Journal of Cleaner Production 243 (2020) 118631

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Experimental and theoretical study on the behaviour of a pickling

solution: The role of ferrous ions
Fangming Yang a, Yan Wu b, *, Xiting Fang b, Lijuan Ma c
a
School of Marine Science and Technology, Tianjin University, Tianjin, 300072, PR China
b
College of Chemical Engineering and Materials Science, Tianjin University of Science & Technology, Tianjin, 300457, PR China
c
School of Chemistry and Materials Science, Shanxi Normal University, Linfen, Shanxi, 041000, PR China

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

Article history: The existence of ferrous ions plays an important role in the performance of pickling liquor as well as the
Received 29 January 2019 recovery of hydrochloric acid from waste pickling liquor. The promotion mechanism and the interaction
Received in revised form between ferrous ions and hydrogen chloride molecules have remained largely unsolved. In this research,
23 September 2019
the fundamental aspects of a simulated hydrochloric acid pickling solution with different concentrations
Accepted 26 September 2019
Available online 27 September 2019
of ferrous ions were experimentally and theoretically studied. The experimental results showed that the
existence of ferrous ions in the pickling liquor effectively inhibited the volatilisation of hydrogen chloride
Handling editor: Prof. Jiri Jaromir Kleme
s from solution and that the inhibition of volatilisation enhanced with an increase in concentration of
ferrous ions. To understand the interaction between ferrous ions and hydrogen chloride molecules, the
Keywords: structure and thermodynamic properties of possible hydration structures were obtained by using mo-
Pickling liquors lecular simulation. The results showed that a new type of cluster, hydrogen chloride-ferrous ion-water,
Ferrous ion was formed in the presence of ferrous ions, which made the hydrogen chloride molecules in the pickling
Volatilisation liquor more stable compared to the same condition without ferrous ions. The existence of ferrous ions in
Molecular simulation
pickling liquor benefits the pickling process from an economic and environmental aspect.
Hydrated hydrogen chloride clusters
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction processes. It is aimed at eliminating impurities and the oxide film

The iron and steel industries are important for every country
that provides primary materials for a wide range of applications,
including construction, transport, and energy (Pan et al., 2016;
Spengler et al., 1998). Although impressive progress has been
made, steel manufacturing still faces many challenges, such as the
high energy required, heavy pollution problems (solid waste,
wastewater, and gas), and large water consumption (Chen et al.,
2017; Gao et al., 2016). In China, over 15% of the total energy con-
sumption and approximately 14% of the total wastewater and waste
gas across the country are contributed by steel manufacturing (Guo
and Fu, 2010). Thus, there is an urgent need to make the entire steel
manufacturing process efficient and clean. Amongst the different
steps, the acid pickling process, which involves a large amount of
strong acids and water, has received increasing attention (Stocks
et al., 2005).
The acid pickling process is an important part of the finishing
* Corresponding author.
E-mail address: wuyan_tust@163.com (Y. Wu).
on the metal surface that are formed during the hot rolling of steel.
In the pickling process, inorganic acids, particularly hydrochloric
acid (Li et al., 2005), sulfuric acid (Quraishi and Rawat, 2001), hy-
drofluoric acid (Li et al., 2005) or a mixture of acids (Lindell and
Pettersson, 2010), have been extensively used as the pickling li-
quor. Among all the acids, hydrochloric acid has been preferentially
chosen for steel production. Compared to using sulfuric acid, using
hydrochloric acid allows a low operation temperature and cost,
faster and cleaner pickling, and greater utilisation of the acid.
Meanwhile, hydrochloric acid is more environmentally safe than
nitric acid and phosphoric acid because it does not release waste-
water enriched with nitrogen and phosphor (Agrawal and Sahu,
2009). Li et al. (2005, 2008) studied the pickling process for 304
stainless steel by using sulfuric acid and hydrochloric acid, and they
found that hydrochloric acid exhibited a higher removal efficiency
compared to that exhibited by sulfuric acid. Yue et al. (2016)
investigated the pickling of ferritic stainless steel by using
different acids. Their results demonstrated that using hydrochloric
acid provides unique advantages, including less pollution, a low
cost of waste acid recovery, and high removal efficiency, for the

