# The Adsorptive Removal of Bengal Rose by Artichoke Leaves: Optimization by Full Factorials Design

^{1}

^{2}

^{3}

^{*}

## Abstract

**:**

_{pzc}), equilibrium pH, iodine number, methylene blue number, phenol number, density, Energy dispersive X-ray spectroscopy (EDX) and Thermo-gravimetric analysis (TGA). Thereafter, the bio-adsorbent was used to study its capability for removing BR dye by testing contact time, initial concentration of dye and temperature. The results show that the saturation of bio-sorbent was reached after 40 min and the removal rate of BR dye by artichoke leaves powder (ALP) was 4.07 mg/g, which corresponds to a removal efficiency of 80.1%. A design of experiences (DOE) based on a two-level full factorial design (2

^{3}) was used to study the effects of different parameters, such as pH, temperature and bio-adsorbent dosage on BR dye removal efficiency. The obtained results show that the highest removal efficiency was 86.5% for the optimized values of pH (4), temperature (80 °C) and bio-adsorbent dosage (8 g/L). Furthermore, a satisfying accordance between experimental and predicted data was observed. The kinetic and isotherm studies show that the pseudo-second order model simulated adequately the obtained data and it was found that Langmuir and Temkin isotherm models are liable and suitable for evaluating the adsorption process performance. Free energy change of adsorption (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were furthermore calculated to predict the nature of the adsorption process.

## 1. Introduction

## 2. Materials and Methods

#### 2.1. Raw Material and Chemical Reagents

_{20}H

_{2}Cl

_{4}I

_{4}Na

_{2}O

_{5}, 973.67 g/mol) dye, with purity that exceeds 99%, was purchased from Sigma Aldrich Company (Chemie GmbH, Eschenstr. 5, 82024 Taufkirchen, Germany).

#### 2.2. BR Solution

#### 2.3. Bio-Adsorbent

#### 2.4. Methods

#### 2.4.1. Bio-Adsorbent Characterization

#### pH at the Point of Zero Charge (pH_{pzc})

_{pzc}) is a significant parameter in the study of the adsorption phenomena, especially when the electrostatic forces are involved. The pH

_{pzc}is a relevant indicator of the chemical and electronic properties of the material used as absorbent. The method used to measure this parameter is as follows: solutions of 50 mL of NaCl (0.01 M) were poured into closed flasks and the initial pH (pH

_{i}) was adjusted in each volume, ranging from 2 to 12, by adding different volumes of NaOH or HCl 0.1 M solutions. In each flask, 0.15 g of bio-adsorbent (ALP)was added. After 78 h of storage at room temperature (25 ± 2 °C), the final pH (pH

_{f}) was measured from each solution. On a graph pH

_{f}= f(pH

_{i}), the intersection of the pH curve with the bisector of the first quadrant axis resulted in the pH

_{pzc}value [30].

#### Iodine Number

_{2}SO

_{3}), as long as the color due to a few drops of a starch solution (indicator) vanishes. The second test consists of adding 0.2 g of bio-sorbent, i.e., ALP, to a beaker which contains 15 mL of a 0.1 N iodine solution and mixing it for 4 min with stirring equipment. After that time, a centrifugation process is carried out, and 10 mL of the filtrate (which contains iodine) is dosed with a 0.1 N solution of sodium thiosulfate (Na

_{2}SO

_{3}), as long as the color due to a few drops of a starch solution (indicator) vanishes [32].

- -
- (V
_{B}− V_{S}) is the difference between titration volumes calculated for blank test and test with bio-sorbent. Such difference is measured in ml of sodium thiosulfate (0.1 N) solution; - -
- N is the normality of the sodium thiosulfate solution (0.1 N);
- -
- 126.9 is the atomic mass of iodine, measured in g/mol;
- -
- m is the mass of the bio-adsorbent, measured in g.

