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Researches on possibility to recover and reuse the iron(II) sulphate from

etching of rolled steels

Article in Environmental Engineering and Management Journal · May 2009

DOI: 10.30638/eemj.2009.074

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Environmental Engineering and Management Journal May/June 2009, Vol.8, No.3, 541-547
http://omicron.ch.tuiasi.ro/EEMJ/

“Gheorghe Asachi” Technical University of Iasi, Romania

______________________________________________________________________________________________

RESEARCHES ON POSSIBILITY TO RECOVER AND REUSE THE

IRON(II) SULPHATE FROM ETCHING OF ROLLED STEELS

Liliana Lazăr, Ion Balasanian, Florin Bandrabur

“Gheorghe Asachi” Technical University Iasi, Faculty of Chemical Engineering and Environmental Protection,
Department of Chemical Engineering, 71 D. Mangeron, Iasi, 700050

Abstract

The etching of iron materials in sulphuric acid solutions allows the dissolution of the iron oxides with formation of iron sulphates.
The relatively low solubility of the formed sulphates imposes their separation for avoiding the contamination of the etching bath,
as well as for preventing the environmental pollution through the wastewater. Within the flow sheet of the processing of the hot or
cold rolled steel, a stage of separation by crystallization of iron sulphate is foreseen. The resulted iron(II) sulphate does not meet
the qualities of the technical product (FeSO4.7H2O), fact that limits its utilization.
In this paper, the possibility of recovering the iron(II) sulphate resulted from preliminary processing of the solution from etching
of rolled steels is studied. The re-crystallization of iron(II) sulphate from saturated solutions was investigated in order to reduce
the free acidity and the content of iron(III) sulphate, as well as to enhance the granulometry spectra. The re-crystallization was
performed in two stages at the temperature of 283.15 K. The obtained product meets the quality requirements for technical iron(II)
sulphate approved by the STAS 2189-80.

Key words: crystallization, environmental protection, iron(II) sulphate, recovery, wastewater

1. Introduction clean surfaces through removal of oxides superficial

films (rust) that is formed onto the surface of the
The technological process of processing the products subjected to mechanical processing and
rolled steels raises a series of problems related to anticorrosion finishing. Solution of hydrochloric acid
environmental pollution (ICCP BREF, 2001) both by (HCl), sulphuric acid (H2SO4) and often acid mixtures
gas emissions and wastewaters discharge or the (HF + HNO3) are used with this purpose. The etching
wastes resulted from the component processes (Fig. in solution of hydrochloric acid is relatively fast and
1). does not need the heating of solution. Due to strong
The main environmental related problems that corrosion behaviour and toxicity of the released
appear in the case of processing the cold rolled steels vapours, most often, the etching in sulphuric acid is
are: the acid wastes and the wastewater resulted from used, irrespective of the fact that the heating of
etching, the oil and acid aerosols, the solid particles solution is needed.
and residual solutions from etching and degreasing The technological process of etching the rolled
the oil containing wastes, and thermal energy as well steels is performed in solutions of sulphuric acid of
(ICCP BREF, 2006; Wiśniewski and Wiśniewska, concentration ranged between 13 and 22 % H2SO4, at
1997). temperatures of 333.15 – 343.15 K. During the
The acid emissions and the content of the process, reactions of dissolution of iron oxides with
wastewaters resulted in the etching process are formation of iron(II) – FeSO4 – and iron(III)
different in function of the used acid (Oniciu and sulphates – Fe2(SO4) 3 – occur, concordant to Eqs. (1)-
Grünwald, 1980). Generally, the etching is achieved (3):
from solutions of inorganic acids aiming at obtaining


Author to whom all correspondence should be addressed: e-mail: [email protected]
 Lazăr et al./Environmental Engineering and Management Journal 8 (2009), 3, 541-547