https://doi.org/10.1016/j.jclepro.2019.118631
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
2 F. Yang et al. / Journal of Cleaner Production 243 (2020) 118631
residual chromium-depleted layer. The entire pickling process
consists of two major steps: pickling and rinsing (Kittisupakorn and
Kaewpradit, 2003). The pickling was performed at a high temper-
ature (50-70
C) and a hydrochloric acid concentration of 15-20% to
remove the oxide layer formed on steel during manufacturing and
hot-working when the surface reacts with oxygen in the air
(Beadle, 1972). The oxidation layer composed of different types of
iron oxides (Fe2O3, Fe3O4, and FeO) reacts with hydrochloric acid to
form ferrous chloride via reactions 1-3 (Tang et al., 2012). Mean-
while, hydrochloric acid penetrates the oxidation layer and
attacked the underlying metal. Ferrous chloride and gaseous
hydrogen are produced by the reaction between hydrochloric acid
and the base steel (reaction 4) (Tang et al., 2012a). Because of this
reaction, the oxidation layer is loosened from the surface, which is
an important action in pickling operation (Staley, 1926). However,
the formed hydrogen adsorbed on base surface can penetrate the
metal lattice, which can weaken the lattice bonding forces and
reduce the ability of the metal to deform (Paatsch, 2011). Due to the
reduced ductility, brittle fracture of the metal materials occurs
when an external tensile load is applied (Treischel, 1919; Kuron,
2000). One of the practical solutions to tackle this problem is the
addition of inhibitors in pickling solution. Inhibitors are specifically
adsorbed on the active sites of the blank steel surface to form a type
of thin layers to prevent the attack of metal from acid (Feser et al.,
2002). Another practical method is to reduce the immersion time of
the metal in pickling solution and therefore reduce the absorption
of hydrogen (Staley, 1926). In addition, hydrogen in solution can act
as the reductant to convert Fe3þ to Fe2þ in pickling solution.
€
(Ozdemir et al., 2006).
Fe2O3 þ Fe þ 6HCl / 3FeCl2 þ 3H2O
Fe3O4 þ Fe þ 8HCl / 4FeCl2 þ 4H2O
FeO þ 2HCl / FeCl2 þ H2O
Fe þ 2HCl / FeCl2 þ H2
To optimise the pickling process using hydrochloric acid, many
factors have been investigated. Shi et al. (2018) studied the role of
components and structure of the oxide layer in hydrochloric acid
pickling process. Hudson et al. (1967) studied the effect of HCl
concentration, dissolved iron, and temperature on pickling process
using hydrochloric acid. Among them, the concentration of ferrous
chloride in solution has been considered one of the key parameters
(Kleingarn, 1988). According to the above reactions, the concen-
tration of ferrous chloride increased with pickling time, and the
concentration of ferric ions in the pickling solution could reach 60-
120 g L1 (Ortiz et al., 2005). Kleingarn (1988) studied the rela-
tionship between acid concentration and ferric ions in pickling li-
quor and found that the pickling process became faster when ferric
ions were present in the solution compared to that in ferrous-free
solutions of the same acid concentration. Meanwhile, a diagram
of the pickling time versus the concentration of hydrochloric acid
and ferric ions (Kleingarn curve) was proposed. This curve is very
helpful in managing the replacement and recycling of hydrochloric
acid pickling liquor under economic optimal conditions. In addition
to handling the pickling process, handling the waste pickling liquor
is also important owing to its high corrosive nature (Regel-Rosocka,
2010). Although hydrochloric acid is relatively inexpensive, the
indirect costs (cost of neutralising chemicals, disposal cost, labour
cost, etc.) associated with the disposal of pickling liquid may go well
beyond the cost of the acid. To reduce the use of chemicals and air
and water pollution, the recovery and regeneration of acid from
