, 1:1) or
2.5ammonia (volume ratio 1:1) was
mL hexamethylenetetramine usedsolution
buffer to adjust the1–2
and pHdrops
valueofof1 the
g/Lsolu-
tion to orange
xylenol 5.0–5.5,indicator
then 2.5weremL added
hexamethylenetetramine
to the sample, and EDTA buffer solution
standard and 1–2
solution wasdrops
used of 1
to
g/Ltitrate until
xylenol the solution
orange indicator changed from purplish
were added red to and
to the sample, bright yellow,
EDTA whichsolution
standard was the was
titration endpoint,
used to titrate and
until thethe contentchanged
solution of rare earths
frominpurplish
it was analyzed. Excess
red to bright concentrated
yellow, which was
EDTA standard solution was added quantitatively to the solution
the titration endpoint, and the content of rare earths in it was analyzed. Excess after titration of rare
concen-
earth, then bathed in water at 90 ◦ C for 10 min, then titrated with zinc standard solution
trated EDTA standard solution was added quantitatively to the solution after titration of
until the solution
rare earth, changed
then bathed infrom
water bright
at 90yellow
°C forto10purple–red, and the with
min, then titrated content
zincof standard
aluminumsolu-
was analyzed. The surface potential of the ore in contact with different solutions was
tion until the solution changed from bright yellow to purple–red, and the content of alu-
determined by a Zeta potentiometer (Zetersizer Nano-ZS90, Malvern, UK). The viscosity of
minum was analyzed. The surface potential of the ore in contact with different solutions
the solution was determined by using a Ubbelohde viscometer.
was determined by a Zeta potentiometer (Zetersizer Nano-ZS90, Malvern, UK). The vis-
cosity
3. of the solution was determined by using a Ubbelohde viscometer.
Results
3.1. Effect of the CTAB Concentration on the Leaching Process of RE and Al
3. Results
In order to investigate the effect of leaching-aid agent on the rare earth leaching process,
3.1. leaching
the Effect of the
massCTAB Concentration
transfer process ofonRE theand
Leaching
Al wasProcess of REusing
discussed and Ala 2% (NH4 )2 SO4
solution
In order to investigate the effect of leaching-aid agent on the concentration
compound with CTAB as a compound. The effects of CTAB on the pro-
rare earth leaching
leaching process of RE and Al are presented in Figure 2.
cess, the leaching mass transfer process of RE and Al was discussed using a 2% (NH4)2SO4
From Figure 2, it can be observed that the concentrations of RE and Al in the leachate
solution compound with CTAB as a compound. The effects of CTAB concentration on the
increase rapidly until reaching a peak and then drop rapidly to zero with the increase in
leaching process of RE and Al are presented in Figure 2.
the outflow of leachate. Compared with the single leaching agent of 2% ammonium sulfate,
From Figure 2, it can be observed that the concentrations of RE and Al in the leachate
the RE leaching curve peaks at a higher concentration and has a narrower pattern when
increase
using therapidly until reaching
CTAB compound a peak
as the andagent.
leaching then drop
This rapidly
suggeststothat
zero with the
adding increase
CTAB can in
improve the RE mass transfer process. However, the peak concentration of the leaching sul-
the outflow of leachate. Compared with the single leaching agent of 2% ammonium
fate, the
curve REisleaching
of Al lower and curve
the peaks at a higher
peak shape concentration
is wider, and that
which indicates has athenarrower
additionpattern
of
when using
CTAB the CTAB
can weaken the Al compound as the
mass transfer leaching
process, agent.
which This suggests
is conducive to thethat adding of
inhibition CTAB
canimpurity
the improvealuminum
the RE mass transfer
leaching. Atprocess. However,ofthe
the concentration peak mol/L
0.00103 concentration
of CTAB,ofthe
theREleach-
ing curve
leaching of Alshows
curve is lower and the
its highest peak
peak shape is wider,
concentration which indicates
and narrowest that resulting
peak shape, the addition
in of
higher
CTAB mass transferthe
can weaken efficiency
Al masscompared
transfer to other concentrations.
process, Additionally,
which is conducive the Al mass
to the inhibition of the
transfer
impurityefficiency
aluminum significantly
leaching. At decreased at this concentration.
the concentration Whenofthe
of 0.00103 mol/L concentration
CTAB, the RE leach-
of
ingCTAB
curveincreases
shows its from 0.00034
highest mol/L
peak to 0.00103 mol/L,
concentration the peak peak
and narrowest concentration of rare in
shape, resulting
earths increases, the peak shape of the leaching curve narrows,
higher mass transfer efficiency compared to other concentrations. Additionally, and the leaching mass
the Al
Minerals 2024, 14, x FOR PEER REVIEW 5 of 18

Minerals 2024, 14, 321
mass transfer efficiency significantly decreased at this concentration. When the concentra-
tion of CTAB increases from 0.00034 mol/L to 0.00103 mol/L, the peak concentration 5 of 18 of
rare earths increases, the peak shape of the leaching curve narrows, and the leaching mass
transfer efficiency increases. As the CTAB concentration continues to increase, the peak
transfer efficiency
concentration of REincreases.
graduallyAsdecreases,
the CTAB theconcentration
peak shapecontinues to increase,
of the leaching curve the peak
gradually
concentration of RE gradually decreases, the peak shape of the leaching curve gradually
widens, and the leaching mass transfer efficiency decreases. When the concentration of
widens, and the leaching mass transfer efficiency decreases. When the concentration of
CTAB is 0.00103 mol/L, CTAB reduces the surface tension of the leaching solution and the
CTAB is 0.00103 mol/L, CTAB reduces the surface tension of the leaching solution and the
leaching agent can better wet the clay mineral particles. The exchange reaction between
leaching agent can better wet the clay mineral particles. The exchange reaction between
NH
NH44 +and
+
andRERE3+isismore
3+
morethorough
thorough and the leaching
and the leachingmass
masstransfer
transferprocess
process is strengthened.
is strengthened.
Therefore,
Therefore, in the subsequent
in the subsequentoptimization
optimizationprocess
process research,
research, 0.00103
0.00103 mol/L
mol/L is the
is the optimal
optimal
process condition for CTAB.
process condition for CTAB.