FeO + H2SO4 = FeSO4 + H2O (1) Table 2 are presented the limit concentrations of the
pollutants in the residual fluxes (ICCP BREF, 2001;
Fe2O3 + 3 H2SO4 = Fe2(SO4)3 + 3 H2O (2)
2006).
Fe3O4 + 4 H2SO4 = Fe2(SO4)3 + FeSO4 + 4 H2O (3) For the recovery of free sulphuric acid from
spent pickle from sulphuric acid etching lines, the
heptahydrate crystallization process (FeSO4.7H2O), is
By using corrosion inhibitors and sulphuric
usually applied in industry (Cheremisinoff, 2003;
acid solutions of concentrations lower than 25 %
IPPC BREF, 2001). With respect to the type of
H2SO4, the metal cracking as a result of released
cooling, the following heptahydrate crystallization
hydrogen that diffuses in the metal surface layer may
processes for regeneration are available:
be avoided as is shown in Eq. (4):
crystallization with indirect cooling, cyclone
crystallization and vacuum cooling crystallization.
Fe + H2SO4 = FeSO4 + H2 (4)
The treatment of spent pickle solution by
crystallization avoids the need to neutralize free acid;
The residual solutions resulted from etching of furthermore the iron is precipitated as heptahydrate
the rolled steels contain 40 up to 80 g/L FeSO4. The and does not have to be subjected to neutralizing
relative low solubility of the formed sulphates either. Within the crystallization processes, a
imposes their separation (Oniciu and Grünwald, 1980; significant enhancement of the wastewater released
Vanya and Mets, 2007). The sulphuric acid recovery and a reduction of the salt load can be achieved.
process by crystallization is based on the solubility With this purpose, the etching solution is
relations of water, sulphuric acid and iron sulphate. subjected to concentration by vacuum evaporation at
Iron sulphate is more soluble at increasing temperatures higher than 315.15 K, followed by a
temperatures and crystallizes out of saturated crystallization process through cooling up to 278.15 –
solutions when being cooled (McLay and Reinhard, 283.15 K. The formed suspension is separated by
2007; Szép, 2000). sedimentation and centrifugation.
The indicators of the etching of rolled steels in
solutions of sulphuric acid are presented Table 1. In

Emissions in air

HCl, HF aerosol oils, aerosol

aerosol acids, thermal SO2 oils, aerosol
NOx, SO2 energy NOx thermal oils,
energy
Etching Rolling Heating Recovery Finishing
processing

acids, acids, oils,

Hot rolled
filtred filtered filtered
steel
substances, substances, substances,
2+ 3+
Fe , Fe , Fe, Cr Fe, Cr,
oil, emulsions, degreasing
waste cooling water solutions,
solutions cooling water

Wastewaters, wastes

Processed
rolled steel

Fig. 1. Technological process in the case of processing cold rolled steels

Table 1. The indicators of the etching of rolled steels in solutions of sulphuric acid

Process indicators Values

Sulphuric acid consumption 7 – 10 kg H2SO4/t steel
Product of FeSO4 recovery 26 – 30 kg FeSO4/t steel
Recovered solution of sulphuric acid 0 – 10 kg solution 20 % H2SO4 /t steel
Energetic use
Thermal energy /steam for bath heating 0.05 – 0.1 GJ/t steel
Electric energy 0.02 – 0.05 GJ/t
Pollutants from the release of the gas resulted at acid recovery SO2, H2SO4

542
 Researches on possibility to recovery and reuse the iron(II) sulphate from etching of rolled steels

Table 2. Best alternative technologies (BAT) decisions for etching in solutions of sulphuric acid

Flux Pollutant Imposed limit BAT

Gases H2SO4 5 – 10 mg/m3 Recovery by condensation, in
SO2 8 – 20 mg/m3 condensers provided with scrubbers
H2SO4 1 – 2 mg/m3 Etching tank totally enclosed or with
SO2 8 – 20 mg/m3 (reduction > 95 %) exhaust hoods / scrubber
Waste Filtered < 20 mg/L Cascade washing by reusing the excess
waters substances (etching baths, scrubber for released
Oil < 5 mg/L gas).
Fe < 10 mg/L Adjustment and establishment of the
Crtotal < 0.2 mg/L whole etching system working without
(at stainless steel < 0,5 mg/L) wastewater.
Ni < 0.2 mg/L Wastewater treatment (neutralization,
(at stainless steel < 0,5 mg/L) flocculation, etc.)
Zn < 2 mg/L

