Purification of H2SO4 of Pickling Bath Contaminated by Fe ... · precision balance brand KERN 770...

Energy Procedia 74 ( 2015 ) 1418 – 1433

ScienceDirect

1876-6102 © 2015 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4 .0/).Peer-review under responsibility of the Euro-Mediterranean Institute for Sustainable Development (EUMISD)doi: 10.1016/j.egypro.2015.07.789

International Conference on Technologies and Materials for Renewable Energy, Environment and Sustainability, TMREES15

Purification of H2SO4 of pickling bath contaminated by Fe(II) ions using electrodialysis process

Abla Chekiouaa, Rachid Delimi* Laboratoire de traitement des Eaux et Valorisation des Déchets Industriels, Faculté des Science, Département de

Chimie, Université de Badji-Mokhtar, Annaba 23000. Université Badji Moukhter Annaba ALGERIE

Abstract

We used in this work electrodialysis (ED) to remove the iron (II) ions of sulfuric acid pickling bath. This technique has proven very useful and effective in our study. Indeed, it allowed us to demonstrate the effect of various parameters (current density, the nature of the membrane and the concentration of Fe (II)) on the efficiency of the electrodialysis process. The results obtained show that the treatment rate increases with increasing the current density in the range 1 to 20 mA.cm-2. However, increasing up to 30 mA.cm-2 led to a clogging of the membrane, involving a substantial increase in the electrical resistance of the system. Moreover the increase in concentration of iron ions in the feed compartment to 52g.L-1 improves the purification rate 70.17 . The study of the influence of the membrane nature has shown that the CMX membrane more effectively than CMV and two Nafion 117 membranes. In parallel with the treatment process is also studied the possibility to refocus sulfuric acid was studied a removal mechanism iron ions and sulfates of the study define the solution for species that might exist in the system Fe - H2SO4 - H2O. It is clear from this analysis that the purification of the solution (Fe (II) -H2SO4) processing will be based on the elimination of Fe2+ ions and HSO4

-. A purification mechanism of the solution based on the transfer of species through the ion exchange membranes has been proposed. Keywords: Pickling, Electrodialysis, Sulfuric acid, Purification. © 2015 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the Euro-Mediterranean Institute for Sustainable Development (EUMISD).

* Corresponding author. Tel. 213-776-461-511:; fax:213-388-765-67 Rachid Delimi university badji mokhtar annaba Algéria [email protected]

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© 2015 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).Peer-review under responsibility of the Euro-Mediterranean Institute for Sustainable Development (EUMISD)

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Abla Chekiouaa and Rachid Delimi / Energy Procedia 74 ( 2015 ) 1418 – 1433 1419

1. Introduction

For many years, the planet has been considered, firstly, as an inexhaustible reservoir of raw materials and, secondly, as a usual destination for domestic waste, industrial and agricultural that may constitute a risk to humans and the environment. Due to the use of a large number of more or less toxic chemicals as well as by the type of reactions involved, the workshops of surface treatment is one of the most polluting industries. Many of these industries generate significant volumes of waste acid. Among the most common acids used in surface treatment baths during pickling it is sulfuric acid H2SO4 [1]. Pickling baths are designed to remove oxides, dusts and metal chips from the surface of the chemically steel using strong acids [2,3]. The steels are usually stripped with sulfuric acid to 200 g.L-1 to 95 -100 ° C [4,5]. When steel is pickled with sulfuric acid, the oxides are dissolved to give iron sulphates (II). In this case the pickling bath loses its activity and becomes ineffective, it is rejected when the iron concentration is approximately 70 g.L-1 [5]. The sulfuric acid solution of the pickling bath can then be processed by various methods. In general, known purification processes are relatively complicated that further recovery would deprive any profitable character, for example; reduction methods, neutralization, precipitation, cooling, evaporation, distillation, thermal decomposition, the solvent extraction [6,7] and carburizing generate a large volume of sludge [8], which leads to a displacement of pollution. The ion exchange can be applied to recovery of the sulfuric acid, however it has the constraint of regeneration cycles [9]. Emulsified liquid membranes techniques allow quickly extracting and highly concentrating the pollutants [10]. The major drawback of this technique lies in the loss of extractants which are expensive products. Electromembrane techniques (electrodialysis) appear to be suitable for the removal of impurities in industrial effluents [11,12,13,14,15]. Moreover, these membranes separation technologies provide solutions for the upgrading by-products, while meeting environmental benefits. Our research focuses in this perspective and aims to study the possibility to purify and refocus a sulfuric acid solution by electrodialysis technology [16,17].