8 (a)
7
CCTAB=0 mol/L
CCTAB=0.00034 mol/L
6
CCTAB=0.00069 mol/L
5 CCTAB=0.00103 mol/L
CRE O /(g/L)

CCTAB=0.00137 mol/L
4
CCTAB=0.00171 mol/L
3
2

3 CCTAB=0.00343 mol/L

0 20 40 60 80 100 120 140 160 180

Retention volume/mL

0.7 (b)

0.6 CCTAB=0 mol/L

CCTAB=0.00034 mol/L
0.5
CCTAB=0.00069 mol/L
CAl O /(g/L)

0.4 CCTAB=0.00103 mol/L

CCTAB=0.00137 mol/L
3

0.3 CCTAB=0.00171 mol/L

2

CCTAB=0.00343 mol/L
0.2

0.1

0.0

0 20 40 60 80 100 120 140 160 180

Retention volume/mL
Figure2.
Figure Effect of
2. Effect of the CTAB
CTAB compound
compoundconcentration
concentrationonon
the leaching
the curves
leaching of (a)
curves RE RE
of (a) andand
(b) Al.
(b) Al.

The chromatographic
The chromatographic plate
platetheory
theorycan
canbebeapplied
appliedtoto
analyze thethe
analyze leaching process
leaching of of
process
RE and Al. According to the dynamic distribution of the chromatographic outflow curve,
RE and Al. According to the dynamic distribution of the chromatographic outflow curve,
the calculation formulas of the theoretical plate number and the theoretical plate height
the calculation formulas of the theoretical plate number and the theoretical plate height
were derived as follows [27]:
were derived as follows [27]: 
VR 2

n = 8 ln 2 × (2)
V1/2
Minerals 2024, 14, 321 6 of 18

HETP = L/n (3)

where n represents the theoretical plate number; V R is the volume of the collected leachate,
mL; V 1/2 is the peak width at half height, mL; HETP is the theoretical plate height, cm; and
L is the length of the packed ore in the glass column, cm.
The chromatographic plate theory is used to analyze the leaching curves of RE and
Al in Figure 2. The leach HETP curves of RE and Al are displayed in Figure 3. The
correlation parameters are listed in Tables 2 and 3. Compared with the single use of
ammonium sulfate, the theoretical plate number of rare earth leaching with compound
leaching agent increases, the HETP decreases, and the mass transfer driving force increases,
which indicated that the addition of CTAB could enhance the leaching mass transfer process
of RE. However, the theoretical plate number of aluminum leaching with the compound
leaching agent decreases, the HETP increases, and the mass transfer driving force decreases,
which suggests that the presence of CTAB can inhibit the leaching mass transfer process
of Al. From Figure 3 and Tables 2 and 3, it can be seen that the HETP of the RE leaching
process decreases first and then increases with the increase in CTAB concentration, so
the RE mass transfer efficiency increases first and then decreases with the increase in
CTAB concentration, which indicates that the reasonable addition of CTAB can effectively
strengthen the mass transfer efficiency of RE. When the CTAB compound concentration is
0.00103 mol/L, the RE mass transfer efficiency is the highest, which can greatly improve
the RE leaching efficiency. The Al mass transfer efficiency first decreases and then increases
with the increase in CTAB compound concentration, indicating that reasonable addition of
CTAB can effectively weaken the Al mass transfer efficiency.

Table 2. Leach HETP and correlation coefficient of RE under different CTAB compound concentrations.

Concentration/(mol/L) L/cm V R /mL V 1/2 /mL n HETP/cm

0 10.30 26.07 42.78 2.06 5.00
0.00034 10.30 24.18 32.75 3.02 3.41
0.00069 10.60 27.23 36.21 3.14 3.38
0.00103 10.10 23.33 27.19 4.08 2.47
0.00137 10.50 32.29 46.24 2.70 3.88
0.00171 10.10 27.85 40.23 2.66 3.80
0.00343 10.20 22.21 35.33 2.19 4.65

Table 3. Leach HETP and correlation coefficient of Al under different CTAB compound concentrations.

Concentration/(mol/L) L/cm V R /mL V 1/2 /mL n HETP/cm

0 10.30 21.50 27.78 3.32 3.10
0.00034 10.30 17.90 41.47 1.03 9.97
0.00069 10.60 16.53 30.25 1.66 6.40
0.00103 10.10 19.26 30.10 2.27 4.45
0.00137 10.50 20.77 43.17 1.28 8.18
0.00171 10.10 21.20 33.85 2.17 4.65
0.00343 10.20 23.25 34.75 2.48 4.11