Usually, the iron(II) sulphate does not meet the Analyzing the phase diagram, one see that
qualities of a technical product (FeSO4.7H2O), due to depending on the temperature and concentration of
the fact that it contains iron(III) sulphate, free the solution, the iron(II) sulphate may crystallize
sulphuric acid, untransformed iron oxides and other under the shape of three hydrates: iron sulphate
impurities above the limits admitted by STAS 2189- heptahydrate FeSO4.7H2O (H7), at temperatures lower
80. All these limit the use of this product, reason for than 329.75 K; iron sulphate tetrahydrate FeSO4.4H2O
which appears the need to investigate the possibility (H4), at temperatures ranged between 329.75 – 337.55
to recovery it for obtaining a quality product that may K and iron sulphate monohydrate FeSO4.H2O (H1), at
be further utilized for water purification, for pigments temperatures higher than 337.55 K. The domain of
manufacture, for catalyst synthesis, in textile industry, the unsaturated solutions decreases at temperatures
etc. above 337 K, when iron sulphate monohydrate
The recovery and reuse of the iron(II) sulphate crystallizes.
resulted through crystallization of the residual At the environmental temperature, the stabile
solutions from rolled steels etching process, may be form is iron sulphate heptahydrate. For obtaining the
carried-out throughout the following possibilities stabile form, the crystallization process should be
(IPPC BREF, 2001): performed at temperatures lower than 329.75 K, the
a) conditioning by re-crystallization; value corresponding to P1. The domain corresponding
b) ammonia conversion yielded in solutions of to crystallization of heptahydrate is delimited by the
ammonia sulphate with 36 – 37 % (NH4)2SO4 and points EP1RQ.
synthetic magnetite (Fe3O4); The laboratory experimental research
c) decomposing using concentrated sulphuric acid concerning the recovery of iron(II) sulphate obtained
with formation of iron(III) sulphate and sulphur by crystallization of residual solutions from rolled
dioxide; steel etching was carried-out through re-
d) thermal decomposing leading to formation of crystallization in two stages. Within a first stage of
sulphur dioxide; crystallization, a solution almost saturated of iron(II)
e) production of several pigments based on sulphate (35 % FeSO4), was prepared de at
iron(III) oxide. temperature of 328.15 K, using the iron(II) sulphate
In this paper, the possibility of conditioning resulted from etching and water (AB line). The
the iron(II) sulphate resulted from etching of rolled solution was further cooled up to la 283.15 K aiming
steels in order to reduce the free acidity and the at crystallization of the stable form (H7). The
content of iron(III) sulphate, as well as to enhance the crystallized iron(II) sulphate was separated by
granulometry spectra is studied aiming at achieving a filtration, dried and analyzed by chemical point of
product that meets the quality requirements for view. In the second stage of re-crystallization, a
technical iron(II) sulphate imposed by the STAS solution of iron(II) sulphate was prepared at
2189-80. temperature of 328.15 K, using the iron(II) sulphate
from the first stage of re-crystallization. The solution
2. Experimental was further cooled to 283.15 K, leading to
crystallization heptahydrate that was subjected to
The establishment of the technologic regime some stages including filtration, drying and chemical
for crystallization of iron(II) sulphate was performed characterization.
on the basis of analysis of the solid – liquid phase The process of crystallization of iron(II)
equilibrium in the system H2O – FeSO4 (Szép and sulphate heptahydrate is plotted through the line BL
Ivaniciuc 1998; Szép, 2000). The equilibrium from phase equilibrium diagram corresponding to the
diagram plotted in the coordinates temperature– system [H2O – FeSO4] – Fig. 2. It was chosen to
concentration of FeSO4 in solution is presented in Fig. obtain the saturated solution at temperature of 328.15
2. K in order not to exceed the crystallization domain of