#### Methylene Blue Index

- -
- Q is the apparent adsorption capacity (mg/g) of activated carbon related to the adsorbate;
- -
- c
_{i}is the initial concentration (mg/L) of methylene blue solution (20 mg/L) - -
- c
_{e}is the residual concentration (mg/L) of methylene blue solution (0.855 mg/L) - -
- V is the volume of methylene blue solution (0.25 L)
- -
- m is the mass (g) of the adsorbent(1 g)

#### Bio-Adsorbent Surface Analysis

_{2}adsorption at 77 K using Quantachrome, Nova instrument, by the Brunauer–Emmett–Teller (BET) method. Fourier Transform Infrared spectroscopy (FTIR) is a diagnostic tool for evaluating the nature of the chemical bonds present in molecules: this technique allows for the identification of some important functional groups that have the capacity to adsorb BR dye. The analysis of the BR dye as well as the bio-adsorbent, prior and after use, were performed by infrared spectroscopy using a JASCO FT/IR-4600 type instrument. The scanning electron microscope (SEM) coupled with Energy Dispersive Spectroscopy X-ray (EDX) analysis was carried out for ALP, prior and after the adsorption process. These analyses were conducted with a FEI Quanta 650/Broker (x/6/10) instrument and identified aspect and morphology of the surface, as well as the elementary composition of materials. The structural characterization of ALP prior and after adsorption was determined by X-ray diffraction analysis (XRD) using a D2 PHASER-BRUKER AXS type device.

#### 2.5. Experimental Design

^{k}) with k = 3 factors, i.e., pH, temperature and bio-adsorbent dosage, respectively. The effects were studied as related to the removal efficiency of the BR dye.

#### 2.6. Mathematical Model Design

_{0}+ a

_{1}× X

_{1}+ a

_{2}× X

_{2}+ a

_{3}× X

_{3}+ a

_{12}× (X

_{1}× X

_{2}) + a

_{13}× (X

_{1}× X

_{3}) + a

_{23}× (X

_{2}× X

_{3}) + ε

- -
- Y is the response of the experiment, i.e., removal efficiency (R %);
- -
- X
_{1}, X_{2}, X_{3}are the different factors investigated. (X_{1}= pH; X_{2}= bio-sorbent dose; X_{3}= Temperature); - -
- a
_{1}, …, a_{23}are the effects of factors (coefficients). - -
- ε is the error of the model.

#### 2.7. Experimental Protocol of Kinetic and Isotherm Adsorption

- -
- c
_{0}is the initial concentration of the BR dyes (mg/L); - -
- c
_{e}is the residual concentration of BR dye at equilibrium (mg/L);

#### 2.8. Thermodynamic Study

_{ads})

- -
- K
_{ads}is theequilibrium constant; - -
- ΔG° is the free energy variation (kJ/mol);
- -
- R is the perfect gas constant (8.314 J/(mol·K
^{−}) - -
- T is the absolute temperature (K);
- -
- ΔH° and ΔS° are calculated by Van’t Hoff Equation (6) as follows:$$\mathrm{ln}({\mathrm{K}}_{\mathrm{ads}})=-\frac{\Delta \mathrm{H}\xb0}{\mathrm{RT}}+\frac{\Delta \mathrm{S}\xb0}{\mathrm{R}}$$

## 3. Results and Discussions

#### 3.1. Bio-Adsorbent Characterization

#### 3.1.1. BET Surface Area Analysis

_{BET}), pore volume (Vp) and pore diameter (pd) were 997.816 m

^{2}/g, 27.148 cm

^{3}/g and 149.875 A°, respectively. These results affect the removal efficiency of BR dye.

#### 3.1.2. FTIR Analysis

^{−1}represents the vibrations of elongation of O–H groups (e.g., carboxyl, phenols or alcohols) or linked (bound) to amine groups (NH)(the width of the peak indicates an H bond) [33,34].

^{−1}is characterized by the asymmetric and symmetric stretching vibration of the –CH

_{3}or –CH

_{2}aliphatic groups [35]. The bands at 1744 cm

^{−1}and 1611 cm

^{−1}are referred to the C=O stretching vibration of the carbonyl group (aldehyde or ester) as well as the symmetrical stretching vibration of the C=C bond, respectively.

^{−1}are due to the C–O elongation vibration and confirm the presence of carboxyl/alcohol/ether/ester functional groups in the molecular composition of the bio-absorbent. The presence of fluorinated aliphatic compounds (C–F) or C–N bonds is likely in the region around 1015 cm

^{−1}of the FTIR spectrum of ALP [36]. The wide band at 523 cm

^{−1}could be due to the –C–H bending vibration of the alkene [37].

^{−1}, for ALP + BR. This result is a consequence of the adsorption of dye onto the adsorbent surface, thus reducing the amount of –C–H– functional groups [33]. Observing Figure 1, spectra of the exhausted bio-sorbent differs from that of the raw bio-sorbent for those wave lengths where the differences between BR dye and raw ALP are more evident (i.e., from 4000 to 1800 cm

^{−1}), thus confirming the adsorption of BR onto ALP.