3.2. Effect of the Leaching Temperature on the Leaching Process of RE and Al

Figure 4 illustrates the impact of the leaching temperature on the leaching process
of RE and Al. From Figure 4a, it was found that as the leaching temperature rises, the
RE peak concentration increases in a small range, the peak shape becomes narrower, and
the mass transfer efficiency becomes higher. This is because the increase in leaching tem-
perature causes a decrease in the viscosity of the leaching agent and the heat movement
of ion exchange accelerates, thus the longitudinal diffusivity and exchangeability of the
solution are enhanced, the tailing phenomenon is weakened, and the mass transfer effect
is enhanced [28]. When the temperature is too high, the peak concentration suddenly
decreases, the peak shape becomes wider, the tailing phenomenon is serious, and the
 lation parameters are listed in Tables 2 and 3. Compared with the single use of ammonium
sulfate, the theoretical plate number of rare earth leaching with compound leaching agent
increases, the HETP decreases, and the mass transfer driving force increases, which indi-
cated that the addition of CTAB could enhance the leaching mass transfer process of RE.
Minerals 2024, 14, 321 However, the theoretical plate number of aluminum leaching with the compound7 leach- of 18
ing agent decreases, the HETP increases, and the mass transfer driving force decreases,
which suggests that the presence of CTAB can inhibit the leaching mass transfer process
of mass transfer
Al. From efficiency
Figure becomes
3 and Tables lower.
2 and 3, itThe
canhighest
be seenconcentration
that the HETP of of
REthe
occurred at a
RE leaching
process decreases first and then increases with the increase in CTAB concentration, soK.
leaching temperature of 308.15 K, while the lowest concentration was observed at 318.15 the
It suggests that excessively high temperatures can impede the mass transfer of RE in the
RE mass transfer efficiency increases first and then decreases with the increase in CTAB
synergistic leaching process of the cationic surfactant CTAB compound system. Therefore,
concentration, which indicates that the reasonable addition of CTAB can effectively
in the leaching process, it is important to choose a suitable temperature, such as in sum-
strengthen
mer, which theis mass
more transfer efficiency
suitable for leachingofoperations
RE. Whentothe CTABhigher
achieve compound concentration
leaching efficiency.
is 0.00103
Figure 4b shows a trend where the peak concentration of Al initially decreases improve
mol/L, the RE mass transfer efficiency is the highest, which can greatly before
thegradually
RE leaching efficiency.
increasing Theincrease
with the Al massintransfer
leachingefficiency first Additionally,
temperature. decreases and thethen
peakin-
creases with the increase in CTAB compound concentration, indicating that
shape starts off narrower and then widens over time, suggesting an initial increase followedreasonable
addition of CTAB
by a gradual can effectively
decrease in Al massweaken
transfer the Al mass transfer efficiency.
efficiency.

4.5 8
(a) n
4.0
HETP

3.5 6

3.0

HETP/cm
n

2.5 4

2.0

1.5 2

Minerals 2024, 14, x FOR PEER REVIEW 7 of 18

0 0.00034 0.00069 0.00103 0.00137 0.00171 0.00343
CCTAB/(mol/L)
4.0 14
(b) n
3.5 HETP 12

3.0
10
2.5
HETP/cm

8
2.0
n

6
1.5

1.0 4

0.5 2

0 0.00034 0.00069 0.00103 0.00137 0.00171 0.00343

CCTAB/(mol/L)
Figure
Figure 3. 3. Theoreticalplate
Theoretical platenumber
numberand
andHETP
HETP at
at different
different CTAB
CTAB compound
compoundconcentrations:
concentrations:(a)
(a)RE
RE
and
and (b)(b) Al.
Al.

Table 2. Leach HETP and correlation coefficient of RE under different CTAB compound concentra-
tions.

Concentration/(mol/L) L/cm VR/mL V1/2/mL n HETP/cm

0 10.30 26.07 42.78 2.06 5.00
0.00034 10.30 24.18 32.75 3.02 3.41
0.00069 10.60 27.23 36.21 3.14 3.38
 the leaching process, it is important to choose a suitable temperature, such as in summer,
which is more suitable for leaching operations to achieve higher leaching efficiency. Fig-
ure 4b shows a trend where the peak concentration of Al initially decreases before gradu-
ally increasing with the increase in leaching temperature. Additionally, the peak shape
Minerals 2024, 14, 321 starts off narrower and then widens over time, suggesting an initial increase followed8 by
of 18
a gradual decrease in Al mass transfer efficiency.

10
(a)

8
278.15 K
288.15 K
6 298.15 K
CRE O /(g/L)
308.15 K
318.15 K
4
3
2

0 20 40 60 80 100 120 140 160 180

Retention volume/mL

0.7 (b)

0.6 278.15 K
288.15 K
0.5 298.15 K
308.15 K
CAl O /(g/L)

0.4 318.15 K

0.3
3
2

0.2

0.1

0.0

0 20 40 60 80 100 120 140 160 180

Retention volume/mL
Effectofofleaching
Figure4.4.Effect
Figure leachingtemperature
temperatureononthe
theleaching
leachingcurves
curvesofof(a)
(a)RE
REand
and(b)
(b)Al.
Al.

