Chemical Engineering Journal 173 (2011) 191–197

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Chemical Engineering Journal

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Extraction and separation of vanadium and nickel from fly ash produced in heavy
fuel power plants
Mohammad A. Al-Ghouti a,b,c,∗ , Yahya S. Al-Degs d , Ayoup Ghrair c , Hani Khoury e , Mahmoud Ziedan f
a
Arts and Sciences Unit, Fahad Bin Sultan University, 15700 Tabuk, Saudi Arabia
b
Applied Medical Science, German Jordanian University, P.O. Box 35247, Amman 11180, Jordan
c
Knowledge Section, Royal Scientific Society, P.O. Box 1438, Amman, Jordan
d
Chemistry Department, Faculty of Science, Hashemite University, Al-Zarqa, Jordan
e
Earth Sciences and Environment Department, University of Jordan, Amman, Jordan
f
Chemistry Department, Hussein Thermal Power Station, Al-Zarqa, Jordan

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

Article history: In Jordan, large amounts of fly ash (FA) are produced as a result of burning heavy fuel in power plants.
Received 10 May 2011 Extraction of metals from FA is an important industrial/environmental issue to assess metals’ mobility
Received in revised form 28 July 2011 and applications. Large amounts of metals (V, Ni, Fe, Ca, Mg, Na, and K) were easily leached from FA under
Accepted 29 July 2011
acidic, basic, and neutral conditions and this makes disposal of this material an important environmental
issue. Extraction and separation of vanadium (V) and nickel (Ni) from FA is achieved using Akita’s proce-
Keywords:
dure with some modifications. In the first step, Ni is selectively eluted from FA using NH4 OH solution and
Fly ash
then precipitated using Na2 S. The Ni/V ratio in final precipitate was 27. On the other hand, V is extracted
Heavy fuel
Vanadium
from Ni-free-FA using Na2 CO3 solution, recovered by 0.1 M tri-ethylamine/toluene, and precipitated by
Nickel NH4 Cl. The V/Ni ratio in the final precipitate was 55. The adopted method showed a reasonable recovery
Separation for both metals from FA, 56 and 45% from Ni and V, respectively. The earlier attempts indicated that
separation of V/Ni by precipitation using OH− or CO3 2− was not successful where both the metals did not
precipitate from solution in the presence of other elements.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
In Jordan, the total power produced by Central Electricity Gen-
erating Company CEGC in 2010 was approximately 7660 GWh [1].
Heavy fuel, diesel and natural gas are the main sources for gener-
ating electricity in Jordan [1]. Diesel (average molecular formula
C12 H23 ) is highly consumed to generate electricity with a total
amount of 68,000 m3 in 2010 [1]. On the other hand, the con-
sumed amounts of heavy fuel and natural gas (mainly methane)
were 837,000 ton and 1.84 × 108 m3 , respectively in 2010 [1]. The
combustion of heavy fuel or diesel by excess oxygen is presented
as: 4C12 H23 + 71O2 → 48CO2 + 46H2 O. However, in real situation,
complete combustion of fuel is not possible and the incomplete
combustion will come out with mixture of substances known as fly
ash FA [2]. The large consumption of heavy fuel and diesel in power
stations leaves about 420 ton of FA [3] and this number is expected
to increase dramatically in the following years due to the natural
∗ Corresponding author at: Knowledge Section, Royal Scientific Society P.O. Box
1438 Amman, Jordan. Fax: +962 65344806.
E-mail addresses: alghoutimohammad@gmail.com, ghoutijo@yahoo.co.uk,
mghouti@rss.gov.jo (M.A. Al-Ghouti).
growth rate of energy demand and shortage of natural gas sup-
plying. In terms of resource recovery and environmental impact,
FA is attracting much attention due to disposing problems and its
harmful impact on the soil because of metal leaching [4,5]. In fact,
research on this topic is rather limited and indicated that FA pro-
duced in heavy fuel power stations is rich in Ni, V, Fe, Mo, Mg, Na
and C and among these metals Ni and V are the most valuable [4,5].
Accordingly, FA would be a source of pollution due to metal leach-
ing and in the same time it is commercially attractive due to the
presence of high levels of V and Ni.
It is important to mention that most of the metals present in fuel
oil fly ash are non-process elements, i.e., those elements that have
no active part in the process (fuel burning in our case). The non-
process elements should be monitored and controlled as they may
lead to operating drawbacks as well as dead load [6,7]. For fly ash
that produced from fuel burning, the main non-process elements
are V, Ni and Mg, the first two elements come with fuel and the latter
one is added to fuel as Mg(OH)2 in order to prevent fuel fouling
upon burning [8]. Other common heavy metals like Fe, Mn, Co, and
Al are originated from the corrosion of the process equipment that
occurred at high temperatures [8].
Before disposing fly ash into the environment, it is important to
extract/separate the valuable elements like V and Ni and to check up