2. Materials and Methods

2.1 Chemical Reagents

The solutions used in this work were prepared from pure chemical reagents for analysis (Table 1). All solutions were prepared with double-distilled water (distilled Aquatron). The weights of the solutes were carried out with a precision balance brand KERN 770 pH measurement was made using a pH meter HANNA, pH211 microprocessor model.

Table 1: Chemical reagents used.

Reactive Purity Brand Concentration of the solution prepared

H2SO4 96% Sigma-Aldrich 150 g.L-1

HNO3 69% Riedel-De Haën 0.1 N

FeSO4.7H2O 98% MERCK 26 g.L-1

2.2.Ion exchangers Materials

The ion exchange membranes used in this work are cation exchange membranes (CMX, CMV, Nafion 117) and an anion exchange membrane (AMX). The main characteristics of these ion exchange materials are given in Table 2.

1420 Abla Chekiouaa and Rachid Delimi / Energy Procedia 74 ( 2015 ) 1418 – 1433

Table 2: Characteristics of ion exchange materials.

MEI Manufacturer WC (%) Rms ( .cm2)

EC

(meq.g-1) tNa+, tCl-

Thickness

( m) Functional

groups

CMX Tokuyama 25-30 2.0-3.5 1.5-1.8 >0.98 170-190 –SO3-

AMX Tokuyama 25-30 2.0-3.5 1.4-1.7 >0.98 120-180 –NR3+

Nafion 117 Dupont de

Nemours 22 1.10 0.9 0.99 220 –SO3

-

CMV Asahi glass 40 2.3 2.0-3.5 >0.91 130-150 –SO3-

MEI: ion exchange membranes; WC (%): Water content; Rms ( cm2): Surface Resistance; EC (meq.g-1): The

ability of ion exchange; tNa+ , tCl-: Number of transport.

3. Experimental setup

3.1. Cell electrodialysis

Treatment solutions of sulfuric acid containing metal impurities (Fe (II)) by electrodialysis were carried out on a

laboratory cell (Figure 1). The cell comprises four compartments: supply chambers (A), anode electrode rinse (EA) of the recipient (R) and cathode rinse (EC). Each compartment has a thickness of 6.5 mm. At the ends of the cell are placed two electrodes, platinized titanium anode into the compartment (EA) and the graphite in the cathode compartment (EC). The floor area of each electrode is 10.87 cm2. The two electrodes are connected to a current generator regular intensity (0 - 2.5 A, 0 - 40V).

Fig.1. Schematic representation of the experimental four compartment electrodialysis operating in closed circuit assembly


We worked in galvanostatic mode to maintain the constant current. Compartments and supports electrodes are

Plexiglas, inert material in the presence of acid. The sealing of the assembly is ensured by seals of thickness 1 mm. In order to monitor the concentrations of metal impurities of Fe (II) ions, samples are taken in different compartments and iron concentration was analyzed by atomic absorption spectroscopy (Shimadzu spectrophotometer AA-6200). Using peristaltic pumps (Masterflex), the various compartments are supplied with the test solution (150 gl-1 H2SO4 + 26 gl-1 of Fe (II) and other solutions (H2SO4 10-1 N HNO3 10-1 N). traffic solutions in the compartments A and R is a closed circuit mode.