543
 Lazăr et al./Environmental Engineering and Management Journal 8 (2009), 3, 541-547

iron(II) sulphate heptahydrate (EP1RQ). The and free acidity. In the pilot or industrial plants, the
saturated solution correspondent to the point B is stock solution may be reused in the process of iron(II)
cooled with occurrence of separation of the solid sulphate crystallization from the residual solution
phase that evolves from point R to point M. The resulted from rolled steels etching.
liquid phase evolves from point B to point N. The block diagram of the experimental
Concordant to NLM, the stock solution resulted from protocol is depicted in Fig. 3. The experimental
the crystallization process contains around 17 % researches were done on laboratory equipment
FeSO4. consisting in a glass reactor foreseen with a mixing
It is not recommended to perform the system with variable rotating speed, inserted in a
conditioning by re-crystallization with recirculation of thermostatic system.
the stock solution after the stages of separation in the The iron(II) sulphate crystallized in each stage
case of preparation of the saturated solutions, due to was decanted, filtered and dried in a dryer at 373.15
the fact that this needs processing related reduction of (±2) K. The samples obtained in each re-
the iron(III) sulphate to iron(II) sulphate and crystallization stage have been chemically analyzed in
neutralization of the sulphuric acid. order to determine content of the iron(II) and iron
Thus, the quality of the iron(II) sulphate is (III) sulphate, as well as of free sulphuric acid.
influenced by accumulation of the iron(III) sulphate

Fig. 2. Phase diagram of solid – liquid equilibrium in the system H2O – FeSO4
(hydrates composition: H7 = 54.7 % FeSO4 şi H7 = 67.8 % FeSO4).

544
 Researches on possibility to recovery and reuse the iron(II) sulphate from etching of rolled steels

Crystallized
iron(II) sulphate

Preparation of saturated solution (at 328,15 K) water

Re-crystallization I by cooling at 283,15 K

Separation by filtration
Stock solution (I)
iron(II) sulphate
(re-crystallization I)

Recirculation to Preparation of saturated solution (at 328,15 K) water

iron sulphate
crystallization from etching
Re-crystallization II by cooling at 283,15 K

Separation by filtration
Stock solution (II)
iron(II) sulphate
(re-crystallization II)

Fig. 3. The bloc diagram of the re-crystallization process of iron(II) sulphate

3. Results and discussion The values obtained from the chemical

analysis of iron(II) sulphate resulted from etching
3.1. Chemical characterization of iron(II) sulphate process were compared with the quality for technical
from etching process iron(II) sulphate, foreseen in STAS 2189-80 (Table
3). Considering the content in iron(II) sulphate, the
The experimental analysis of chemical sulphate formed in the etching process may be
composition of the iron(II) sulphate resulted in included in the II group of technical product.
processing by crystallization of the residual solutions The content in free sulphuric acid, iron(II)
from rolled steel etching was carried-out concordant sulphate and other impurities but also the less
to STAS 2189-80. With this purpose, the volumetric commercial aspect of the of iron(II) sulphate
method was employed using solution of potassium separated from etching solutions imposes the need to
permanganate (KMnO4 0.1 N) for analyzing iron find a technical possibility to obtain a product that
sulphates and solution of bicarbonate de sodium may be commercialized. A contribution to the aspect
(NaHCO3, 0.1 N), respectively for determining the unfavourable to commercialization has also the direct
free acidity. The obtained experimental data are bulk storage of the centrifuged product, when, due to
presented in Fig. 4. humidity (around 6 % H2O), aggregates that retain
powders from the atmosphere are formed.

100 3.2. Re-crystallization of iron(II) sulphate and its

chemical characterization
C oncentration,

75
In every attempt, for achievement of a
%wt.

50
saturated solution, the ratio water/iron(II) sulphate
25 from etching was calculated on the basis of mass
balance taking into account the following values:
0 volume of experimental reactor (1000 mL), space
FeSO4.7H2O Fe2(SO4)3 H2SO4, free
factor ( = 0.8) and solution concentration of 35 %
crystallization 96.7 1 0.36 FeSO4 (respectively, solution density equal to 1269.5
kg/m3).
Fig. 4. The chemical composition of iron(II) sulphate The mass balance for obtaining the solution of
resulted from etching iron(II) sulphate necessary for re-crystallization
process is presented in Table 4.