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.07.080
192 M.A. Al-Ghouti et al. / Chemical Engineering Journal 173 (2011) 191–197
the mobility of the rest of cations which would be beneficial to the
soil. Extraction of metals-containing wastes by different solvents,
also known as sequential extraction is a good practice to evaluate
the mode of metals binding within solid matrix and to evaluate
the metal mobility in different environments. In sequential extrac-
tion, the solid material is successively exposed to different solvents
of different types or chemistries in order to collect the extracts in
different fractions which is essential to assess the mode of metals
binding with the solid matrix [9].
The main aim of this work is to determine the extractable metals
in FA produced in the Jordanian Central Electricity Generating Com-
pany (Hussein Thermal Power Station) in which heavy fuel is used
as a source of energy. The extraction of metals by different solvents
is also studied to evaluate the leachability of metals into natural
waters if FA contacted with the soil. Moreover, many attempts are
made to separate Ni and V (which present in large amounts in
FA) from each other using either direct selective precipitation or
extractive precipitation methods.
2. Experimental procedures
2.1. Collection and diagnosis of fly ash FA
There are two kinds of power stations in Jordan: stations used
heavy fuel/diesel fuel and the other type applied natural methane
gas. FA samples (total amount 10 kg) were collected from the Jor-
danian Central Electricity Generating Company (Hussein Thermal
Power Station) over the period 10/2010 to 4/2011. It is impor-
tant to mention that, the collected FA was generated from burning
heavy fuel in that station. The used heavy fuel is grade-6 type
which employed to power two adjacent plants of capacities 33 and
66 MWh. The employed boilers in these plants are water-tube type.
Chemical analysis of employed heavy fuel indicated the presence of
V (40–60 mg/L), Ni (10 mg/L) and Mg (2.5%). Five samples were col-
lected on different occasions and finally combined together to get
a representative sample for the extraction experiments. The origi-
nal FA particles have variable particle size range 45–500 ␮m. Before
use, FA was crushed manually and then sieved into particle size less
than 100 ␮m. The FA material has a black colour with an apparent
density of 0.42 g/cm3 . The organic content of FA was estimated by
doing loss on ignition LOI test a following [10]: 2.0 g of dry FA was
heated at 550 ◦ C for 5 h, the cooled ash was weighed and the mass
lost was estimated from the initial mass. The pH of FA solution was
estimated as following [11]: 1.0 g of dry FA was gaited (at room
temperature) with CO2 -free distilled water for 5 h and after set-
tling FA particles pH was measured using pre-calibrated pH meter
(Weilheim, Germany). The chemical and textural properties of FA
were evaluated by running SEM/EDX analyses (FEI-INSPECT-F50 of
SEM/EDX, Netherlands).
2.2. Extraction of metals from FA by different solvents
The following extraction solvents were prepared: ammonium
nitrate NH4 NO3 1.0 M, ethylenediaminetetraacetic acid (EDTA)
C10 H16 O8 N2 1.0 M, sodium acetate CH3 CH2 COONa 1.0 M, ammo-
nium oxalate NH4 O2 CCO2 H 1.0 M and NaCl 0.01 M. The employed
reagents were of high purity and used as received (Sigma® com-
pany).
The metals were extracted from FA according to the following
procedure [4]: 1.0 g dry FA was added to 50.0 mL of a certain elution
solvent and the mixture was placed in a mechanical shaker (GFL
Shakers, Germany) for 24 h at 35 ◦ C. After that, the filtrate was care-
fully filtered and the eluted metals were directly quantified. The
extraction process carried out at 35 ◦ C. Extraction procedures were
repeated three times to obtain better accuracy and averaged results
were reported in all cases. Atomic absorption spectrophotometer
AAS (Shimadzu AA-6300, Japan) and inductivity coupled plasma
atomic emission spectrometer ICP-AES (Shimadzu ICP-7510, Japan)
were used to identify and quantify the metal cations. Before analy-
sis, calibration graph for each metal was constructed and verified.
The total contents of metals in FA were quantified as following [6]:
2.0 g dry FA was placed in a platinum crucible and 10 mL HCl–HNO3
mixture (1:3 by vol) was added and the final mixture was heated
in a sand bath at 250 ◦ C for 5 h. The cooled solution was filtered in
a 100 mL volumetric flask and diluted with distilled water before
analysis by ICP-AES. Metal contents were determined using the
earlier calibration graphs and this was carried out using special
software equipped with the instrument.
2.3. Separation of metal cations using selective precipitation by
NaOH or Na2 CO3
Separation of V and Ni from each other and from the rest of
metals (impurities) was carried out by applying different analyt-
ical procedures and the main targets were V and Ni due to their
commercial importance. Selective separation by NaOH or Na2 CO3
was carried out at 25 ◦ C as following. 50 mL (±0.01 mL) burette was
filled with 0.001 M NaOH or 0.001 M Na2 CO3 and used to titrate
100 mL of metal solution (EDTA-extract). NaOH or Na2 CO3 were
added carefully to metal solution and the titration process was ter-
minated until no precipitate is observed. The final mixture was left
for 2 h and then the precipitate is removed by suction filtration and
metal contents in solution were measured by ICP-AES or AAS.
2.4. Selective extraction and separation of Ni or V from FA
The following extraction procedure was employed for obtaining
Ni from FA [5]: 150 mL of 2.0 M NH4 Cl and 2.0 M NH3 is added to
8.0 g of FA. The mixture was agitated for 6 h at 50 ◦ C to complete
elution of Ni from the FA. The FA was removed by filtration. Then,
100 mL of 1.0 M Na2 S was gradually added to the filtrate with stir-
ring until precipitate is formed. The precipitate (NiS) was removed
