Trans. Nonferrous Met. Soc.

China 22(2012) 2282−2288

Extraction of aluminum by pressure acid-leaching method from coal fly ash

WU Cheng-you1, 2, YU Hong-fa1, 3, ZHANG Hui-fang1, 2
1. Qinghai Institute of Salt Lake, Chinese Academic of Sciences, Xining 810008, China;
2. The Graduate University of Chinese Academy of Sciences, Beijing 100049, China;
3. Department of Civil Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
Received 27 September 2011; accepted 24 December 2011

Abstract: Aluminum was leached out from coal fly ash by pressure acid-leaching method. The effects of coal fly ash size, sulfuric
acid concentration, reaction time and reaction temperature on extraction efficiency of aluminum were investigated comprehensively.
The phase and morphology of coal fly ash and solid residues after reaction were analyzed by XRD, SEM and IR. The optimal
technological conditions for extracting aluminum from coal fly ash were eventually confirmed that coal fly ash with size of 74 μm
and sulfuric acid with concentration of 50% are mixed in pressure reaction kettle to react for 4 h at 180 °C. Under the optimal
conditions, the extraction efficiency of aluminum can reach 82.4%.
Key words: coal fly ash; aluminum; pressure acid-leaching; extraction efficiency

Alkali sintering process involves the following

1 Introduction procedures: calcination of the mixture of coal fly ash and
calcium oxide (or calcium carbonate or sodium carbonate)
Coal fly ash, the solid residue of coal combustion, is at high temperature to produce aluminates which can
mainly emitted from heat-engine power station. Irregular dissolve in sodium carbonate molten salt. Eventually,
accumulation and inappropriate disposal of coal fly ash Al2O3 was attained through self-decomposition, alkali
will lead to occupancy of vast lands, and serious dissolution and desilication treatment, Bayer cycle
pollution of soil, air, water and even organism. process [9−11]. High extraction efficiency of aluminum
Comprehensive utilization of coal fly ash has been can be obtained by this method. However, alkali
studied since 1970s [1] when energy crisis, resource sintering process requires high energy-consumption and
exhaustion, and environmental contamination have been produces more solid wastes, which have restricted the
paid more attention around the entire world. For example, large-scale application of alkali sintering process in
coal fly ash has been used as cement concrete admixture extracting aluminum from coal fly ash.
[2−4] and water treatment agent recently [5,6]. In Thorough separation of silica from aluminum can
addition, coal fly ash, generally abundant in Al2O3 [7,8], be achieved by acid leaching method. However, one
is a kind of potential raw material for extracting major shortcoming of this method is that the aluminum
aluminum. At present, bauxite, the main aluminum extraction efficiency by direct acid leaching method is
source for various industrial applications, is generally obviously lower than that by alkali sinter process
dependent upon import in China. Therefore, extraction of [12−14]. NAYAK and PANDA [15] revealed that
aluminum from coal fly ash is quite significant for aluminum extraction from coal fly ash at a low acid
disposing and utilizing waste materials and developing concentration and ambient temperature is not suitable for
new aluminum source, and has attracted extensive high recovery of aluminum. In order to improve the
attention recently. aluminum extraction efficiency, various researches have
Alkali sintering process or acid leaching method been developed. LI et al [16] provided the optimum
(including sulphuric acid, hydrochloric and nitric acid) conditions of acid leaching process with leaching
has been used for extracting aluminum from fly ash. temperature of 200−210 °C, leaching time of 80 min, and

Foundation item: Project (BO210(2008)) supported by the Foundation of “Hundred Talent Program” of Chinese Academic of Sciences; Project
(2008-G-158) supported by the Scientific and Technological Project of Qinghai Province, China
Corresponding author: WU Cheng-you; Tel: +86-971-6320622; E-mail: wuchengyou86@163.com
DOI: 10.1016/S1003-6326(11)61461-1
 WU Cheng-you, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2282−2288 2283
volumetric ratio of acid to coal fly ash of 5:1, and the 74, 154, 243 μm), sulfuric acid concentration (30%, 40%,
extraction efficiency of Al2O3 can reach 87%. BAI et al 50%, 60%), reaction temperature (140, 160, 180, 200,
[17] and MATJIE et al [18] represented that the 220 °C) and reaction time (1, 2, 3, 4, 5 h). The
aluminum extraction efficiency by acid leaching method temperature of exhaust and filter were fixed at 85−90 °C
can be improved through adding calcium oxide (or to make sure that aluminum sulfate formed after reaction
calcium sulfate or lime) in coal fly ash and calcining the does not crystallize and dissolve out at room
mixture at high temperature before acid-leaching temperature.
reaction. BAI et al [19] also boosted the alumina The milling of coal fly ash was carried out on a
extraction efficiency by sintering the mixture of coal fly planet ball mill (QM-3SP2, Nanjing University, China).
ash and concentrated sulfuric acid at 300 °C to transform Solid residue of coal fly ash after leading was separated
from liquid through the vacuum suction filter. The phase
most of aluminum in coal fly ash into aluminum sulfate,
composition and morphology of coal fly ashes before
which can be extracted out from coal fly ash by hot
and after leaching were analyzed by X-ray diffraction
water.
(XRD) and scanning electron microscopy (SEM). And an
In the present study, the pressure acid-leaching
inductively coupled plasma-atomic emission
method was adopted to extract aluminum from coal fly
spectrometer (ICP-AES) was used to determine the
ash, aiming to reduce reaction temperature and acid
contents of aluminum in the leaching liquid to calculate
concentration appropriately based on high extraction the extraction efficiency, which was obtained by the
efficiency in meeting energy conservation and pollution following formula:
reduction targets.
mES (Al 2 O 3 )
η= × 100% (1)
2 Experimental mCFA (Al 2 O 3 )