waste pickling liquor has been investigated (Leonzio, 2016).
Evaporation and membrane separation that could recover most of
the hydrochloric acid have been considered as important options
(Regel-Rosocka, 2010). As reported by many papers, the existence
of ferrous ions in the waste pickling liquor could help the recovery
of hydrochloric acid from the solution, but the mechanism is still
unclear (Tomaszewska et al., 1998).
Overall, the existence of ferric ions in pickling liquor plays an
important role in the performance of the pickling solution as well
as the recovery of hydrochloric acid from waste pickling liquor.
However, the interaction mechanism between ferric ions and
hydrogen chloride molecules in pickling process has been rarely
reported. A better understanding of the mechanism is helpful for
the energy-efficient and cost-effective design of pickling process
and recovery of hydrochloric acid from spent pickling liquor.
Moreover, it is well known that a significant disadvantage of hy-
drochloric acid is its high volatility under pickling conditions,
gaseous hydrogen chloride will cause corrosion to equipment
during and after the pickling process and increase the cost of the
pickling solution (Sittig, 1985; Evans et al., 2011). The effect of ferric
ions on the volatilisation of hydrochloric acid is still unknown. So,
this study aimed to find out the role of ferric ions on the volatili-
sation of hydrochloric acid during the pickling process by means of
experiments and molecular simulation. The volatilisation of a
simulated hydrochloric acid pickling solution with different con-
centrations of ferric ions and molecular simulations using density
functional theory (DFT) that has rarely been reported in studies of
the pickling solution were employed.
2. Experimental
(1) 2.1. Materials
(2) Hydrochloride acid (analytical reagent), methyl orange
(analytical reagent), sodium hydroxide (analytical reagent), and
(3) calcium carbonate (analytical reagent) were purchased from Bei-
fang Tianyi Chemical Company. Iron(II) chloride (FeCl2, analytical
(4) reagent) was obtained from Beichen Fangzheng Chemical Reagent
Company. Ethylenediaminetetraacetic acid (EDTA) was bought
from TCRY. Calcium-EDTA (Ca-EDTA) was synthesised based on a
procedure reported in a former study (Huang et al., 2003). The
simulated pickling solutions with hydrochloric acid concentrations
of 10 wt%, 15 wt%, and 20 wt% were prepared by diluting concen-
trated hydrochloric acid (37 wt%) in a 2-L volumetric flask using
deionised water. A certain amount of FeCl2 was added to the pick-
ling solution to prepare the pickling solution with ferrous ions.
2.2. Volatilisation of hydrochloric acid
Volatilisation of hydrochloric acid from solution is the process
that the hydrogen chloride molecules escape from the gas-liquid
interface. In this research, the volatilisation of the simulated pick-
ling solutions with different concentrations of hydrochloric acid
was carried out in the temperature range of 50-70
C for 1 h.
Different amounts of FeCl2 were added to the hydrochloric acid
solution to investigate its impact on volatilisation. The experi-
mental set-up is shown in Fig. 1. In a typical process, 150 mL of the
pickling solution was added into the vessel, and then the vessel was
placed in a water bath with a preset temperature. The volatilisation
process lasted for 60 min to simulate the pickling process in prac-
tical application. The concentration of the hydrochloric acid solu-
tion was measured using a concentration calibration method with a
sodium hydroxide titration solution. 0.1 mL of hydrochloric acid
solution was added to a small beaker containing 30 mL of ultrapure
water and methyl orange indicator (the pH range for the colour
change was 5.2-5.6). Then 2 mL of the masking agent, Ca-EDTA, was
 F. Yang et al. / Journal of Cleaner Production 243 (2020) 118631 3