3.2.Operating Principle

The principle of removing impurities from the iron (II) from sulfuric acid by electrodialysis is shown schematically in Figure (2). The solution to be treated flows in the supply compartment (A) while the sulfuric acid solution 0.1 N in the compartment (EA). In the receiver (R) which was to transfer compartment metallic impurities, circulates a nitric acid solution 0.1 N. In the compartment (EC) is also circulated a solution of nitric acid at 0.1 N. EA compartments A and are separated by an anionic membrane (AMX) while compartments A and R are separated by a cationic membrane (CMX). AMX membrane separating the compartments R and EC prevents the transfer of cations to Ec. Under the effect of the electric field ferrous ions contained in the solution to be processed are transferred into the receiver compartment where they are concentrated.

Thus the acid solution circulating in the A compartment is purged of impurities of iron (II).

Fig.2.Principle of purifying sulfuric acid containing Fe (II) by electrodialysis

1: Sub rinse anode electrode (EA)

2: Sub-power (A)

3: Sub-recipient (R)

4: rinse compartment cathode electrode (CE)

5: Tanks solutions

6: A peristaltic pump

7: Ammeter

8: Power supply

9: Magnetic Stirrer


4. Expression of results

4.1. Purification rate:

The treatment rate is the number of cations extracted from the original number of cations in the solution to be treated. It is expressed as a percentage.

(1) Ci et Cf : :Initial and final concentrations of iron (II) in the feed compartment.

4.2. Energy consumption

The energy consumption of a treatment by electrodialysis operation can be calculated from the following relationship:

(2) Where We (kwh.kg-1): is the Energy, U (V): is the voltage of the cell, I (A): is the Intensity of current applied t (h): is the Length of experience, m (g):is the product mass in the feed compartment.

5. Results and discussion In order to examine the effect of the current density applied to the removal of iron (II), we performed a series of

experiments at different electrodialysis current densities. Results were analyzed and the purification efficiency of the acid and the evolution of the voltage in the process at different densities were also followed.

5.1. Effect of current density

In order to examine the effect of the current density applied to the removal of iron (II), we performed a series of experiments at different electrodialysis current densities. Results were analyzed and the purification efficiency of the acid and the evolution of the voltage in the process at different densities were also followed.

5.1.1. Removal efficiency of Fe (II) ions

The results were analyzed in terms of purification rate (Table 3) show that the increase of the current density of 1 to 20 mA.cm-2 causes an increase of the purification rate of 7.43 to 66.32 %. However the increase in density up to 30 mA.cm-2 leads to a reduction of the purification rate at 60.49 %. At the end of the experiment at 30 mA.cm-2, it was observed the formation of a deposit on the surface of the membrane, which separates the compartments (A) and (R). The single metal cation is present in the solution of iron (II), therefore the nature of the deposit is likely iron


hydroxide. The test solution is very acidic (pH = 0.26) and the formation of iron hydroxide is not possible, unless there are local variations in pH.

It is known that changes in pH by the membrane may take place as a result of dissociation of water due to the exceeding of the limit value of the current [18].

Table 3: Rates of treatment (%) at different current densities (CMX membrane, 50 mL min-1, 25 ° C; 7h).

i (mA.cm-2) 1 5 10 20 30

TE (%) 7.43 19.65 51.09 66.36 60.49

5.1.2. Determination of limiting current density

To test the hypothesis of exceeding the current limit, we proceeded to determine the current limit. Determining the current limit is to apply to the electrodialysis cell intensity variable current and record the potential difference [19,20].

Fig.3. current-potential curve of the electrodialysis of a sulfuric acid solution containing iron (II)

The intensity curve - given potential is recorded in Figure (3). We notice the curve a limiting current year corresponding bearing (258.7 mA) and a current density of 23.8 mA.cm-2. This stage corresponds to a total concentration polarization in the layer near the diffusion membrane. The increased recovery is achieved by majoritairent protons and hydroxyl ions from the dissociation of water at the surface of the membrane [21, 22]. Under the influence of electric fields, the protons move towards the cathode and hydroxyl ions (OH-) to the anode where they met with the Fe (II) through the membrane, leads to the precipitation of the hydroxide surface of the membrane.

We find that the current density (30.0 mA.cm-2) to which the training takes place on the membrane of the deposit beyond the limiting current density (23.8 mA.cm-2).