ToTofurther
furtherelaborate
elaborateon
onthe
thefindings,
findings,the
theleaching
leachingcurves
curvesofofREREand
andAlAlatatvarious
various
leaching temperatures were analyzed using chromatographic plate
leaching temperatures were analyzed using chromatographic plate theory. Thetheory. The correlation
parameters can be found in Tables 4 and 5. Figure 5 displays the leach HETP curves for
RE and Al. It is evident that as the leaching temperature rises, the HETP of RE leaching
initially decreases before increasing, while the mass transfer driving force follows a pattern
of initial increase followed by a decrease and the mass transfer efficiency exhibits a similar
trend of increasing firstly and then decreasing. When the leaching temperature is 298.15 K,
the HETP of RE leaching is the lowest, the theoretical plate number is the largest, and the
RE mass transfer efficiency is the highest. As the leaching temperature increases, the HETP
of Al leaching initially decreases before eventually increasing, while the Al mass transfer
efficiency initially increases before eventually decreasing. When the leaching temperature is
278.15 K and the HETP of aluminum leaching is the highest, the Al mass transfer efficiency
is the lowest. Via comprehensive analysis, it can be seen that choosing to operate at higher
 exhibits a similar trend of increasing firstly and then decreasing. When the leaching tem-
perature is 298.15 K, the HETP of RE leaching is the lowest, the theoretical plate number
is the largest, and the RE mass transfer efficiency is the highest. As the leaching tempera-
ture increases, the HETP of Al leaching initially decreases before eventually increasing,
Minerals 2024, 14, 321 while the Al mass transfer efficiency initially increases before eventually decreasing. 9 of 18
When the leaching temperature is 278.15 K and the HETP of aluminum leaching is the
highest, the Al mass transfer efficiency is the lowest. Via comprehensive analysis, it can be
seen that choosing
temperatures to operate
in summer at higher temperatures
can effectively utilize CTAB in summer leaching
synergistic can effectively utilize
to improve the
CTAB synergistic leaching to improve the RE mass transfer efficiency, as well as greatly
RE mass transfer efficiency, as well as greatly improve the mass transfer efficiency of CTAB
improve the mass
in inhibiting transfer
Al on efficiency
mineral of thereby
surfaces, CTAB ineffectively
inhibiting accelerating
Al on mineral surfaces,
the thereby
RE leaching rate
effectively accelerating the RE leaching
and inhibiting the impurity Al leaching. rate and inhibiting the impurity Al leaching.

4.5 8
(a) n
HETP
4.0

6
3.5

HETP/cm
3.0
n

2.5

2.0
2

1.5
280 290 300 310 320

T/K
3.0 10
(b)
2.8 n
HETP
2.6
8
2.4

2.2

HETP/cm
6
2.0
n

1.8

1.6 4

1.4

1.2
2
1.0

280 290 300 310 320

T/K
Figure 5. Theoretical plate number and HETP at different leaching temperatures: (a) RE and (b)Al.

Table 4. Leach HETP and correlation coefficient of RE under different leaching temperatures.

Temperature/K L/cm V R /mL V 1/2 /mL n HETP/cm

278.15 10.60 17.82 24.21 3.00 3.53
288.15 10.10 26.88 35.92 3.10 3.25
298.15 10.10 23.33 27.19 4.08 2.47
308.15 10.60 18.76 23.39 3.57 2.97
318.15 10.80 18.36 32.01 1.82 5.92
Minerals 2024, 14, 321 10 of 18

Table 5. Leach HETP and correlation coefficient of Al under different leaching temperatures.

Temperature/K L/cm V R /mL V 1/2 /mL n HETP/cm

278.15 10.60 12.99 27.66 1.22 8.66
288.15 10.10 21.02 29.59 2.80 3.61
298.15 10.10 19.26 30.10 2.27 4.45
308.15 10.60 15.37 29.85 1.47 7.21
318.15 10.80 11.36 22.19 1.45 7.43

3.3. Effect of pH on the Leaching Process of RE and Al

The effects of pH on the leaching process of RE and Al are presented in Figure 6.
From Figure 6a, RE concentration gradually increases until it reaches a maximum and
then decreases rapidly as the leachate volume increases. As the pH of the leaching agent
gradually increases to 6, the RE peak concentration gradually increases, the peak shape
becomes narrow, and the mass transfer efficiency becomes higher. At a pH of 6, the RE
leaching curve exhibits the highest peak concentration, the narrowest peak shape, and
the highest mass transfer efficiency. Conversely, at a pH of 2, the RE peak concentration
is relatively low, suggesting that a low pH hinders the RE mass transfer process in the
cationic surfactant CTAB composite system. However, at this time, the RE leaching curve
peak shape is wider and the trailing phenomenon is serious, which is due to the fact that
strong acid conditions will lead the adsorbed colloidal phase rare earth elements in the RE
ores to partially dissolve, which leads to a certain degree of RE leaching process peak shape
widening. As can be seen in Figure 6b, with the increase in leachate volume, the aluminum
concentration gradually increases until it reaches the maximum and then rapidly decreases
to the minimum. With the increase in pH, the Al peak concentration increases and then
decreases and the peak shape becomes narrower and then wider, indicating that the Al
mass transfer efficiency increases and then decreases. This may be due to the fact that
CTAB acts on the surface of mineral particles, thereby inhibiting the leaching efficiency of
aluminum. At a pH of 2, the peak width of the aluminum leaching curve is the widest and
the peak concentration is higher, which is due to the strong acid conditions that will lead
the adsorbed hydroxy-aluminum in the RE ores to partially dissolve, due to the adsorbed
state of the hydroxy-aluminum in the mineral samples accounting for a large percentage
and resulting in more dissolved content; at the same time, it will also produce a serious
drag-out phenomenon and the impurity of the Al leaching rate is significantly increased.
Therefore, the strong acid system is not recommended for leaching operations; otherwise,
the increase in impurity aluminum content in the leach solution will lead to the subsequent
removal of higher costs.
The leaching curves of RE and Al at various pH were analyzed by chromatographic
plate theory. Correlation parameters were calculated and are listed in Tables 6 and 7.
Figure 7 illustrates the leach HETP curves of RE and Al. The results reveal that the HETP of
RE leaching initially decreases and then increases with the pH of the compound leaching
solution and the RE mass transfer efficiency follows a similar trend of increasing and then
decreasing. When the pH of the leaching solution is 6, the theoretical plate height of RE
leaching is the lowest and the RE mass transfer efficiency is the highest. The theoretical
plate height of aluminum leaching decreases first and then increases with the increase in
the pH of the compound leaching solution. At a pH of 6, the theoretical plate height of Al
leaching is the lowest and the mass transfer efficiency is the highest. Because the pH value
of the compound leaching agent solution is 5.2–5.5, the pH value can be selected not to be
adjusted in the actual rare earth ore leaching operation.
Minerals 2024,
Minerals 14,14,
2024, x FOR
321 PEER REVIEW 11 of 18
11 of 18

8
(a)
pH=2
6 pH=4
pH=6
pH=8
CRE O /(g/L)
4
3
2

0 20 40 60 80 100 120 140 160 180

Retention volume/mL
0.5
(b)

0.4 pH=2
pH=4
pH=6
0.3 pH=8
CAl O /(g/L)

0.2
3
2

0.1

0.0

0 20 40 60 80 100 120 140 160 180

Retention volume/mL
Figure
Figure6.
6. Effect
Effect of
of compound leachingagent
compound leaching agentpH
pHononthe
the leaching
leaching curves
curves of (a)
of (a) RE RE
andand
(b) (b)
Al. Al.