shown in Fig. 2. It can be found that temperature and concentration

of hydrochloric acid are the key parameters that determining the
volatilisation of hydrochloric acid. Fig. 2a shows that the volatili-
sation process was accelerated by increasing the temperature and
acid concentration. The volatilisation loss of the 10-wt% hydro-
chloric acid solution was 14.3% at 50
C for 60 min, which was
almost doubled (25.3%) as the temperature and concentration of
hydrochloric acid increased to 70
C and 20 wt%, respectively.
Fig. 2b shows the change in concentration of hydrochloric acid as a
function of time at different temperatures. Clearly, a linear rela-
tionship between the concentration of hydrochloric acid in solution
and time was observed for all concentrations, indicating that the
volatilisation rate of hydrochloric acid was kept constant within
60 min. Therefore, the average volatilisation rate within 1 h was
also calculated. With an increase in the concentration of

Fig. 1. Experimental apparatus for volatilisation experiments.

added before the titration to avoid interference from the Fe2þ ions.
In addition, the change in the concentration of hydrochloric acid
with time was also investigated in which the concentration of hy-
drochloric acid in solution was measured every 10 min during a 1-h
volatilisation experiment.

2.3. Computational simulations

Molecular modelling studies and geometry optimisation were

carried out by using Gaussian 03 (Frisch et al., 2004). Based on
empirical potential Tip4p, a molecular dynamics simulation
annealing optimisation algorithm, and gene optimisation algorithm
methods (Kaplan, 1998), the most stable structure of water clusters,
(H2O)n, was first obtained, which acted as the basic 3D model to
design hydrogen chloride-water and hydrogen chloride-ferrous
ions-water clusters. Considering the concentration of hydrochlo-
ric acid and ferric ions in solution and during the volatilisation,
([Fe(H2O)n]2þ(HCl) (n ¼ 4-10)) were chosen as the possible
hydrogen chloride-ferrous ions-water cluster in solution. The pro-
posed structure was first optimised by using the HF/STO-3G basis
set in Gaussian 03; then, further optimisation was carried out using (a)
B3LYP/6-31þG(d,p) to ensure that the obtained structures
possessed the lowest potential energy surface. The final optimisa-
tion and frequency calculation of the cluster structure was
computed by the B3LYP/6-311þþG(d,p) basis set, which was used
to calculate the single-point energy based on the MP2/6-
311þþG(d,p) level. A zero-point energy (ZPE) correction was
accordingly accomplished. To investigate the impact of ferric ions
on the cluster structure, the hydrogen chloride-water cluster,
(HCl)n(H2O)10 (n ¼ 0-e3), was also optimised and calculated using
the same procedure.

3. Results and discussion

3.1. Volatilisation of the acid pickling solution

In pickling process using hydrochloric acid, the high volatility of

hydrochloric acid bas been the main concern under pickling con-
dition. High temperature benefits the pickling process, pickling
efficiency can be approximately doubled by the rise of 10
C
(Garverick, 1994). However, the volatilisation of hydrochloric acid
accelerates with increasing temperature due to the endothermic
nature of volatilisation process. To better understand the volatili- (b)
sation of the pickling solutions, the volatilisation of different con- Fig. 2. Volatilisation performance of hydrochloric acid solutions: (a) total HCl volati-
centrations of hydrochloric acid under a simulated pickling lisation of the HCl solutions; (b) volatilisation curves of hydrochloric acid solutions
temperature of 50-70
C was investigated, and the results are with time.
4 F. Yang et al. / Journal of Cleaner Production 243 (2020) 118631

hydrochloric acid, the average volatilisation rate sharply increased

to 0.019 mol L1 min1 (20 wt% hydrochloric acid solution at 50
C),
which was three times higher than that of 10 wt% hydrochloric acid
solution at 50
C (0.0065 mol L1 min1). This may be attributed to
the existence of a concentration difference and mass transfer
phenomenon at the gas/liquid interface. It indicated that the vol-
atilisation of hydrochloric acid became much faster with increase of
the concentration of hydrochloric acid in solution. In industry ap-
plications, pickling liquor containing higher concentration of hy-
drochloric acid suffers more from the volatilisation process.