0

50

100

150

200

250

300

350

0 0,1 0,2 0,3 0,4 0,5

I(m

A)

U(V)

ilimit


5.2. Influence of the type of membrane

5.2.1.Removal efficiency of Fe (II) ions

The results expressed in terms of levels of purification (Figure 4) show that membrane CMX provides the best treatment of the solution (66.32 %). We attribute the CMX membrane performance compared to the two other membranes best compromise it has, between the exchange capacity and permselectivity (Table 2). The CMX membrane is retained for further study.

Fig.4. sewage rates obtained with different membranes.

5.2.2. Energy consumption

Energy consumption for a processing operation carried out with different cationic membranes (CMX, Nafion 117, CMV) is presented in Table 4, which shows that the values of energy consumption for the CMX and Nafion 117 membranes are roughly equivalent. However, the power consumption obtained with the CMV membrane is significantly higher than those of the two other membranes.

Table 2 shows that the CMV membrane differs from the other two membranes with a higher water content (40%) and lower permselectivity (0.91).

Table 4: Energy consumption with different membranes.

Membrane Type CMX Nafion 117 CMV

We (KWh.kg-1) 1.85 2.10 5.69

5.3. Effect of ions Fe (II) concentration

5.3.1. Removal efficiency of Fe (II)

0

10

20

30

40

50

60

70

CMX Nafion 117 CMV

TE (%

)


To study the influence of the initial concentration of iron in the feed solution on the efficacy of the method, we tested several concentrations (1, 10, 26 and 52 g.L-1). The results of removal rate of the iron according to the concentration of iron ions are shown in Table 5. It is noted that when the concentration of Fe (II) is equal to 52 g L-1 of the purification rate achieved the value 70.17%. Yanxin et al [23] found in their study on the removal of NaBr by electrodialysis, an increase in removal efficiency of NaBr with increasing concentrations of NaBr in the range 6000-11000 mg.mL-1. Jinki et al [24] also noticed in their study on the recovery of sulfuric acid by dialysis, the recovery rate decreases with increasing the concentration of sulfuric acid. They explained this result by reducing the diffusion coefficient with increasing acid concentration. Table 5: Values of the purification rate of the treated solution at different initial concentrations of Fe (II) (Membrane CMX; 20 mA.cm-2, 50 mL · min-1; 25 ° C; 7h).

C de Fe

(g L-1)

1 10 26 52

T (%) 35.31 59.39 66.32 70.17

In order to find an explanation for this result we measured the pH of initial solutions (Table 6). Note that

the pH of the solution increases with the concentration of FeSO4 salt. For cation transport of iron across a cation exchange membrane, the proton is a competitive cation [24]. Interpreting the increase in the removal efficiency of the iron ions by the reduction of the protons compete with the iron ions due to the decrease of the proton concentration (pH increase). This pH increase results from the combination of protons sulphate which they are emerging from the dissolution of FeSO4 by the following reaction (Eq 3).

FeSO4 Fe2+ + SO42-

(3)

Calculating the concentration of the species is consistent with this hypothesis. Indeed, the percentage of species HSO4

- (70.2 to 72.2%) and SO42- (1.4 to 2.6%) (Table8) confirmed that the 04 reaction is almost complete.

Table 6 : Valeurs de pH des solutions de FeSO4

C de Fe

(g.L-1)

1 10 26 52

pH (initial) 0.15 0.21 0.26 0.55

5.3.2. Energy consumption:

Figure 5 shows the effect of the concentration of iron ions on the energy consumption. It is noted that with the increase of the concentration of Fe (II), the energy consumption decreases. This decrease is probably due to the decrease in electrical resistance caused by the increase in the concentration of Fe (II) ions in the [23] receiver compartment.