from solution, washed with water, and finally dried at 100 ◦ C for
24 h. The following extraction procedure was used for obtaining V
from FA [5]: 200 mL of 2.0 M NH4 Cl and 2.0 M NH3 is added to 10 g of
the FA. The mixture was agitated for 6 h at 50 ◦ C to extract V from FA.
The FA was removed by filtration and washed with distilled water.
The FA was then added to 150 mL of 2.0 M Na2 CO3 and the mixture
was agitated for 6 h at 70 ◦ C. After that time, FA was removed by fil-
tration and the pH of the filtrate was adjusted to 5.5 and the mixture
was extracted with 50 mL of 0.1 M tri-ethylamine (CH3 CH2 )3 N (in
toluene). The organic layer was removed and extracted with 50 mL
of 2.0 M Na2 CO3 for 3 h. The extracted V in the aqueous layer was
precipitated as NH4 VO3 by adding 7.0 g NH4 Cl and few seed crys-
tal. The earlier mixture was kept at 20 ◦ C for 24 h before collecting
the precipitate (NH4 VO3 ). The precipitate was washed with 3% NH3
solution and dried before recording the final mass.
3. Results and discussion
3.1. Diagnosis of FA
FA is a powdery residue that generated in large amounts in our
local power stations that applied diesel/heavy oil as a fuel source.
FA poses a threat to the environment due to the presence of toxic
heavy elements as will be shown soon. At the same time, it con-
tains valuable metals, including vanadium and nickel that are easily
extractable from FA and this gives FA more value for improving
chemical and physical properties of the soil. The SEM and EDX of
collected FA are given in Fig. 1.
 M.A. Al-Ghouti et al. / Chemical Engineering Journal 173 (2011) 191–197
Fig. 1. SEM of FA magnified at 5000× (A) and 12,000× (B) and EDX of FA (C).
As mentioned earlier, the main aim of this study is to reduce the
potential dangerous effect of FA by extraction and separation of V
and Ni and evaluating the mobility of other metals under by apply-
ing extraction using different solvents. The general features of FA
are viewed at different magnification powers (5000× and 12,000×)
for more assessment (Fig. 1). At 5000× magnification, the picture
(Fig. 1A) indicated the porous structure of the FA that created high
temperatures upon fuel burning (2500 ◦ C). Large particle of diam-
eter more than 30 ␮m is shown in Fig. 1A. Fig. 1B which is taken at
higher magnification power indicated the presence of needle-like
structure of average length 10 ␮m which may back to metal oxides
of Ni and V that created at high temperatures. As expected, the EDX
spectrum of FA proved the presence of C, V, Na, Mg, S, and O. The
high contents of V and Mg are expected because they are present
in heavy fuel in good amounts. Similar SEMs are reported in the
literature [12,13]. The high porosity of the FA would be useful for
other industrial applications. The FA has fine particles with very low
density (0.42 g/cm3 ) which makes direct disposal very difficult. The
pH of FA solution was alkaline (10.9) indicating the basic nature of
the surface of FA which would be attributed to the basic organic
functional groups that usually created at high temperatures [11].
In its present form, FA would be applied as a soil conditioner or as
amendment agent [6]. Alkaline pH values of many fly ashes were
reported in the literature [14]. LOI test indicated that the percent
of carbon is 64% and this expected because FA is generated from
heavy fuel which is mainly made up of carbon. In a similar study,
the percent of carbon was 79% in a fly ash generated from a certain
heavy fuel [4].
3.2. Extraction power of different elution solvents: assessment of
metal mobility
As mention earlier, few studies were reported on extraction and
separation of V and Ni from diesel/heavy fuel FA. For example, a
193
novel process using air oxidation in the presence of ammonia has
been proposed in Kashima-kita electric power corporation in Japan
[5]. Extraction of V from FA containing a large amount of ammo-
nium sulphate has been studied under weak acidic and reducing
conditions [15]. Vanadium metal was selectively extracted (95%)
with 0.1–0.2 M H2 SO3 at 323–363 K, with an ash/reagent ratio of
1/4 and extraction time of 45 min [15]. In a similar study, FA was
heated at moderate temperatures (150 ◦ C), a de-carburization and
de-sulphurisation (pre-treatment) stage, and finally a smelting step
in an electric-arc-furnace [2]. The results indicated that Vi was
obtained with recovery of more than 89% [2]. Furthermore, several
parameters were studied to optimize the smelting stage including
operating temperature, aluminium addition, and using ferrosilicon
as reducing agent [2].
An oxidation process was adopted for solubilisation of vana-
dium from the coke as sodium vanadate [16]. The process operates
at 300 ◦ C and pH of 9.5 and a high-purity fused V2 O5 was obtained
[16]. The influence of iron on the alkali extraction of vanadium has
been investigated by Burriesci and co-workers [17]. The extraction
yield is influenced by factors such as the dimensions and morphol-
ogy of the particles and the occlusion of vanadium in alkali-resistant
particles, together with the presence of vanadium in the tetrava-
lent state [17]. In an interesting study, V in oil FA was leached by
NaOH and then precipitated (after removing Al) at pH 5 using NH4 Cl
[18]. The earlier process gave a high V recovery from oil FA [18]. In
conclusion, extraction and separation of V and Ni from FA is not
a straightforward process and many extractants and precipitants
agents are involved in the process [4,5,18].
A number of common solvents having variable acidities were
tested for metals extraction from FA. The content of the extracted
metals is presented in Table 1. Besides that, the total contents of
metals in FA are also provided in Table 1.
The tested solvents have different chemistries: slightly strong
acid (1.0 M EDTA, pH 0.71) weak acid (NH4 NO3 , pH = 4.6) weak
194 M.A. Al-Ghouti et al. / Chemical Engineering Journal 173 (2011) 191–197