3.2. Effect of ferrous ions on volatilisation of hydrochloric acid

solution

During the pickling process, the iron oxides on the surface dis-
solved into the HCl solution. It has been reported that most of the
iron in solution is in the form of ferrous ions, as shown in reactions
1-4, and the concentration of ferrous ions could reach 60-120 g L1
(Ortiz et al., 2005). According to Kleingarn Curve, ferrous ions in
pickling liquor has a significant impact on pickling process.
Compared to fresh pickling liquor, a certain level of ferrous ions
existing in solution can substantially improve the pickling effi-
ciency (Kleingarn, 1988) while the role of ferrous ions is still un- (a)
clear. To investigate the effect of ferrous ions on the pickling
solution, volatilisation experiments of simulated pickling solutions
(10-20 wt%) with various concentrations of ferrous ions (20-
120 g L1) were carried out. As shown in Fig. 3, the existence of
ferrous ions in the hydrochloric acid solution could effectively
inhibit the volatilisation of hydrochloric acid, and clearly the inhi-
bition of volatilisation of hydrochloric acid was governed by the
concentration of ferrous ions in solution and the operation tem-
perature. The volatilisation rate of hydrochloric acid continuously
decreased with an increase in concentration of ferrous ions in so-
lution. For example, the volatilisation rate of 10 wt% hydrochloric
acid solution decreased linearly from 20.37% to 17.31% as the con-
centration of ferrous ions increased from 0 to 60 g L1, and a further
drop to 14.56% was observed when the concentration of ferrous
ions increased to 90 g L1. A similar trend was also observed for the
15 wt% and 20 wt% hydrochloric acid solutions. A 37% drop in the
volatilisation rate from 21.39% (0 g L1) to 13.51% (60 g L1) was
observed for the 20 wt% hydrochloric acid solution at 50
C. For the
15 wt% hydrochloric acid solution, a higher concentration of
ferrous, 120 g L1, was also investigated. As shown in Fig. 3, the
volatilisation rate sharply decreased by 42% to 14.58% at 70
C
compared to that for the 15-wt% hydrochloric acid solution without
(b)
ferrous ions, which was the lowest among all the samples. Mean-
while, ferrous ions could achieve a better inhibition of volatilisation Fig. 3. Volatilisation performance of hydrochloric acid solutions containing ferrous
at a higher concentration of the hydrochloric acid solution. For ions: (a) total volatilisation of the hydrochloric acid solutions with different concen-
instance, the volatilisation rate of the 20 wt% hydrochloric acid tration of ferrous ions; (b) volatilisation curves of solutions containing ferrous ions
with time.
solution was reduced by 29% when the concentration of ferrous
ions was 60 g L1. It was much higher than that of the 10% and 15%
hydrochloric acid solutions, which showed 20% and 26.9% loss ferrous ions further increased to 120 g L1, as shown in Fig. 3a, a
under the same conditions, respectively. In addition to the con- similar volatilisation rate was observed in the temperature range
centration of hydrochloric acid solution and ferrous ions in solu- from 50 to 70
C, indicating that a good inhibition of volatilisation
tion, the operation temperature was also an important parameter. could be achieved at the tested temperature range. Fig. 3b presents
The decrease in volatilisation rate became smaller with tempera- the change in concentration of hydrochloric acid solutions with
ture. At the concentration of 60 g L1, the decrease in the volatili- different concentrations of ferrous ions as a function of time.
sation rate of the 10 wt% hydrochloric acid solution declined from Clearly, the volatilisation rate was slowed down with an increase in
19.6 to 15.0 wt% as the temperature increased from 50
C to 60
C concentration of ferrous ions in solution, indicating that ferrous
and from 26.9 to 36.8 wt% to 6.2 and 24.5 wt% with further increase ions make the ionized hydrogen chloride molecules more stable in
in temperature to 70
C for the 15 wt% and 20 wt% hydrochloric acid pickling solution. This will help to improve the effectivity of acids in
solution, respectively. The reason may be that hydrogen chloride pickling liquor and therefore the whole pickling efficiency, which
molecules became active and the mass transfer at the gas/liquid can be a reasonable explanation of Kleingarn Curve.
interface increased at higher temperature, which makes inhibition
of volatilisation more difficult. However, when the concentration of
 F. Yang et al. / Journal of Cleaner Production 243 (2020) 118631 5

3.3. Inhibition mechanism of Fe2þ in solution Table 1

Total energies of the system of (HCl)n(H2O)10 (n ¼ 0e-3) clusters on B3LYP/6-31G.

The experimental results demonstrated that the existence of Cluster NO. E(a.u.) DEB(kJ/mol)
ferrous ions can significantly improve the stability of pickling liquor (H2O)10 a 764.234 2006497
and reduce its volatilisation loss under pickling conditions. How- (HCl)3(H2O)10 b1 2115.463 5554149
ever, the interaction mechanism between ferrous ions and (HCl)3(H2O)10 b2 2115.392 5553962
hydrogen chloride in pickling process has been rarely reported. (HCl)3(H2O)10 b3 2115.402 5553988
(HCl)2(H2O)10 c1 1660.248 4358981
Basically, as a strong acid, hydrogen chloride molecules are fully
(HCl)2(H2O)10 c2 1660.301 4359121
ionized in water to form stable ion pairs with water molecules by (HCl)2(H2O)10 c3 1660.246 4358977
intermolecular hydrogen bonds and weak interactions originating (HCl)2(H2O)10 c4 1660.288 4359087
from various forces. Therefore, at the molecular level, volatilisation (HCl)(H2O)10 d1 1205.087 3163956
(HCl)(H2O)10 d2 1205.067 3163904
is actually the process in which hydrogen chloride molecules are
(HCl)(H2O)10 d3 1205.082 3163943
dissociated from hydrogen chloride-water clusters and go into the
ambient environment. In this work, a molecular simulation based 1a.u. ¼ 2625.5 kJ/mol.