Fig.5. Change in energy consumption with the concentration of Fe (II) ions (CMX Memrane; 20mA.cm-2; 50 mL ·

min-1; 25; 7 am) 5.3.3. The Variation in pH in the anodic compartment: To study the influence of the concentration of FeSO4 salt in the power compartment on the effectiveness of re-concentration sulfuric acid in the anode compartment by electrodialysis process, we conducted four experiments with different salt concentrations (1.10, 26, 25 g.L-1), the current density applied is 30 mA.Cm-2 and flow, 50 ml min-1, the hard experiences is 7 fortunes. In course of time the concentrations in the anode compartment was analyzed. The results obtained are expressed by Figure 6 and table 7. Logically will be noted in Figure 6 that the concentration in the anode compartment increases with the salt concentration in the feed compartment. This increase can be explained by the increase in proton permeability by aditions sulfate these metal ions in the salt solutions to effect, or has any other meaning the salt additions same anion as the acid can promote the diffusion of protons [25,26] which are reacted with sulfate ions (SO4

-2) formed for the bisulfats ions (HSO4

-) which causes increase in the concentration of the acid in the anode compartment. It was also confirmed by measuring pH of the solution in the anode compartment that the higher the concentration the pH decreased more augment Table 7.

0

1

2

3

4

5

6

7

8

9

0 10 20 30 40 50 60

We (k

wh.

kg-1

)

C (g.L-1)


Fig.6.The variation of the concentration of the acid in the anode compartment as a function of time with different

salt concentrations in the central compartment (membrane AMX, 20 mA.Cm-2, 50ml.min-1.7h)

Table 7: Measure pH in the anode compartment (membrane AMX, 20 mA.Cm-2, 50ml.min-1,7h)

5.3.4. Percentage of acid reconcentration: To assess the effect of salt addition on the reconcentration of the acid in the anode compartment was tested four concentrations of FeSO4 with sulfuric acid in the feed compartment (1, 10, 26, and 52 g.L-1) .The test results allows calculates the percentage of reconcentration of the sulfuric acid in the anode compartment. Figure 7 shows that the percentage despreading augment as a function of time with different salt concentrations in the feed compartment. When the salt concentration in the central compartment is low 1 g.L-1, the percentage of re-concentration of acid in the anode compartment after 7 experiences is 9.80 fortunes, and the final acid concentration is 14.7g.L-1. But in the case of increasing the addition of salt in the center compartment 52 g.L-1, the percentage increases to 16.72 with a final concentration of acid is 25.08g.L-1. The results confirmed well the advantage of the addition of FeSO4 salt same anion as the acid H2SO4 [27].

0

5

10

15

20

25

30

0 100 200 300 400 500

C (g

.L-1

)

C (g.L-1) de FeSO4

1 g/ l 10 g/ l

26 g/ l 52 g/ l

C (g.L-1) H2SO4 0 1 10 26 52

pH 1.50 1.14 1.07 0.9 0.86


Fig.7.The percentage of reconcentration of the sulfuric acid in the anode compartment with different concentration of FeSO4 (membrane AMX, 20 mA.cm-2, 50 mL.min-1.7h)

5.4. Speciation and purification mechanism Given the existence of a large number of neutral or charged complex compounds containing iron ions and sulphate and to elucidate the mechanism of removal of iron ions and the transfer of the test solution sulfates define the relative species that might exist in the system Fe - H2SO4 - H2O. The species in question will be defined from previously published work [28,29,30,31,32,33]. The most important equilibrium reactions in the system studied could include: The reactions of association between H+ and SO4

2- to give HSO4-:

(4)

And the reactions of association between iron ions and ions SO4

2- and HSO4-

(5)

(6)

(7)

(8)

0

2

4

6

8

10

12

14

16

18

0 100 200 300 400 500

R (%

)

Time (min)

1 g/l 10 g/l26 g/l 52 g/l


(9)

The concentration of these species in solution depends on the solution composition and temperature. Our reasoning is based primarily on the work of Casas et al [31], the experimental conditions are very similar to ours (Table 8). Table 8: Comparison of composition of the test solution with that of Casas et al [31].

composite FeSO4 H2SO4 Temperature

initial concentration

27 g.L-1 2.2 mol.kg-1 25 °C Casas et al. (2005)

26 g.L-1 1.53 mol.kg-1 25 °C Our solution

The concentration of Fe (III) analyzed in the initial solution of FeSO4-H2SO4 by the UV-visible spectrophotometric method to phénontroline is equal to 1.10g.L-1. Other compounds may exist in solution as FeH (SO4)2 whose presence has been demonstrated using a spectral study Raman Casas et al.