Table 1
Extracted metals from FA at 35 ◦ C.a Values between parentheses are either the concentration of reagents or percent of metal leaching.

Metal Total content NH4 NO3 (1.0 M) EDTA (1.0 M) CH3 CH2 CO2 Na (1.0 M) NH4 O2 CCO2 H (1.0 M) NaCl (1.0 M)
c c c
V 6.10% 565 mg/L 1.6%
Ni 0.79% 0.19% 0.37% 0.36% 478 mg/L 0.41%
Mg 9.60% 5.57% 6.07% 5.30% 0.32% 5.10%
b c
Al 0.27% 0.19% 0.24% 0.14%
c
Ca 4.21% 0.56% 0.62% 0.32% 2.50%
c
Na 3.53% 1.93% 2.20% 1.90% 1.60%
K 2.92% 0.48% 0.49% 948 mg/L 398 mg/L 0.11%
b c
Fe 2.50% 2.20% 2.40% 3.70%
a
Extraction conditions. Mass of FA = 1.0 g, volume of solution 50 mL, extraction time 24 h (at 35 ◦ C).
b
Not measured.
c
Below detection limit.

bases (CH3 CH2 CO2 Na, pH = 9.4, (NH4 )2 O2 CCO2 , pH = 9.0) and neural
solvent (NaCl, pH = 7). The aim of selecting the earlier solvents was
to simulate the mild environmental conditions which range from
pH 5.4 to moderately basic systems of pH 9.8 [19]. As reported in
literature, conducting metal elution and hence mobility from solid
wastes like FA under harsh acidic/basic/oxidizing/reducing condi-
tions is not, in most cases, realistic and the obtained results may
end-up with misleading outputs or conclusions [6]. As can be con-
cluded from Table 1, FA is a good source for valuable metals like V
and Ni with a mass percent of 6.1 and 0.79% for V and Ni, respec-
tively. In the same time, it would have a dangerous influence on
the environment due to the possible leaching of the earlier metals.
FA is a good source of plant nutrients because it has high concen-
tration of easily leachable cations like Ca, Mg, Fe, and K. According
to Österås and co-workers, a solid waste containing large fractions
of soluble plant nutrients would be applied to poor soil like for-
est soils [20]. However, in our case, it is necessary to extract V/Ni
metals from FA to prevent their toxic effect on natural soil and
groundwater in case of metal mobility. Besides the given metals,
Cu, Zn, Cr, Pb, and Co were detected in FA but in small concen-
trations (<150 mg/L). The following conclusions are drawn from
Table 1: (a) there are eight metals in FA and this is quite large
number which makes separation process is a hard task, (b) among
the tested solvents, EDTA was the best extractant and this indi-
cated from the amounts of eluted metals. The excellent extraction
power of EDTA is attributed to the strong complexing ability of this
molecule with most metals and to the low acidity of extraction
solution (pH = 0.71), (c) V & Ni are the most abundant and valuable
metals in the ash. In fact, the rest of metals like Ca, Mg, Na, and K
are also present in most of the tested extractants and these met-
als are important for the soil, (d) complete separation of this large
number of metals would be a hard task, therefore, the separation
processes were limited to V and Ni, and (e) it is interesting to notice
that NaCl solution was effective for metals leaching from FA and
this would indicate that some metals were not strongly attached
to FA surface and the metals present in their ionic form. As indi-
cated in Table 1, NaCl solution was not effective for V elution from
FA.
The overall extraction powers of the tested solutions were com-
pared with respect to V, Ni, Mg, Ca, and K where the ultimate levels
of those metals are provided in Table 1. Generally speaking, the
acidic solvents (especially EDTA solution of pH 0.71) were more
effective for metal elution compared to basic and neutral ones.
For example, no V and Mg were detected in acetate and oxalate
and even in NaCl solutions. Larger amounts of Ca, Na, and K were
extracted in acidic solvents than in basic/neutral ones. The results
presented in Table 1 indicated that FA would be a toxic material and
has a high risk on the soil and this conclusion was deduced from
the large amounts of extracted metals by neutral NaCl solution. The
earlier observation indicated the metal mobility taking into account
their simple elution, therefore, disposal of FA is not recommended
and permission from governmental agencies is needed for disposal
or even for its use in other applications.
3.3. Metal separation
In general, EDTA has outperformed other extractants for metal
elution from FA. About 30 and 50% of total V and Ni in FA were
obtained by EDTA. The high acidity of EDTA solution (pH 0.71), in
fact, would help for extraction of more metals from FA besides the
high complexing ability of EDTA. Accordingly, separation studies
were carried out on EDTA extract because it contains large fraction
of metals.
3.3.1. Stepwise precipitation of V and Ni by NaOH
Precipitation reactions can sometimes be applied to separate
ions from each other [21,22]. Selective separation of V/Ni ions
was employed by adding 0.001 M NaOH or Na2 CO3 as precipitat-
ing agents to metal solution. The earlier precipitating agents were
selected due to the large differences in Ksp values of hydroxide and
carbonate complexes of Ni and V as indicated in Table 2. Table 2
shows the Ksp values for extracted metals along with precipitation

Table 2
Ksp values and pH of precipitation for the extracted metals.

Metal Concentration (M)a Ksp – hydroxides (at 25 ◦ C) pHppt b (precipitation) Ksp – carbonates (at 25 ◦ C)c
−24
VO3 +
0.31 3 × 10 2.5 1.0 × 10−11
Ni2+ 0.063 6 × 10−16 7.0 1.3 × 10−7
Mg2+ 2.51 6 × 10−10 9.2 3.5 × 10−8
Al3+ 0.10 3 × 10−34 3.2 –
Ca2+ 0.155 6.5 × 10−6 11.8 4.5 × 10−9
Na+ 0.96 n.d. –
K+ 0.125 n.d. –
Fe2+ 0.446 1.6 × 10−39 2.5 2.1 × 10−11

Ksp values were obtained from [22–23].