#### 3.1.3. SEM Analysis

#### 3.1.4. Energy Dispersive Spectroscopy (EDX)

#### 3.1.5. X-ray Analysis

#### 3.1.6. Thermo Gravimetric Analysis

_{2}) volatilization [41]. The third step, from 220 to 322 °C, shows a remarkable mass loss of 58.7% in 10 min. This mass loss indicates the decomposition of the main constituents of the biomaterial. The last step, from 322 to 900 °C, amounts to a weight loss of 92.6% caused by the cracking of the phenyl group as well as the loss of the hydrocarbon parts [42]. Finally, the first step, from 25 to 220 °C, is due to the water (moisture). The second stage is due to the degradation of hemi-cellulose and cellulose, while the third stage is due to the decomposition of residual lignin [43]. A similar result is present in the international literature; a TGA analysis for artichoke leaves during a pyrolysis process showed five decomposition steps with a total weight loss of 81.8% [44].

#### 3.1.7. The pH Zero Charge Point (pH_{pzc})

_{pzc}. At pH = 4.3 the surface charge is zero (neutral surface). For pH values higher than pH

_{pzc}the bio-sorbent surface charge is negative. Otherwise, if the pH of the solution is lower than the pH

_{pzc}, the surface of the material is positively charged.

_{solution}< pH

_{pzc}).

#### 3.1.8. Iodine and Methylene Blue Index

#### 3.2. Factorial Design

^{2}= 88.2 and desirability D = 0.98 (Figure 11).

#### 3.3. Parametric Study of the Adsorption of BR Dye onto the ALP Surface

#### 3.3.1. Effect of Contact Time

#### 3.3.2. Effect of Temperature

#### 3.3.3. Effect of Initial Concentration of RB Dye

_{0 BR}= 100 mg/L, the adsorption capacity is almost fourfold that obtained with C

_{0 BR}= 20 mg/L. This result can be explained by the presence of a strong gradient of BR dye concentration between the solution and the surface of the adsorbent.

#### 3.4. Kinetics Study of the Adsorption of BR Dye by ALP

^{2}for the linear plots of the pseudo-second-order equation were close to 1, with a value of 0.999 for all the investigated concentrations.

#### 3.5. Adsorption Isotherm

^{2}) are the highest values for all studied systems, but that of Langmuir is not too far from the unit. However, for the Langmuir isotherm, the adsorbed quantity calculated by this model (11.11 mg/g) is different from the experimental adsorbed quantity (about 14 mg/g), but it was very close to the value obtained with the Temkin model (13.3 mg/g).

Type of Isotherm | Linearization of Equations | Constants | R^{2} |
---|---|---|---|

Langmuir | $\frac{1}{{\mathrm{q}}_{\mathrm{e}}}=\frac{1}{{\mathrm{q}}_{\mathrm{max}}}+\frac{1}{{\mathrm{K}}_{\mathrm{L}}\times {\mathrm{C}}_{\mathrm{e}}\times {\mathrm{q}}_{\mathrm{max}}}$ | q_{max} = 11.11 (mg/g)K _{L} = 0.058 (L/mg) | 0.912 |

Freundlich | $\mathrm{ln}\left(\mathrm{q}\right)=\mathrm{ln}\left({\mathrm{K}}_{\mathrm{f}}\right)-\raisebox{1ex}{$1$}\!\left/ \!\raisebox{-1ex}{$\mathrm{n}$}\right.\times \mathrm{ln}\left({\mathrm{C}}_{\mathrm{e}}\right)$ | K_{f} = 1.13 (mg·g^{−1}·(L·mg^{−1})^{1/n})1/n = 0.725 | 0.92 |

Temkin | ${\mathrm{q}}_{\mathrm{e}}=\frac{\mathrm{RT}}{{\mathrm{b}}_{\mathrm{T}}}\times \mathrm{ln}\left({\mathrm{A}}_{\mathrm{T}}\right)+\frac{\mathrm{RT}}{{\mathrm{b}}_{\mathrm{T}}}\times \mathrm{ln}\left({\mathrm{C}}_{\mathrm{e}}\right)$ | RT/b_{T} = 3.52ln(A _{T)} = 0.074 | 0.98 |