TableThe leaching
6. Leach HETPcurves of RE and
and correlation Al at various
coefficient pHdifferent
of RE under were analyzed by chromatographic
leaching agent pH values.
plate theory. Correlation parameters were calculated and are listed in Tables 6 and 7. Fig-
pH L/cm V R /mL V 1/2 /mL n HETP/cm
ure 7 illustrates the leach HETP curves of RE and Al. The results reveal that the HETP of
2
RE leaching initially10.20
decreases and27.99
then increases 45.11
with the pH 2.13of the compound4.78 leaching
4 10.10 22.03 30.50 2.89 3.49
solution and the RE mass transfer efficiency follows a similar trend of increasing and then
6 10.30 22.96 27.41 3.89 2.65
decreasing.
8 When the pH of the leaching
10.00 36.33 solution
47.00is 6, the theoretical
3.31 plate height
3.02 of RE
leaching is the lowest and the RE mass transfer efficiency is the highest. The theoretical
plate height of aluminum leaching decreases first and then increases with the increase in
the pH of the compound leaching solution. At a pH of 6, the theoretical plate height of Al
leaching is the lowest and the mass transfer efficiency is the highest. Because the pH value
of the compound leaching agent solution is 5.2–5.5, the pH value can be selected not to be
adjusted in the actual rare earth ore leaching operation.
 Minerals 2024, 14, 321 12 of 18

Table 7. Leach HETP and correlation coefficient of Al under different leaching agent pH values.

pH L/cm V R /mL V 1/2 /mL n HETP/cm

2 10.20 22.34 48.82 1.16 8.78
4 10.10 17.17 35.39 1.31 7.74
Minerals 2024, 14, x FOR PEER REVIEW 6 10.30 19.05 33.57 1.79 5.77 12 of 18
8 10.00 21.84 42.74 1.45 6.91

4.5 6
(a) n
HETP
4.0
5

3.5

HETP/cm
4
n

3.0

3
2.5

2.0 2

2 4 6 8

pH of leaching agent
2.0 10
(b)
n
1.8
HETP 9

1.6 8
HETP/cm
n

1.4 7

1.2 6

1.0 5

2 4 6 8

pH of leaching agent
Figure
Figure7.7.Theoretical plate
Theoretical number
plate and
number HETP
and at at
HETP different pHpH
different values of of
values leaching agent:
leaching (a)(a)
agent: RERE
and
(b) Al.(b) Al.
and

3.4. Effect
Table of the
6. Leach Flowand
HETP Rate on the Leaching
correlation Process
coefficient of RE
of RE anddifferent
under Al leaching agent pH values.
The illustration in Figure 8 shows the effect of the flow rate on the leaching process
of REpH L/cm 8a, it is evident
and Al. In Figure VR/mL that withV1/2an/mL n
increase in leachate HETP/cm
volume, the
2 concentration
leaching 10.20 27.99
of rare earths 45.11
first reaches its maximum value 2.13and then rapidly
4.78
4 until it reaches
decreases 10.10zero. At a flow
22.03rate of 0.6 mL/min,
30.50 2.89 concentration
the rare earths’ 3.49
6 10.30 22.96 27.41 3.89 2.65
reaches its maximum and the peak shape is the narrowest, indicating that the mass transfer
8 10.00 36.33 47.00 3.31 3.02

Table 7. Leach HETP and correlation coefficient of Al under different leaching agent pH values.

pH L/cm VR/mL V1/2/mL n HETP/cm

 The illustration in Figure 8 shows the effect of the flow rate on the leaching process
of RE and Al. In Figure 8a, it is evident that with an increase in leachate volume, the leach-
ing concentration of rare earths first reaches its maximum value and then rapidly de-
creases until it reaches zero. At a flow rate of 0.6 mL/min, the rare earths’ concentration
Minerals 2024, 14, 321 13 of 18
reaches its maximum and the peak shape is the narrowest, indicating that the mass trans-
fer driving force is large and the mass transfer efficiency is high at this time. While the
leaching flowisrate
driving force largeisand below 0.6 mL/min,
the mass the leaching
transfer efficiency is highagent
at this penetrates
time. While thetheleaching
mineral at a
slower rate and NH 4 + undergoes lateral diffusion, resulting in reverse adsorption, poor
flow rate is below 0.6 mL/min, the leaching agent penetrates the mineral at a slower rate
mass
and NH transfer
+ efficiency, and a more serious tailing phenomenon. While the leaching flow
4 undergoes lateral diffusion, resulting in reverse adsorption, poor mass transfer
rate exceeds
efficiency, and0.6a more
mL/min, NHtailing
serious 4+ mainly diffuses longitudinally
phenomenon. While the leachingwithout sufficient
flow rate exceeds ion ex-
+
change, leading
0.6 mL/min, NH4to mainly
a reduced efficiency
diffuses in masswithout
longitudinally transfer. The peak
sufficient shape and
ion exchange, peak con-
leading
to a reduced
centration efficiency
of RE in mass transfer.
in the leaching The peak
curve remain shapewhen
similar and peak concentration
the leaching of RE
solution flowin rates
the0.8
are leaching
mL/min curve
andremain similarindicating
1.2 mL/min, when the leaching
that thesolution flow rates
mass transfer are 0.8 of
efficiency mL/min
RE remains
consistent. In Figure 8b, it is evident that the leaching concentration of Al initiallyInpeaks
and 1.2 mL/min, indicating that the mass transfer efficiency of RE remains consistent.
Figure 8b, it is evident that the leaching concentration of Al initially peaks and then sharply
and then sharply declines to zero with an increase in leachate volume. At a flow rate of 0.6
declines to zero with an increase in leachate volume. At a flow rate of 0.6 mL/min, the peak
mL/min, the peak concentration of aluminum is the lowest, the peak shape is narrow, and
concentration of aluminum is the lowest, the peak shape is narrow, and the mass transfer
the mass transfer
efficiency is low. efficiency is low.