a
The molar concentration of the metals is calculated from the values given in Table 1.
b
For dications: pHppt = 14 + log(CM /Ksp )1/2 and for trications: pHppt = 14 + log(CM /Ksp )1/3 ; where CM and Ksp are the metal content (in M) and solubility product constant,
respectively.
c
The amount of Na2 CO3 needed for cation precipitation was determined from initial metal content and the corresponding Ksp value.
 M.A. Al-Ghouti et al. / Chemical Engineering Journal 173 (2011) 191–197
Table 3
Metal content in the solution before and after precipitation (RSD < 5% in all cases).
System OH− precipitation metal content (mg/L)a,c
V Ni Mg
Original solution 405.0 57.0 1625.0
Solution after precipitation 312.0 52.0 400.0
System CO3 2− precipitation metal content (mg/L)b,c
V Ni Mg
Original solution 120 13.5 430
Solution after precipitation 101 13.7 326
a
Precipitation process was terminated at pH 11.3 (no precipitation was observed
after this point).
b
Precipitation process was terminated after adding 5.0 mL of 0.001 M Na2 CO3
solution. No precipitation was observed after this volume.
c
Metal contents were reported taking into account the dilution of the original
solution.
conditions. Precipitation calculations were carried out assuming
that ions are present in their most stable ionic state.
Separation of V/Ni ions is possible taking into account the values
presented in Table 2. For example, mixture of V/Ni would be sep-
arated because at pH 2.5 V ions precipitated before Ni ions which
start to precipitate at pH 7.0. Moreover, (VO3 )2 CO3 is precipitated
before NiCO3 as Ksp for the former is much lower than the latter
(1.0 × 10−11 compared to 1.3 × 10−7 ). The high Ksp value of MgCO3
(3.5 × 10−8 ) would indicate its earlier precipitation leaving Ni/V
and other soluble cations like Na and K.
As can be seen from Table 2, the pHppt of the metals is different
from metal to metal, however, in some cases pHppt is similar for
two systems which make their separation by OH− precipitation is
rather limited. For example, at solution pH 2.6 both V and Fe ions
would be precipitated leaving other cations in solution. Based on
the data given in Table 2, V and Fe ions would precipitate at pH 2.6,
Al at pH 3.2, Mg at pH 9.2, Ca at pH 11.8. KOH and NaOH are highly
soluble salts.
It seems that many factors would affect separation of metals
by OH− in this complex situation. The experimental observations
indicated that the precipitation is started around pH 11 and no
precipitate is formed beyond this point. After completion of pre-
cipitation by NaOH, the metal contents in the original solution are
given in Table 3.
It is important to mention that not all metals were tested after
precipitation processes and this attributed our interest in V/Ni
system. It seems that selective precipitation by NaOH is useful
for eliminating Mg from V/Ni cations, the level of Mg2+ has been
reduced from 1625 to 400 mg/L after precipitation as shown in
Table 3. About 23% of V ions were separated from Ni by OH-
precipitation, the metal content reduced from 405 to 312 mg/L. It
seems that Ni ions were not separated from V ions by selective
precipitation. In fact, the results presented in Table 3 do not sup-
port the earlier postulate that V and Ni could be separated as both
metals have large difference in their pHppt values (2.5 for V and
7.5 for Ni). It seems that precipitation from a complex system (8
metals) is a complicated process and cannot be presented by clas-
sical precipitation reactions. In fact, adsorption of soluble cations on
the surface and within the pores of metals-hydroxide-precipitates
is another possible mechanism of metal separation/removal from
solution [22]. For example, co-precipitation of Mg ions with V/Ni-
hydroxide complexes is a possible mechanism for Mg ion removal
from solution and this, in fact, make metal separation by selective
precipitation is a hard task. It should be mentioned that the colour
of precipitate that collected at pH 11.3 was brown and this indicated
the precipitation of Fe ions which are present in large amounts in