Elovich | $\mathrm{ln}\left(\frac{{\mathrm{q}}_{\mathrm{e}}}{{\mathrm{C}}_{\mathrm{e}}}\right)=\mathrm{ln}\left({\mathrm{K}}_{\mathrm{E}}\times {\mathrm{q}}_{\mathrm{m}}\right)-\frac{{\mathrm{q}}_{\mathrm{e}}}{{\mathrm{q}}_{\mathrm{m}}}$ | q_{m} = 13.3 (mg/g)K _{E} = 0.083 | 0.65 |

- -
- q
_{e}and q_{max}are the equilibrium and maximum capacity of adsorption (mg/g); - -
- C
_{e}is the equilibrium concentration of BR (mg/L); - -
- K
_{L}, K_{f}, K_{E}are the Langmuir, Freundlich and Elovich constants, respectively; - -
- R is the universal gas constant, 8.314 J/(mol·K);
- -
- T is the absolute temperature (K);
- -
- b
_{T}is the change in the adsorption energy (J/mole) - -
- A
_{T}is the Temkin constant (L/mg)

_{L}) of the Langmuir isotherm can be defined by Equation (8). The value of R

_{L}indicates whether the adsorption process is irreversible (R

_{L}= 0), favorable (0 < R

_{L}< 1), linear (R

_{L}= 1),or unfavorable (R

_{L}> 1) [46].

_{L}value ranges between 0.147 and 0.812 for BR at the different initial concentrations (4–10–20–50–100 mg/L). This result proves the favorable adsorption of BR dye onto ALP [47].

#### 3.6. Thermodynamic Study

_{ads}) as a function of (1/T). This curve has a slope, i.e.,ΔH°/R and Y-intercept, i.e., ΔS°/R. The adsorption thermodynamic parameters were determined from the experimental results obtained at different temperatures (Figure 16).

## 4. Conclusions

_{pzc}. The study of the effects of several physicochemical parameters on the BR adsorption process by ALP was carried out, and the experimental results showed that both pH and temperature have important effects on the adsorption process, and the optimal values were pH = 4 and T = 24 °C, respectively.

^{3}factorial design of experiments were used to study the effects of three factors (pH, temperature and bio-adsorbent dosage) on the adsorption capacity related to BR dye. The linear model fit well with the experimental data according to the correlation coefficient R

^{2}= 88.2 and desirability D = 0.98. Furthermore, the interaction parameters were studied. The statistical analysis of the results obtained shows that the mutual interaction between pH and bio-adsorbent dosage strongly affects the BR dye removal efficiency. Optimal values of pH, bio-adsorbent dosage and temperature were 4; 8 g/L and 80 °C, respectively. The maximum removal efficiency was 88%. Finally, ALP is an inexpensive and easy-to-produce bio-adsorbent with solid–liquid separation, which can be used successfully in the treatment and removal of dyes, such as BR, from industrial wastewater.

## Author Contributions

## Funding

## Acknowledgments

## Conflicts of Interest

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**Figure 2.**SEM of ALP prior adsorption with different magnifications ((

**a**): 5 µm), ((

**b**): 20 µm), ((

**c**): 50 µm) and ((

**d**): 400 µm).

**Figure 3.**SEM of ALP after adsorption with different magnifications ((

**a**): 5 µm), ((

**b**): 20 µm), ((

**c**): 50 µm) and ((

**d**): 400 µm).

Parameters | Minimum Value | Maximum Value |
---|---|---|

pH | 4 | 10 |

Bio-adsorbent dosage (g) | 0.5 | 2 |

Temperature (°C) | 24 | 80 |

Tests | pH (X_{1}) | Bio-Adsorbent Dosage (g) (X_{2}) | Temperature (°C) (X_{3}) |
---|---|---|---|

1 | 4 | 0.5 | 24 |

2 | 10 | 0.5 | 24 |

3 | 4 | 2 | 24 |

4 | 10 | 2 | 24 |

5 | 4 | 0.5 | 80 |

6 | 10 | 0.5 | 80 |

7 | 4 | 2 | 80 |

8 | 10 | 2 | 80 |

Time (min) | 5 | 10 | 30 | 60 | 90 | 120 |
---|---|---|---|---|---|---|

absorbance (664 nm) | 0.3279 | 0.2975 | 0.2961 | 0.1758 | 0.1782 | 0.201 |

Q (mg/g) (v = 250 mL) | 4.60 | 4.64 | 4.64 | 4.79 | 4.78 | 4.75 |

R (%) | 92.02 | 92.76 | 92.79 | 95.72 | 95.66 | 95.11 |

**Table 4.**Results of factorial design in terms of capacity and removal efficiency of BR dye onto ALP.

pH | Mass (g) | Temperature (°C) | Q (mg/g) | Efficiency (%) |
---|---|---|---|---|