where η is the extraction efficiency of aluminum,

2.1 Materials and instruments mES(Al2O3) and mCFA(Al2O3) denote the mass of Al2O3 in
Coal fly ash samples in this study were collected the leaching solution and coal fly ash before leaching,
from a heat-engine power station in the Inner Mongolia respectively.
Autonomous Region, China. The sulfuric acid with the A FTIR spectrometer was used to detect the
concentration of 95% (mass fraction) used in this study difference of chemical composition of coal fly ashes
was of industrial grade and purchased from Zibo before and after leaching under various conditions. In
Chemical Factory, China. All other chemicals were of addition, XRF was used to determine the elemental
analytically grade. compositions of coal fly ash and residue.
High pressure reaction kettle (GS-1L) was made in
Jingda Chemical Machinery, China. Both the inner 3 Results and discussion
container and the agitator blade of high pressure reaction
kettle were specially made of pure zirconium. 3.1 Characterization of coal fly ash
Ball-milling can decrease particle size and enlarge 3.1.1 Chemical composition of coal fly ash
superficial area of coal fly ash, and also can break the Table 1 lists the chemical composition of coal fly
ash analyzed by XRF. The content of Al2O3 in coal fly
aluminum silicon glass to some degree, which are
ash used in this study is 37.7% (mass fraction), rather
advantageous to the reaction between sulfuric acid and
larger than that of other metal oxides in the coal fly ash.
coal fly ash. Pure zirconium is required as the inner
So, this coal fly ash is obviously suitable for producing
container material of high pressure reactor to avoid
aluminum sulfate or alumina oxide.
corrosion under high pressure and strong acid. And in
this study, the inner container has not been corroded
Table 1 Chemical composition of coal fly ash used in the
obviously after all extraction experiments. present work (mass fraction, %)
Al2O3 SiO2 Fe2O3 CaO MgO LOI
2.2 Experimental process and analytical methods 37.7 49.9 4.38 3.74 0.540 1.92
Extraction experiments of aluminum were carried LOI: Loss on ignition.
out by adding 50.0 g coal fly ash, a certain amount of
95% H2SO4 and water into the high pressure reactor. The According to the contents of metal oxide in coal fly
mass ratio of coal fly ash and 95% H2SO4 was fixed ash, the dosage of 95% sulphuric acid is 65.6 g based on
depending on the contents of metal oxides in coal fly ash. the assumption that Al2O3, Fe2O3, CaO and MgO in coal
Extraction of aluminum was investigated fly ash were converted to Al2(SO4)3, Fe2(SO4)3, CaSO4
comprehensively by varying coal fly ash size (D90: 11, 38, and MgSO4 after acid leaching reaction.
2284 WU Cheng-you, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2282−2288
3.1.2 Phase composition of coal fly ash 74−11 μm. The reason may be that the smaller the coal
The crystal composition of coal fly ash material fly ash size is, the larger the specific surface area is,
used in this study can be observed from Fig. 1. The peak which is quite advantageous for the reaction between
of mullite is very strong and the peak of free-state Al2O3 coal fly ash and sulfuric acid. However, when coal fly
is weak, which indicates that mullite is the main form of ash size is less than 74 μm, particle aggregation restrains
aluminum. Figure 2 shows SEM image of coal fly ash. the increase of surficial area. Therefore, coal fly ash of
Round particle in SEM image may be aluminum−silica 74 μm is appropriate for the extraction of aluminum here.
glass and mullite exists as anomalous particles [20].
Based on the analysis above, we can affirm that the
uppermost existence form of aluminum is mullite and
glass in coal fly ash. So conditions of pressure acid
leaching must make the mullite and glassy phase
decompose as soon as possible to attain high aluminum
extraction efficiency.