solution.
195
3.3.2. Stepwise precipitation of V and Ni by Na2 CO3
Selective precipitation of V/Ni metals using Na2 CO3 is possi-
ble due to the large difference between Ksp values of carbonate
complexes of the earlier metals. However, and as the case in OH-
precipitation, we did not notice more than one precipitation point.
Only one precipitation point (5 mL of Na2 CO3 was needed for com-
plete precipitation) has been observed and after that point no
carbonate was added to the solution. Table 3 shows the metal con-
tents before and after adding Na2 CO3 to the solution. It seems that
precipitation by carbonate was not effective for V/Ni but it can be
applied for eliminating Mg ions from solution. The collected pre-
cipitate has a white colour (not brown as in OH− case) and this
may be ruled out the precipitation of Fe ions in this case. Selec-
tive precipitation V/Ni and from other ions by carbonate is rather
a complex process. Based on that, more specific extraction proce-
dures are needed to separate Ni/V ions from each other and from
other ions.
3.4. Selective recovery of V and Ni from fly ash
3.4.1. Ni recovery from FA
In fact, recovery of V and Ni from the complex FA matrix, which
contains Mg, Al, Ca, Na, K, and Fe was not possible using precipi-
tation techniques. In fact, there are few studies on this important
subject [4,5,18]. As our earlier attempts on V/Ni separation by selec-
tive precipitation was not successful, other procedures were tested.
Among the published procedures, two were carefully applied and
modified in some instances for selective extraction and separation
of V and Ni that present in FA produced in power plants. The first one
was developed for recovery of V only from oil fly ash and reported
by Vitolo and co-workers [4]. In this procedure, V is leached from
2.0 FA using 150 mL 1.0 M H2 SO4 and then precipitated from the
solution as V2 O5 by the action of NaClO3 . The obtained mass of
V2 O5 was 0.0256 g and this indicated that only 10% of total V in
the sample was recovered. A poor recovery of V was reported and
this would be attributed to; (a) low extraction of V ions by H2 SO4
solution, (b) the chemical nature of FA understudy may be not suit-
able for running this procedure, and (c) the adopted procedure is
limited to V and cannot be applied for Ni or any other cation.
The other tested protocol was the one proposed by Akita & co-
workers in 1995 [5]. The procedure was simple and developed
for FA that produced from burning heavy oil in power stations is
applied for recovering V and Ni in the same time. Table 4 displays
the main important results for recovering Ni (in the presence of
other cations) by Akita’s procedure, however, with some modifica-
tion [5].
Simply, in this procedure Ni is leached before V from the FA
using NH4 Cl/NH3 mixture and then precipitated by the action of
Na2 S. The main factors that affect Ni recovery are the concentration
of NH4 Cl/NH3 leachant, extraction time, solution temperature, and
precipitant (Na2 S) concentration. Among these factors, we stud-
ied the effect of extraction time and the concentration of Na2 S on
the Ni recovery. The recovery of Ni by this procedure, as calculated
from the mass of precipitate (NiS) and the total content of Ni in FA
is (0.79%). As shown in Table 4, Ni recovery from FA is dependent
on the extraction time but not on the Na2 S content. The Ni recov-
ery was increased from 24.3 to 52.3% when the extraction time
increased from 3 to 6 h. It seems that longer times are necessary to
extract Ni from the FA. It should be mentioned that the selective
elution of Ni from the FA was accomplished using (NH4 Cl/NH3 )
mixture and this is an important step in the procedure. The selec-
tive elution of Ni by NH4 Cl/NH3 is attributed to the high formation
constant for the reaction: Ni2+ + 6NH3 → Ni(NH3 )6 2− , Kf = 106 [22].
The following reaction steps are proposed to occur during Ni
recovery from FA:
196 M.A. Al-Ghouti et al. / Chemical Engineering Journal 173 (2011) 191–197