(a)
8

0.4 mL/min
6 0.6 mL/min
0.8 mL/min
CRE O /(g/L)

1.0 mL/min
4 1.2 mL/min
3
2

0 20 40 60 80 100 120 140 160 180

Retention volume/mL
(b)
0.6

0.5
0.4 mL/min
0.6 mL/min
0.4 0.8 mL/min
CAl O /(g/L)

1.0 mL/min
0.3 1.2 mL/min
3
2

0.2

0.1

0.0

0 20 40 60 80 100 120 140 160 180

Retention volume/mL
Figure 8. Effect of leaching agent flow rate on the leaching curves of (a) RE and (b) Al.
Minerals 2024, 14, x FOR PEER REVIEW 14 of 18

Minerals 2024, 14, 321 14 of 18

Figure 8. Effect of leaching agent flow rate on the leaching curves of (a) RE and (b) Al.

The
Theanalysis
analysisofofleaching
leachingcurvescurvesfor forrare
rareearths
earthsand andaluminum
aluminumatatvariousvariousflowflowrates
rates
was conducted using chromatographic plate theory. The calculated
was conducted using chromatographic plate theory. The calculated correlation parameters correlation parame-
ters
cancan
be be found
found inin Tables
Tables 8 8andand9.9.Figure
Figure99 displays
displays the the leach
leach HETP
HETPcurvescurvesforforrare
rareearths
earths
and
andaluminum.
aluminum. It illustrates
It illustrates thatthat
the HETP
the HETP for rare
for earth leaching
rare earth initially
leaching decreases,
initially then
decreases,
rises,
thenand finally
rises, decreases
and finally again again
decreases as theas flowthe rate
flowofrate theofcompound
the compound leaching solution
leaching in-
solution
creases. Moreover,
increases. Moreover, thethe
mass masstransfer
transfer efficiency
efficiency follows
follows a pattern
a pattern ofof increasing
increasingfirst
firstand
and
then decreasing. At a flow rate of 0.6 mL/min, the HETP of rare
then decreasing. At a flow rate of 0.6 mL/min, the HETP of rare earth leaching is the earth leaching is the lowest,
the number
lowest, the of theoretical
number plates is plates
of theoretical the largest,
is the and the and
largest, RE mass
the RE transfer efficiency
mass transfer is the
efficiency
highest. The aluminum
is the highest. leaching’s
The aluminum theoretical
leaching’s plate height
theoretical plateis observed to initiallytorise
height is observed and
initially
then
risedecrease
and thenasdecrease
the flowas ratetheofflow
the leaching
rate of the solution
leaching compound
solution increases.
compound The maximum
increases. The
theoretical
maximumplate height plate
theoretical of aluminum
height ofleaching,
aluminum accompanied by the minimum
leaching, accompanied by the theoretical
minimum
plate numberplate
theoretical and the lowestand
number mass thetransfer
lowestefficiency of aluminum,
mass transfer efficiencyoccurs when the leach-
of aluminum, occurs
ing solution
when flow rate
the leaching is 1.0 mL/min.
solution flow rateTo optimize
is 1.0 mL/min. conditions,
To optimizea flow rate of 0.6a mL/min
conditions, flow rate
was selected,
of 0.6 mL/min resulting in the fastest
was selected, RE mass
resulting in the transfer
fastestefficiency. This adjustment
RE mass transfer efficiency.weak-
This
adjustment
ened weakened
the Al mass transfer theprocess
Al masstotransfer
a certain process
extent, towhich
a certain
was extent, whichtowas
conducive conducive
strengthen-
to the
ing strengthening
RE leachingthe andREinhibiting
leaching and the Alinhibiting
leaching.the Al leaching.

4.5 35
(a) n
4.0 HETP
30
3.5
25
3.0

HETP/cm
2.5 20
n

2.0 15

1.5
10
1.0
5
0.5

0.4 0.6 0.8 1.0 1.2

Flow rate/(mL/min)
3.0 10
(b)
2.8 n
HETP
2.6

2.4 8

2.2
HETP/cm

2.0
n

1.8 6

1.6

1.4

1.2 4

1.0

0.4 0.6 0.8 1.0 1.2

Flow rate/(mL/min)
Figure 9. Theoretical plate number and HETP under different flow rates: (a) RE and (b)Al.
Minerals 2024, 14, 321
x FOR PEER REVIEW 15
15of 18
of 18

Figure8.9.Leach
Table HETP plate
Theoretical and correlation
number and coefficient
HETP underof REdifferent
under different flow(a)rates
flow rates: of leaching
RE and (b)Al. agent.