on quantum chemistry was employed to understand the dissocia-

tion of hydrogen chloride molecules from aqueous solution and the
the volatilisation of HCl from the clusters, the energy requirement
effect of ferrous ions on the hydrogen chloride-water clusters on
was calculated by using the method proposed by Ochterski (2000)
the molecular level.
(see Eq. (5)):

3.3.1. Hydrogen chlorideewater clusters in solution
Hydrogen chloride (HCl)-water (H2O) clusters have been widely
investigated as prototypical systems to understand the molecular
mechanism of acid dissociation in solution, and different low-
energy minima structures of (HCl)m(H2O)n have been developed
(Lin and Paesani, 2014). Lin and Paesani (2013) investigated the
structural and thermodynamic properties of (HCl)(H2O)n (n ¼ 4-10)
clusters. Morrison et al. (2010) studied the structures of
(HCl)m(H2O)n (m:n ¼ 1:1, 2:1, 3:1, and 2:2). In this study, consid-
ering the concentration of hydrochloric acid solution, large
hydrogen chloride-water clusters, (HCl)n(H2O)10 (n ¼ 1-3) and a
pure water cluster (H2O)10, were designed and investigated. As
shown in Fig. 4, our calculation at the B3LYP/6-311þþG(d,p) level
showed the extended cuboid structure to be one of the stable
structures of (H2O)10, which was employed as the baseline to
calculate the energy requirement for volatilisation. The lowest
energy structures of (HCl)n(H2O)10 (n¼1-3) calculated at the B3LYP/
6-311þþg(d,p) level are shown in Fig. 4, and the total energies of
the possible clusters are shown in Table 1. Structures b1, c2, and d1
were the most stable structures with the lowest energies for
(HCl)n(H2O)10 (n ¼ 1, 2, 3), respectively. The volatilisation of HCl
molecules from solution actually involved the rearrangement of
hydrogen chloride-water clusters from a stable structure to an
unstable structure; then, n generally reduced from 3 to 0, and en-
ergy was required for the rearrangement of the clusters. To evaluate
Fig. 4. The lowest-energy structures of (HCl)n(H2O)10.
DE ¼ E((HCl)n-1 (H2O)10þE(HCl)  E((HCl)n-1 (H2O)10 (5)
where E(HCl) and E(HCl)n(H2O)10 are the binding energies of HCl
molecules and the cluster, respectively. E(HCl)n-1(H2O)10 is the
binding energy of the rearranged cluster after volatilisation. Owing
to the vaporisation of hydrogen chloride, the (HCl)3(H2O)10 cluster
gradually changed into (HCl)(H2O)10. Based on Equation (5), the
energy required for the rearrangement of the (HCl)3(H2O)10 cluster
to (HCl)2(H2O)10 was calculated as 68.339 kJ mol1, whereas it
increased three times to 205.233 kJ mol1 when (HCl)2(H2O)10
changed into (HCl)(H2O)10. This indicates that the volatilisation of
hydrochloric acid became harder as the concentration of HCl
decreased, which is consistent with the experimental results
shown in Fig. 2a.
3.3.2. Hydrogen chloride-ferrous ions-water cluster in solution
The existence of ferrous ions in water solution can change the
structure of the water clusters. Numerous studies have investigated
the hydration clusters of ferrous ions via molecular simulations
(Ensing and Baerends, 2002). Remsungnen and Rode (2003) stud-
ied the hydration cluster of ferrous ions using quantum mechani-
cal/molecular mechanical molecular dynamics (QM/MM-MD)
calculations, and their results showed that two hydration shells
were formed in the ferrous hydration cluster. The octahedral
structure of the first hydration shell was occupied by six water
molecules, while the second hydration shell had 12.4 water mole-
cules. Until now, the structure of the first shell has been commonly
accepted, while the second hydration shell is still ambiguous. Lei
et al. (2012) investigated the geometrical structures of hydrated
ferrous ion ([Fe(H2O)n]2þ (n ¼ 1-19)) clusters and found that the
second hydration shell contained seven water molecules.
In this study, the hydrogen chloride-ferrous ions-water cluster
was designed based on the structure of hydrated ferrous ion, and
one HCl molecule was introduced into the designed structure,
which was in the form of [Fe(H2O)n]2þ(HCl) (n ¼ 1-10). According to
the references above, two hydration shells were employed when