Fig. 3 Effect of coal fly ash size on extraction efficiency of

aluminum (Sulfuric acid concentration 30%, reaction
temperature 180 °C and time 4 h)

3.2.2 Effect of sulfuric acid concentration on extraction

efficiency of aluminum
Figure 4 displays the effect of sulfuric acid
Fig. 1 XRD pattern of coal fly ash material used in this study concentration on the extraction efficiency of aluminum.
The aluminum extraction efficiency increases from
65.7% to 82.4% when sulfuric acid concentration ranges
from 30% to 50% (mass fraction), but dramatically
diminishes to 57.8% as sulfuric acid concentration
increases from 50% to 60%. Figure 5 shows XRD
patterns of the leached coal fly ash. The peaks of mullite
become weaker, and the characteristic peaks of calcium
sulfate and quartz become sharper as the concentration of
sulphuric acid raises from 30% to 50%. The change of
phase composition in leached residue reveals that mullite
tends to decompose at a high concentration of sulphuric
acid because the contact chance between H+ and coal fly
ash increases with increasing the sulfuric acid
Fig. 2 SEM image of coal fly ash material used in this study concentration. However, the peaks of mullite are weaker
than those of other leached coal fly ash when the
3.2 Influencing factors on aluminum extraction concentration of sulphuric acid increases to 60%. The
efficiency phenomenon contradicts the decrease of aluminum
3.2.1 Effect of coal fly ash size on extraction efficiency extraction efficiency. Moreover, the residue that did not
of aluminum dissolve in water easily adheres to the bottom of high
The effect of coal fly ash size on the extraction pressure reaction kettle after aluminum extraction
efficiency of aluminum is shown in Fig. 3. The reaction with sulphuric acid of 60%.
extraction efficiency of aluminum increases as coal fly In order to study the reason why aluminum
ash size (D90) decreases from 243 μm to 74 μm, but extraction efficiency decreases as sulphuric acid
generally remains constant with coal fly ash size of concentration increases to 60%, the phase composition of
 WU Cheng-you, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2282−2288 2285
results in the present study and previous works [17,19]
that coal fly ash begins to decompose when the
temperature is higher than 150 °C under atmospheric
pressure. NAYAK and PANDA [15] also revealed that
aluminum extraction from coal fly ash at ambient
temperature was not suitable for high recovery.

Fig. 4 Effect of sulfuric acid concentration on extraction

efficiency of aluminum (Coal fly ash size 74 μm, reaction
temperature 180 °C and time 4 h)

Fig. 6 XRD pattern of sediment adhered to bottom of high

pressure reactor after reaction with 60% sulfuric acid (Coal fly
ash size 74 μm, reaction temperature 180 °C and time 4 h)

Fig. 5 XRD patterns of solid residues with different sulfuric

acid concentrations (Coal fly ash size 74 μm, reaction
temperature 180 °C and time 4 h)

residue adhered to the bottom of high pressure reaction

kettle was analyzed by XRD (Fig. 6). As seen from
Fig. 6, the residue adhered to the bottom of high pressure
reaction kettle after aluminum extraction mainly consists
of Al2(SO4)3·5H2O, CaSO4, mullite and quartz. Therefore, Fig. 7 Effect of reaction temperature on extraction efficiency of
the reason can be inferred that aluminum sulfate formed aluminum (Coal fly ash size 74 μm, sulfuric acid concentration
after acid-leaching reaction can not diffuse timely into 50%, and reaction time 4 h)
the solution from reaction position and is encased by
calcium sulfate, quartz and mullite because the system of IR spectra of revealed coal fly ashes before and
60% sulphuric acid and 50.0 g of coal fly ash powder after leaching at different reaction temperatures (at 140
exhibits a high-viscosity [21]. °C, 160 °C and 180 °C) are given in Fig. 8. IR spectrum
3.2.3 Effect of reaction temperature on extraction of coal fly ash before leaching shows strong absorption
efficiency of aluminum bands at 1100, 893, 742, and 561 cm−1 for mullite. The
The effect of reaction temperature on the extraction leached residue shows sharp bands at 1100, 796, 673,
efficiency of aluminum is shown in Fig. 7. The 465 cm−1 for quartz. In addition, the adsorption bands of
extraction efficiency of aluminum increases from 50.2% quartz become sharper as the reaction temperature
to 85.7% as the reaction temperature increases from 140 changes from 140 °C to 180 °C, which can prove that
°C to 220 °C. Reaction activation energy may be great aluminum silicon glass and mullite in coal fly ash tend to
between coal fly ash and sulfuric acid according to the decompose at high temperature.
2286 WU Cheng-you, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2282−2288
flake-like, clubbed and porous particles eventually with
the size of coal fly ash particle reduced to less than 10
μm. However, the increase rate of aluminum extraction
efficiency decreases with extending reaction time. For
example, the extraction efficiency of aluminum only
increases by about 5% when the reaction time extends
from 4 h to 5 h. Therefore, 4 h is considered the optimal
reaction time for raising production efficiency of
aluminum sulfate preparation from coal fly ash by
autoclaved acid-leaching method.