Flow
Table 8. Leach HETP and
L/cmcorrelation coefficient
V R /mL of REVunder
1/2 /mLdifferent flow
n rates of leaching
HETP/cm agent.
Rate/(mL/min)
Flow0.4Rate/(mL/min)
10.60 L/cm 22.39 VR/mL89.54 V1/2/mL 0.35 n HETP/cm
30.57
0.6 0.4 10.10 10.60 23.33 22.3927.19 89.54 4.08 0.35 30.57
2.47
0.8 0.6 10.80 10.10 20.09 23.3330.16 27.19 2.46 4.08 4.39
2.47
1.0 0.8 10.60 10.80 29.85 20.0969.82 30.16 1.01 2.46 10.46
4.39
1.2 1.0 10.80 10.60 21.16 29.8538.90 69.82 1.64 1.01 6.58
10.46
1.2 10.80 21.16 38.90 1.64 6.58
Table 9. Leach HETP and correlation coefficient of Al under different flow rates of leaching agent.
Table 9. Leach HETP and correlation coefficient of Al under different flow rates of leaching agent.
Flow
Flow Rate/(mL/min)
L/cm L/cmV R /mL VR/mL
V 1/2 /mL V1/2/mL n n HETP/cm
HETP/cm
Rate/(mL/min)
0.4 10.60 16.98 25.58 2.44 4.34
0.4 0.6 10.60 10.10 16.98 19.2625.58 30.10 2.44 2.27 4.34
4.45
0.6 10.10 19.26 30.10 2.27 4.45
0.8 10.80 17.10 28.66 1.97 5.47
0.8 10.80 17.10 28.66 1.97 5.47
1.0 10.60 21.76 45.62 1.26 8.40
1.0 10.60 21.76 45.62 1.26 8.40
1.2 1.2 10.80 10.80 18.31 18.3134.33 34.33 1.58 1.58 6.85
6.85

3.5. Leaching Promoting Mechanism

3.5. Leaching Promoting Mechanism
3.5.1. Viscosity
3.5.1. Viscosity Analysis
Analysis
Wu et
Wu et al.
al. [26]
[26] found
found that
that surfactants
surfactants can
can reduce
reduce the
the viscosity
viscosity of
of the
the leaching
leaching solution
solution
and improve the penetration efficiency of the leaching solution. Therefore,
and improve the penetration efficiency of the leaching solution. Therefore, this paperthis paper stud-
studied the viscosity change in the leaching solution after adding CTAB. The viscosity of 2%
ied the viscosity change in the leaching solution after adding CTAB. The viscosity of 2%
ammonium sulfate,
ammonium sulfate, 2%2% ammonium
ammonium sulfate
sulfate and
and 0.00034
0.00034 mol/L
mol/L CTAB
CTAB compound
compound solution,
solution,
2% ammonium
2% ammonium sulfate
sulfateandand0.00103
0.00103mol/L
mol/L CTAB
CTABcompound
compound solution, 2% ammonium
solution, 2% ammonium sul-
fate andand
sulfate 0.00171 mol/L
0.00171 CTABCTAB
mol/L compound solution,
compound and 2%and
solution, ammonium sulfate and
2% ammonium 0.00343
sulfate and
mol/L CTAB
0.00343 mol/L compound solutionsolution
CTAB compound were determined by a Uchscher
were determined viscometer.
by a Uchscher The results
viscometer. The
are shown
results in Figure
are shown 10.
in Figure 10.

1.8
Kinematic viscosity/(mm2/s)

1.6

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0
2 % (NH4)2SO4 0.00034 mol/L 0.00103 mol/L 0.00171 mol/L 0.00343 mol/L
CTAB+ CTAB+ CTAB+ CTAB+
2 % (NH4)2SO4 2 % (NH4)2SO4 2 % (NH4)2SO4 2 % (NH4)2SO4

Figure 10.
Figure 10. Comparison
Comparison of the viscosity
of the viscosity of
of different
different extracts.
extracts.

It can be seen from Figure 10 that the viscosity of the leaching solution can be reduced
by adding a certain concentration of CTAB. But when the viscosity of CTAB exceeds the
critical micelle concentration, the viscosity of the leaching solution increases, even higher
Minerals 2024, 14, 321 16 of 18
Minerals 2024, 14, x FOR PEER REVIEW 16 of 18

than that of 2% ammonium sulfate solution, which is consistent with the result of the effect
than that of
of CTAB 2% ammonium
compound sulfate solution,
concentration which
on the rare earthis leaching
consistent with the
process. result
That of the
is, the effect
addition
of CTAB compound concentration on the rare earth leaching process. That is,
of appropriate amount of CTAB can effectively reduce the viscosity of the leaching agentthe addition
of appropriate
solution, amount
accelerate theofpenetration
CTAB can effectively
speed of thereduce
leachingthe viscosity of the in
agent solution leaching
the oreagent
body,
solution, accelerate
and effectively the penetration
promote speed of
the mass transfer the leaching
process agent solution in the ore body,
of leaching.
and effectively
Accordingpromote thesand
to Darcy’s masspermeability
transfer process
test, of
theleaching.
permeability rate is [29]
According to Darcy’s sand permeability test, the permeability rate is [29]
2 γ𝛾
K𝐾==Cd 𝐶𝑑 2η (4)
𝜂 (4)

where
where KK isis permeability,
permeability, md; md; C C is
is aa constant
constant term,
term, which
which depends
dependson on porosity
porosityand
andother
other
factors;
factors; dd is
is the
the ore
ore particle
particle size, mm; γ γ is the density of leaching solution, g/cm33;;and
solution, g/cm and ηη isis
the
theviscosity
viscosityof ofthe
the solution,
solution, mm mm22/s.
/s.
The
TheCC and and dd of of the
the ore
ore body
body are
are constant
constant values
values and
and the
the permeability
permeability KK is is inversely
inversely
proportional to the viscosity ŋ of the leach solution. Combined with the above viscosity
proportional to the viscosity η of the leach solution. Combined with the above viscosity
testresults,
test results, itit shows
shows thatthat the
the surfactant
surfactant can can reduce
reduce the
the viscosity
viscosity of
of the
the leaching
leaching solution
solution
to improve
to improve the the permeability
permeability of of the
the ore
ore body
body andand effectively
effectively improve
improve the the mass
mass transfer
transfer
efficiencyof
efficiency ofthetherare
rare earth
earth leaching
leaching process.
process.