4 | 0.5 | 24 | 7.42 | 68.46 |

10 | 0.5 | 24 | 2.84 | 26.24 |

4 | 2 | 24 | 1.35 | 50.11 |

10 | 2 | 24 | 1.59 | 58.6 |

4 | 0.5 | 80 | 8.11 | 74.8 |

10 | 0.5 | 80 | 0.64 | 5.95 |

4 | 2 | 80 | 2.34 | 86.5 |

10 | 2 | 80 | 1.88 | 69.66 |

Pseudo First-Order | Pseudo Second-Order | Intra Particle Diffusion | ||||||
---|---|---|---|---|---|---|---|---|

Kinetic $\mathbf{ln}\left({\mathbf{q}}_{\mathbf{e}}-{\mathbf{q}}_{\mathbf{t}}\right)={\mathbf{ln}\mathbf{q}}_{\mathbf{e}}-\frac{{\mathbf{K}}_{1}}{\mathbf{2.303}}\text{}\mathrm{t}$ | Kinetic $\frac{\mathbf{t}}{\mathbf{q}}=\frac{1}{{\mathbf{K}}_{2}\xb7{{\mathbf{q}}_{\mathbf{e}}}^{2}}+\frac{1}{{\mathbf{q}}_{\mathbf{e}}}\mathbf{t}$ | Model ${\mathbf{q}}_{\mathbf{t}}={\mathbf{K}}_{\mathbf{in}}\times {\mathbf{t}}^{\mathbf{1}/\mathbf{2}}$ | ||||||

C_{0} (mg·L^{−1}) | R^{2} | K_{1} (min^{−1}) | q_{e} (mg/g) | R^{2} | K_{2} (g·mg^{−1}·min^{−1}) | q_{e} (mg/g) | R^{2} | K_{int} (mg·g^{−1}·min^{−1/2}) |

4 | 0.8132 | 0.103 | 4.17 | 0.9994 | 3.4 | 0.96 | 0.801 | 0.0344 |

10 | 0.5743 | 0.1038 | 2.32 | 0.9999 | 2.9897 | 2.03 | 0.7039 | 0.0778 |

20 | 0.761 | 0.1756 | 1.15 | 0.9999 | 0.5377 | 4.29 | 0.8922 | 0.0601 |

50 | 0.8289 | 0.1194 | 2.85 | 1 | 0.4513 | 8.63 | 0.8444 | 0.4482 |

100 | 0.8018 | 0.155 | 3.39 | 0.9998 | 0.3575 | 14.06 | 0.7527 | 0.7527 |

Parameters | Temperature (K) | ||
---|---|---|---|

297 | 323 | 353 | |

ΔG° (kJ/mol) | −2.411 | −2.314 | −1.948 |

ΔS° (J/(mol·K) | −8.129 | ||

∆H° (kJ/mol) | −4.86 | ||

R^{2} | 0.9745 |

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## Share and Cite

**MDPI and ACS Style**

Khalfaoui, A.; Khelifi, M.N.; Khelfaoui, A.; Benalia, A.; Derbal, K.; Gisonni, C.; Crispino, G.; Panico, A.
The Adsorptive Removal of Bengal Rose by Artichoke Leaves: Optimization by Full Factorials Design. *Water* **2022**, *14*, 2251.
https://doi.org/10.3390/w14142251

**AMA Style**

Khalfaoui A, Khelifi MN, Khelfaoui A, Benalia A, Derbal K, Gisonni C, Crispino G, Panico A.
The Adsorptive Removal of Bengal Rose by Artichoke Leaves: Optimization by Full Factorials Design. *Water*. 2022; 14(14):2251.
https://doi.org/10.3390/w14142251

**Chicago/Turabian Style**

Khalfaoui, Amel, Mohamed Nadir Khelifi, Anouar Khelfaoui, Abderrezzaq Benalia, Kerroum Derbal, Corrado Gisonni, Gaetano Crispino, and Antonio Panico.
2022. "The Adsorptive Removal of Bengal Rose by Artichoke Leaves: Optimization by Full Factorials Design" *Water* 14, no. 14: 2251.
https://doi.org/10.3390/w14142251