the clusters were designed. Considering the concentration of hy-
drochloric acid and ferrous ions in solution, the structures of
[Fe(H2O)n]2þ(HCl) (n ¼ 4-10) were optimised and calculated. The
lowest energy structures of [Fe(H2O)n]2þ(HCl) (n ¼ 4-10) are shown
in Fig. 5. The existence of hydrogen chloride molecules in solution
did not change the structure of the hydrated ferrous ion clusters in
which the first hydration shell was still an octahedral structure
occupied by six water molecules (Lei et al., 2012). A hydrogen bond
between hydrogen chloride and one of the water molecules in the
6 F. Yang et al. / Journal of Cleaner Production 243 (2020) 118631
Fig. 5. The lowest-energy structures of [Fe(H2O)n]2þ(HCl) (n ¼ 4-10).
hydrated ferrous ion cluster was observed. Similar to the hydrogen
chloride-water clusters, the method proposed by Ochterski (2000)
was used to calculate the energy required for volatilisation from the
solution (See Eq. (6)):
DE ¼ E([Fe(H2O)n-1]2þ(HCl)) þE(H2O)  E([Fe(H2O)n]2þ(HCl))
where E([Fe(H2O)n-1]2þ(HCl)) and E(H2O) are the binding energies
of the HCl molecule and the cluster, respectively.
E([Fe(H2O)n]2þ(HCl)) is the binding energy of the rearranged cluster
after volatilisation of hydrochloric acid. To investigate the differ-
ence between volatilisation of hydrochloric acid in water and in a
solution containing ferrous ions, the energy requirement for vola-
tilisation from aqueous solution with/without ferrous ions were
calculated. Fig. 6 shows the energy requirement for volatilisation of
hydrogen chloride from [Fe(H2O)4]2þ(HCl) to [Fe(H2O)5]2þ(HCl) and
Fig. 6. Thermodynamic analysis of hydrochloric acid solution and hydrochloric acid
solution containing ferrous ions.
from [Fe(H2O)5]2þ(HCl) to [Fe(H2O)10]2þ(HCl) in ferrous ions con-
taining solution and from (HCl)3(H2O)10 to (HCl)2(H2O)10 and from
(HCl)2(H2O)10 to (HCl)(H2O)10 in water solution. It can be seen that
the energy requirement of volatilisation of hydrochloric acid from
the [Fe(H2O)n]2þ(HCl) cluster was much higher compared to that
from the (HCl)n(H2O)10 cluster under similar conditions. It means
that the presence of ferrous ions in solution changed the cluster
structure from hydrogen chloride-water to more stable hydrogen
chlorideeferrous ionsewater and therefore increase the stability of
ionized hydrogen chloride molecules in solution to reduce the
evaporation loss of hydrogen chloride and therefore increase the
efficiency of pickling solution, which is in consistent with the
experimental results. However, the higher dissociation energy is
required for hydrogen ions from hydrogen chloride-ferrous ions-
water cluster, which makes hydrogen ions less active. At the
boundary layer, the reaction rate between iron oxides and
hydrogen ions (reaction 1-3) is reduced. It has been reported that
the existence of the salt of the acid in pickling solution caused the
retardation of activity (Staley, 1926). This can be well explained by
our results from a molecular level. At the same time, due to the
reduced activity of acid, the reaction between hydrogen ions and
base metal is supressed and the hydrogen formation also slowed
down.
In addition, the simulation results could also explain why the
diffusion of hydrogen chloride molecules through the membrane
was easier than for water in the presence of ferrous ions
(Tomaszewska et al., 2000). In solution, hydrogen chloride mole-
cules were in the second hydration shell of the ferrous ions-water-
hydrogen chloride cluster, where the first shell was water and the
number of water molecules in the cluster was much higher than
hydrogen chloride molecules. This means that the interaction be-
tween water and ferrous ions is much stronger than that between
water and hydrogen chloride molecule. Thus, under vacuum con-
(6)
ditions, the concentration of hydrogen chloride is higher in the gas
phase. All the results above confirmed that molecular simulation
could be effectively used to study the pickling liquor.
3.4. Potential contributions to acid pickling process
According to the experimental and simulation results, the
pickling process can be further optimised by controlling ferrous