3.5.2.Zeta
3.5.2. ZetaPotential
PotentialAnalysis
Analysis
Surfactantcan
Surfactant canchange
changethe
thesurface
surface potential
potential of of rare
rare earth
earth ore,ore, so surface
so the the surface
ZetaZeta
po-
potential
tential of rare
of rare earthearth ore was
ore was measured
measured inpaper.
in this this paper. Therare
The raw raw rareore
earth earth
andore
theand the
differ-
ent solutions were mixed and sonicated in an ultrasonic cleaner for 1 h to form a suspen-a
different solutions were mixed and sonicated in an ultrasonic cleaner for 1 h to form
suspension,
sion, which
which was thenwas then to
allowed allowed to stand
stand for 15 minforand15their
min Zeta
and potentials
their Zeta were
potentials were
measured
measured with a Zeta potential analyzer. The test results are shown
with a Zeta potential analyzer. The test results are shown in Figure 11. in Figure 11.

Figure 11. Comparison of Zeta potentials.

Figure 11. Comparison of Zeta potentials.
From Figure 11, the surface Zeta potential of rare earth minerals is negative when the
rare earth Figure
From minerals11,are
theleached
surface Zeta
with potential of rare earth sulfate,
water or ammonium mineralswhile
is negative whenZeta
the surface the
rare earth minerals are leached with water or ammonium sulfate, while the surface
potential of rare earth minerals is positive when the cationic surfactant CTAB is added. The Zeta
potential of rare that
possible reason earththe
minerals
potentialis on
positive when of
the surface therare
cationic
earth surfactant CTAB is positive
minerals becomes added.
The possible reason that the potential on the surface of rare earth minerals
is that the concentration of CTAB is excessive relative to the rare earth minerals, so becomes posi-
the
tive is that the concentration of CTAB is excessive relative to the rare earth
double layer adsorption is formed on the surface of rare earth minerals. CTAB acts on the minerals, so
the double
mineral layer adsorption
surface, increases the is formed on of
thickness thethe
surface of rare
diffusion earthdouble
electric minerals. CTAB
layer actsclay
on the on
the mineral
surface, surface,
reduces increases
the Zeta the thickness
potential, and reducesof the
the diffusion electric double
negative electricity on thelayer on the
clay surface,
clay surface, reduces the Zeta potential, and reduces the negative electricity on the clay
Minerals 2024, 14, 321 17 of 18

thus inhibiting the expansion of clay minerals to a certain extent and strengthening the rare
earth leaching process.

4. Conclusions
The addition of CTAB in ammonium sulfate leaching solution can effectively enhance
the RE mass transfer process and inhibit the Al leaching. The optimal conditions are
0.00103 mol/L of the CTAB concentration, 0.6 mL/min of flow rate, pH 5.2–5.5 of the
leaching solution, and room temperature. With the leaching temperature increases, the
theoretical number plates for RE and Al leaching increases, resulting in a decrease in
HETP, an increase in mass transfer driving force, and, ultimately, an improvement in mass
transfer efficiency. Moreover, the RE mass transfer efficiency is higher than that of Al.
When the temperature is too high, the HETP increases and the mass transfer efficiency
decreases, indicating that summer is conducive to the leaching operation of weathered
crust elution-deposited rare earth ore.
As the pH of the leaching solution increases, the theoretical number of plates for RE
and Al leaching increases, while the HETP gradually decreases, leading to a higher mass
transfer driving force and improved leaching mass transfer efficiency. Minimum HETP
reached at pH 6. Due to the good pH buffering properties of clay minerals, there is no
need to adjust the pH of the leaching solution in the leaching operation of rare earth ore.
As the flow rate of the leaching solution increases, the theoretical number of RE plates
increases and HETP decreases. The driving force for mass transfer in rare earth leaching
is greater and the mass transfer efficiency is higher. As the HETP of aluminum increases,
the efficiency of mass transfer decreases. Moreover, the efficiency of mass transfer for RE
is greater than that of Al. When the optimal flow rate of the composite leaching agent is
0.6 mL/min, it has the highest RE mass transfer efficiency and inhibits Al leaching to a
certain extent. This suggests that the compound leaching agent comprising ammonium
sulfate and CTAB holds significant potential for practical utilization in extracting rare earth
from weathered crust elution-deposited rare earth ore.

Author Contributions: Conceptualization, X.W. and J.F.; methodology, X.W.; software, X.W. and
C.L.; validation, J.F.; formal analysis, X.W.; investigation, X.W.; resources, R.C.; data curation, X.W.;
writing—original draft preparation, X.W.; writing—review and editing, X.W. and J.F.; visualization,
F.Z.; supervision, J.F.; project administration, R.C.; funding acquisition, X.W. All authors have read
and agreed to the published version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China (No.
52204278) and the Natural Science Foundation of Wuhan Institute of Technology (No. K202265).
Data Availability Statement: Data are contained within the article.
Acknowledgments: Thanks for the great effort of the editors and reviewers.
Conflicts of Interest: The authors declare no conflicts of interest.

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