(10)

As against other species have not been considered: -Complexes of iron hydroxides.

In fact the pH of this solution is very acidic (pH = 0.26) and in this case the hydrolysis of the iron ions is negligible

- Iron bisulfate ions and FeHSO42+ and FeHSO4

+ deviated because of evidence reported by Tremaine et al. [31] who studied the Fe-H2O-H2SO4 system by Raman spectroscopy and they have found no evidence of contact ion pairs between HSO4

- and iron cations. In their model species concentration calculation in the system Fe (II) -Fe (III) - H2O - H2SO4 Casas et al have not considered the bisulfate iron ions. The results of the calculation of cash concentrations at 25 ° C depending on the model proposed by Casas et al.


Table 9: Distribution of species Fe (II), Fe (III) sulfate

Specie Distribution of species Fe (II), Fe (III) sulfate

Fe2+ Fe3+ SO42- HSO4

- FeSO40 FeSO4

+ Fe(SO4)2- FeH(SO4)2

0

Fe(II) 78- 83% 17- 22%

Fe(III) 0.2– 1.3% 2.1– 5.9% 93.9- 96.6%

Sulfate species 1.4-2.6% 70.2- 72.2 % 2.3-3.39% 0.5-1.4% 22.5-23.2%

We note that for the distribution of Fe (II) and Fe (III) are the dominant species Fe2+ and FeH (SO4)2

0 78-83 with 93.9% and - 96.6% respectively. We recall that in our case the total concentration of Fe (III) is very small compared with Fe (II). However, for the distribution of sulfates, dominant species are the bisulfate ions with 70.2 - 72.2%. As regards transport sulfates and bisulfates species through anion exchange membranes (AEM) studies on transport of sulfuric acid across an anionic membrane AEM, Marti et al. [34] Pourcelly et al. [35] Lorrain et al. [36] showed that only SO4

2- ions pass through the membrane AEM. We interpreted this result by the dissociation of the ion bisulfate, at the interface of the AEA membrane, H+ and SO4

2- and under the effect of the electric field it passes through only the MEA membrane to be transferred into the compartment anodic. Martí et al. [34], and Xuan et al. [37] have explained this dissociation the predominant role of the gel phase of the MEAs membrane (obtained for high ion exchange capacity) was suggested to be the reason for the stronger Donnan-exclusion of co-ion, leading to the dissociation of HSO4

- ions. It is clear from this analysis that the purification of the solution (Fe (II) -H2SO4) processing is based on the elimination of Fe2+ ions and HSO4

-. We express the purification mechanism of the solution of the central compartment and the reconcentration of the sulfuric acid in the anode compartment by the diagram given in Figure 8. Indeed, under the effect of the electric field the Fe2+ ions are transferred to the receiver compartments where they will be contained at the same time the HSO4

- ions attracted by the anode dissociate into contact with the MEA membrane H+ and SO4

2- where they continue their movement through the MEA membrane to go concentrate sulfuric acid in the anode compartment. The combination of SO4

2- with H+ in the anode compartment is provided by the production of H+ ions at the anode.


Fig.8.mechanism purification and reconcentration of sulfuric acid by electrodialysis Conclusion

This study showed that it is possible to eliminate the iron ions present as an impurity in a sulfuric acid solution. The influence of some parameters on the removal efficiency of Fe (II) ions was studied. The results showed that increasing the current density in the range 1-20 mA cm-2 results in improved removal efficiency of Fe (II) ions. Increasing the concentration of the solution to Fe (II) has a positive effect on the effectiveness of treatment. The purification level obtained for an iron containing acid solution (II) at a concentration 52 g L-1 is equal to 70.17%. Among the three studied membranes, the CMX membrane proved more effective than the other two (CMV and Nafion 117). A speciation of species present in the test solution has been made and the major species were defined. A transfer mechanism of the charged species across the membranes, leading to the elimination of Fe (II) ions and the reconcentration of the sulfuric acid has been proposed.

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