ions in solution. Ferrous ions and hydrogen chloride molecules in
solution will form stable hydrogen chloride-ferrous ions clusters,
which improve the stability of hydrogen chloride molecules in so-
lution. This means that more hydrogen chloride molecules in
pickling solution will react with iron oxide in the presence of
ferrous ions, which potentially reduces the consumption of fresh
acid solution per unit. The presence of ferrous ions in solution could
also benefit the management of the pickling liquor. Fig. 7 shows the
optimum pickling time curve developed by Kleingarn and the effect
of ferrous ions on the pickling time. The plots in the figure repre-
sent the concentration of hydrochloric acid and ferrous ions in
solution after 60 min of volatilisation, as discussed in Section 3.3.
This indicated that the pickling time decreased with an increase in
concentration of ferrous ions. Meanwhile, the existence of ferrous
ions in solution reduced the loss of hydrochloric acid under the
same operation conditions and thus, the plots moved to the top
right closer to the optimum pickling time, which indicated that the
inhibition of volatilisation of hydrochloric acid by ferrous ions also
contributed to the reduction in the pickling time. In addition,
instead of replacing the entire spent acid bath with fresh acid, the
spent pickling solution can be used by controlling the acid and iron
concentrations, which requires an even faster pickling time. This
could reduce the water consumption and volume of pickling solu-
tion waste. More importantly, our research demonstrated that
 F. Yang et al. / Journal of Cleaner Production 243 (2020) 118631
Fig. 7. Selected samples with respect to Kleingarn acid system.
molecular simulation, which has never been used in pickling pro-
cess, could be a powerful tool to predict the properties and per-
formance of the pickling liquor without time-consuming and
complicated experiments. In real pickling liquor, it contains not
only ferrous ions but also other metal ions like zinc, chromium or
nickel, molecular simulation could also be used to predict the
properties of pickling liquor with complex composition and
manage the pickling process.
4. Conclusions
In this study, simulated pickling liquor prepared by using hy-
drochloric acid and ferrous chloride was used to investigate the role
of ferrous ions in the behaviour of pickling liquor. The volatilisation
experiments of pickling liquor reveal that both acid concentration
and pickling temperature play an important role in the volatility of
pickling liquor. The existence of ferrous ions in the pickling liquor
was able to effectively reduce the volatilisation of hydrochloric acid,
and the volatilisation rate of hydrochloric acid decreased with an
increase in concentration of ferrous ions. It indicates that the sta-
bility of ionized hydrogen chloride in solution improved by the
ferrous ions. In order to understand the interaction mechanism
between ferrous ions and hydrogen chloride, molecular simulation
was employed for the first time. The simulation results demon-
strated that ferrous ions in solution form a new type of hydrogen
chloride-ferrous ions-water cluster in the form of
[Fe(H2O)n]2þ(HCl), which make the hydrogen chloride molecules
much more stable in the pickling liquor than the case without
ferrous ions under similar conditions This will cause retardation of
acid activity and therefore reduce the reaction rate between acid
and metal oxides/base metal. From an environmental and eco-
nomic perspective, the findings of this research can be helpful to
reduce pollution and the cost of the pickling process. This research
for the first distinguishes the role of ferrous ions from a molecular
level and also opens a potential way for evaluating the performance
of pickling liquor using molecular simulation.
Acknowledgments
We gratefully acknowledge our colleagues for assistance with
some of the experimental work. Additionally, this work was sup-
ported by the National Natural Science Foundation of China [grant
7
number 21107080].
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