Table 4
Conditions for Ni recovery from FA.a

NH4 Cl (M) NH3 (M) Elution time (h) Temperature (◦ C) Na2 S (M) Ni % recoveryb

2.0 2.0 3 50 1.0 24.3

2.0 2.0 4 50 1.0 36.4
2.0 2.0 5 50 1.0 45.6
2.0 2.0 6 50 1.0 52.3
2.0 2.0 6 50 0.5 54.6
2.0 2.0 6 50 2.0 55.4
2.0 2.0 6 50 3.0 56.3
a
Conditions: FA mass 8.0 g, volume of leachant = 150 mL, and volume of Na2 S = 100 mL.
b
The level of Ni in the FA is 0.79% as shown in Table 1.

Step one: selective extraction of Ni from FA by NH3 :
FA (V, Ni, Ca, Mg, Fe . . .) + NH3 → Ni(NH3 )6 3− , K f (Ni(NH3 )6 3− ) =suitable
The high Kf value is proved the selective uptake of Ni ions compare
to other ions.
Step two: precipitation of Ni ions according to the following reac-
tion:
Ni2+ (aq) + S2− (aq) → NiS(s)
Step three: washing NiS precipitate to remove any soluble ions
like Ca, Mg, K, and Na ions.
For more investigation on the final precipitate, chemical analy-
sis was carried to assess the feasibility of this procedure for V/Ni
separation. Analysis revealed that Ni/V ratio was 27 in the final
precipitate (compare to 4.3 in EDTA extract) and this reflected the
effectiveness of the applied procedure. It is important to mention
FeS would be precipitated or co-precipitated with NiS and this was
proposed because of the high level of Fe in final precipitate.
3.4.2. V recovery from FA
On the other hand, more steps were involved in V separation
from FA. In V extraction, Ni was removed beforehand by NH4 Cl/NH3
and then a new extraction by Na2 CO3 was employed to leach
V and other metals like Ca, Mg and Fe. An extra extraction by
tri-ethylamine (CH3 CH2 )3 N/toluene was employed for a selective
uptake of V. Finally, V was transfer to Na2 CO3 solution and finally
precipitated as NH4 VO3 using NH4 Cl. Effect of other experimental
factors on the V recovery from FA was investigated. The results are
presented in Table 5.
As shown in Table 5, three factors were investigated on V recov-
ery, which are: elution time, pH of the extract and the concentration
of tri-ethylamine in the organic layer. The main conclusions that
would be obtained from Table 5 are: (a) time of the extraction
and pH of the extract are important factors and should be set at
6 h and 5.5, respectively, (b) longer times are needed for com-
plete recovery of V from the FA which is expected due to the
high content of V in FA as indicated in Table 1, (c) pH of the
extract has a significant effect on V recovery and pH 5.5 was
106
for complexation with tri-ethylamine, (d) on the other
side, a slight effect was observed between the concentration of
tri-ethylamine and metal selective recovery. Increasing concentra-
tion of tri-ethylamine from 0.1 to 0.5 M did not affect V recovery
and a maximum recovery of (45%) was obtained in all cases, (e)
the earlier experiments indicated that the content of Na2 CO3 and
NH4 Cl have no effect on V recovery the FA, (f) it is important to
mention that the original procedure of Vitolo and co-workers rec-
ommended tri-octylamine not tri-ethylamine. However, this work
proved that tri-ethylamine is a good alternative to tri-octylamine
for V extraction, and (g) as indicated from Table 5, the pro-
posed method indicated that the optimum extraction conditions
for V recovery are: FA mass = 10 g, volume of Na2 CO3 = 200 mL
(2.0 M), volume of tri-ethylamine/toluene = 50 mL, concentration
of tri-ethylamine/toluene = 0.1 M, extraction time = 6 h, NH4 Cl con-
centration = 1.3 M, and crystallisation time = 20 h.
From chemical point of view, the following reaction steps are
proposed during V recovery from FA:
Step one: selective extraction of Ni from FA by NH3 :
FA (V, Ni, Mo, Fe . . .) + NH3 → Ni(NH3 )6 3−
Step two: extraction of V and other metals by action of CO3 2− :
FA (V, Mo, Fe . . .) + CO3 2− → V–CO3 2− , Mo–CO3 2− , Fe–CO3 2−
Step three: extraction of V by tri-ethylamine N(CH2 CH3 )3 from
other metals-carbonates:
V–CO3 2− , Mo–CO3 2− , Fe–CO3 2− + N(CH2 CH3 )3 → V–N(CH2 CH3 )3
Step four: release V from V–N(CH2 CH3 )3 by CO3 2− :
V–N(CH2 CH3 )3 + CO3 2− → V–CO3 2−