545
 Lazăr et al./Environmental Engineering and Management Journal 8 (2009), 3, 541-547

Table 3. Quality requirements of the iron(II) sulphate resulted from etching

Technical iron(II) sulphate

iron(II) sulphate
(STAS 2189-80)
from etching
Quality superior I II
Colour light green grey- green grey greenish
FeSO4.7H2O (%wt. min) 98.5 97.5 95.0 96.70
% Fe2(SO4)3 (%wt. max.) 0.5 - - 1.00
% H2SO4 (%wt. max.) 0.1 0.2 0.3 0.36

Table 4. The mass balance for obtaining the saturated solution of iron(II)

Molecular
Component weight, kg/kmol Components amounts

FeSO4 151.85 m FeSO4  350 g -

FeSO4 .7H2O 277.85 - m FeSO4 7H 2O  640.4 g

H2O 18 m H 2O  650 g m H 2O  359.6 g
Total - mL = 1000 g mL = 1000 g

Table 5. Quality requirements of iron(II) sulphate re-crystallized from etching

Quality Technical iron(II) sulphate (STAS

Iron(II) sulphate re-crystallized in laboratory
2189-80)
Type superior I II re-crystallization I re-crystallization II
Colour light grey -
grey greenish light green
green green
.
%wt. FeSO4 7H2O 98.5 97.5 95.0 97.19 98.68
%wt. Fe2(SO4)3 0.5 - - 0.31 0.3
%wt. H2SO4 0.1 0.2 0.3 0.19 free acidity

The experimental results achieved from

analysis of the chemical composition of the re- The iron(II) sulphate resulted in the second
crystallized I and II iron(II) sulphate are presented in stage of re-crystallization is framed in the superior
Fig. 5. One may observe that the re-crystallized II quality group of the technical product (Table 5).
iron(II) sulphate has no acidity and exhibits a content
of 98.68 % FeSO4.7H2O and 0.3 % Fe2(SO4)3. 4. Conclusions

Sulphuric acid solution can be regenerated by

100 crystallizing ferrous sulphate. These techniques have
been used for many years in large facilities. The
C oncentration,

75
economics of these processes, however, usually are
%wt.

50 not favourable for smaller facilities. Iron in the waste

is used as a coagulant in wastewater treatment
25
systems.
0 The possibility of recovery the iron(II)
FeSO4.7H2O Fe2(SO4)3 H2SO4 sulphate resulted from etching bath of the rolled steels
re-crystallized I 97.19 0.31 0.19 by re-crystallization, aiming at increasing the content
re-crystallized II 98.68 0.3 0 in iron(II) sulphate, as well as diminishing the content
in iron(III) sulphate and free acidity, was investigated.
Fig. 5. Chemical composition of the iron(II) sulphate as a After the first stage of re-crystallization, the
result of re-crystallization content in iron(II) sulphate reached 97.19 %
FeSO4.7H2O (meaning an increase of only 0.5 %), the
Comparing the experimental results content in free sulphuric decreased to a 0.19 %
concerning the colour and chemical composition I and H2SO4, while that of iron(III) sulphate decreased to
II of the re-crystallized iron(II) sulphate with the 0.31 % Fe2(SO4)3. One may state that re-
technical requirements admitted by STAS 2189-90, crystallization allows the formation of a clean product
one may see that the re-crystallized product in the corresponding to the first quality group concordant to
stage I may be framed in the first quality group. requirements of STAS 2189-80.

546
 Researches on possibility to recovery and reuse the iron(II) sulphate from etching of rolled steels

After the second stage of re-crystallization, the IPPC BREF, (2006), Integrated Pollution Prevention and
content in iron(II) sulphate attained 98.68 % Control – Reference Document on Best Available
FeSO4.7H2O, the final product not exhibiting free Techniques for the Surface Treatment of Metals and
acidity. In this case, the content in iron(III) sulphate is Plastics, European Commission, August 2006, on line
at: www.anpm.ro.
of 0.3 % Fe2(SO4)3. In these conditions a product McLay Dedietrich W.J., Reinhard F.P., (2007), Waste
corresponding to S quality group imposed by STAS minimization and recovery technologies, Metal
2189-80 can be obtained. Finishing, 105, 715-742.
The experimental results show that application Oniciu L., Grünwald M., (1980), Corrosion and its
of re-conditioning by double re-crystallization leads reduction in chemical industry, Scientific and
to high quality technical sulphate, which does not Encyclopaedic Publishing House, Bucharest.
exhibit free acidity. STAS 2189-80, Technical iron(II) sulphate. Technical
quality requirements and methods of analysis.
Szép Al., Ivaniciuc M., (1998), Technology of inorganic
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