3.3 Composition and mass of leached residue

As studied above, optimal conditions of pressure
acid leaching method for extracting aluminum from coal
Fig. 8 IR spectra of coal fly ash before (a) and after leaching at fly ash with sulphuric acid figured out that coal fly ash of
140 °C (b), 160 °C (c) and 180 °C (d) 74 μm and 50% sulphuric acid are mixed and react at
180 °C for 4 h. And aluminum extraction efficiency can
Furthermore, the extraction efficiency increases reach 82.4% under this leaching condition. Elemental
slightly from 82.4% to 85.7% with increasing reaction compositions of coal fly ash after leaching under the
temperature from 180 °C to 220 °C. Therefore, 180 °C is optimal conditions were analyzed by XRF and listed in
considered the optimal reaction temperature taking Table 2. It is clearly indicated that aluminum is extracted
energy consumption into account. into solution from coal fly ash and silica is enriched into
3.2.4 Effect of reaction time on extraction efficiency of residue after pressure acid leaching reaction.
aluminum
Figure 9 represents the effect of reaction time on the Table 2 Composition of coal fly ashes before and after leaching
extraction efficiency of aluminum. The result shows that (mass fraction, %)
the extraction efficiency of aluminum rapidly increases Composition Al2O3 Fe2O3 CaO MgO SiO2
from 32.6% to 85.9% when reaction time increases from Before leaching 37.7 4.38 3.78 0.540 49.9
1 h to 5 h. The reason can be explained that aluminum- After leaching 8.93 0.70 4.94 0.067 68.9
silicon glass with a low reaction activity in coal fly ash
requires enough reaction time to completely decompose. The mass of coal fly ash after leaching decreased to
Figure 10 displays SEM images of coal fly ash and solid 36.2 g from 50.0 g of raw coal fly ash. It shows that
residues after aluminum extraction reaction with pressure acid-leaching method for extracting aluminum
different reaction time. It can be clearly observed that as not only makes good use of coal fly ash, also reduces
reaction time extends from 1 h to 5 h, near-sphere coal residues and keeps environmental contamination low
fly ash particles have been gradually decomposed to compared with alkali sintering method.

4 Conclusions

1) The pressure acid leaching method was used to

extract aluminum from coal fly ash, and the effects of
coal fly ash size, sulfuric acid concentration, reaction
temperature, and reaction time on extraction efficiency of
aluminum were investigated.
2) The extraction efficiency of aluminum increases
with diminishing coal fly ash size, and increasing
appropriately sulfuric acid concentration, reaction
temperature and reaction time.
3) The optimal technological conditions for
extracting aluminum from coal fly ash have been
Fig. 9 Effect of reaction time on extraction efficiency of eventually confirmed that coal fly ash with size of 74 μm
aluminum (Coal fly ash size 74 μm, sulfuric acid concentration and sulfuric acid with concentration of 50% are mixed in
50% and reaction temperature 180 °C) the pressure reaction kettle to react for 4 h at 180 °C.
 WU Cheng-you, et al/Trans. Nonferrous Met. Soc. China 22(2012) 2282−2288 2287

Fig. 10 SEM images of coal fly ash after

leading for 1 h (a), 2 h (b), 3 h (c), 4 h (d),
5 h (e) (coal fly ash size 74 μm, sulfuric acid
concentration 50%, and reaction temperature
180 °C)

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加压酸浸法从粉煤灰中提取铝

吴成友 1, 2，余红发 1, 3，张慧芳 1, 2

1. 中国科学院 青海盐湖研究所，西宁 810008；

2. 中国科学院 研究生院，北京 100049；
3. 南京航空航天大学 土木工程系，南京 210016

摘 要：利用加压酸浸法从粉煤灰中提取铝。研究了粉煤灰粒度、硫酸浓度、反应时间、反应温度对铝提取率的
影响。 通过 XRD、SEM、IR 对反应前、后的粉煤灰进行物相和形貌分析。确定的最佳工艺条件为粉煤灰粒度
74 μm，硫酸浓度 50%，反应时间 4 h，反应温度 180℃。在最佳工艺条件下，氧化铝的提取率为 82.4%。
关键词：粉煤灰；铝；加压酸浸；提取率
(Edited by YANG Hua)