Table 5
Conditions for V recovery from the FA.a

Na2 CO3 (M) pH of the extract Elution time (h) Tri-ethylamine/toluene (M) NH4 Cl (M) V% recoveryb

2.0 5.5 4 0.1 1.3 32.6

2.0 5.5 5 0.1 1.3 39.6
2.0 5.5 6 0.1 1.3 44.2
2.0 2.0 6 0.1 1.3 45.3
2.0 10.0 6 0.1 1.3 33.4
2.0 5.5 6 0.2 1.3 43.5
2.0 5.5 6 0.3 1.3 44.6
2.0 5.5 6 0.5 1.3 45.8
a
Conditions: FA mass 10 g and volume of Na2 CO3 = 200 mL, volume of tri-ethylamine/toluene = 50 mL.
b
The level of V in the FA is 6.1% as shown in Table 1.
 M.A. Al-Ghouti et al. / Chemical Engineering Journal 173 (2011) 191–197
Step five: precipitation of V as NH4 VO3 by action NH4 Cl as:
V–CO3 2− + NH4 Cl → NH4 VO3 .
Analysis that carried out on the final precipitate revealed that V/Ni
ratio was more than 55 indicating the effectiveness of the applied
procedure for metal separation. Again, it is important to mention
that the final precipitate is contaminated with other ions that co-
precipitate with vanadium complexes.
4. Conclusions
The FA generated in our local power stations, which powered
by heavy fuel, was found to be rich with V, Ni, Mg, and Fe. V and
Ni were the most abundant with mass percents of 6.1 and 0.79%,
respectively. The best extraction results were observed using 1.0 M
EDTA solution of initial pH 0.71. Separation of V and Ni by direct
precipitation using NaOH and Na2 CO3 solutions was not achieved
and the content of both metals do not significantly changed after
adding precipitating agents. However, 25% of Mg was precipitated
from other metals using NaOH. The procedure of Akita & co-workers
was adopted in this work, however with some modifications, for
V/Ni separation. With reasonable recovery (56%), Ni was directly
extracted from FA using NH4 Cl/NH3 solution and then precipitated
using Na2 S solution. The most significant factor on Ni recovery
was the extraction time and the optimum time was 6 h. On the
other hand, V was recovered from Ni-free-FA by a multi-step pro-
cedure which started with leaching by Na2 CO3 , selective extraction
by tri-ethylamine, extraction by Na2 CO3 and finally precipitated
using NH4 Cl. The best extraction conditions were (45% recov-
ery): FA mass = 10 g and volume of Na2 CO3 = 200 mL, concentration
of Na2 CO3 = 2.0 M, volume of tri-ethylamine/toluene = 50 mL, con-
centration of tri-ethylamine/toluene = 0.1 M, extraction time = 6 h,
NH4 Cl concentration = 1.3 M and crystallization time = 20 h. The
maximum recovery was 45% which calculated against the ultimate
V level in FA, 6.1%. Chemical analysis on both metals precipitate
revealed that the metal separation was satisfactory; however, co-
precipitation of other metals like Fe was accomplished especially
with Ni ions.
Acknowledgements
The authors are thankful for The Higher Council for Science
and Technology, Jordan for the financial support. Furthermore, the
authors are also grateful for the analysts, institutions, and universi-
ties that collaborate with us in carrying out this national research.
A special thanks to the Royal Scientific Society for their valuable
moral support.
197
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