Preparation and Application of Efficient Biobased Carbon Adsorbents Prepared from Spruce Bark Residues for Efficient Removal of Reactive Dyes and Colors from Synthetic Effluents
Abstract
:1. Introduction
2. Materials and Methods
2.1. Preparation of BBCs
2.2. BBC Characterization
2.2.1. Textural Properties
2.2.2. Elemental Analysis, Yield (%), Raman Spectroscopy, and Zeta Potential
2.2.3. Water Vapor Sorption and Hydrophobicity/Hydrophilicity
2.3. Dye Adsorption Analysis
2.3.1. Batch Adsorption Studies
2.3.2. Adsorption Kinetics and Equilibrium Analysis
2.3.3. Preparation of the Dyeing Synthetic Effluents
2.3.4. Analytical Control of the Measurements and Statistical Evaluation of Nonlinear Models
3. Results and Discussion
3.1. BBC Characteristics
3.1.1. Textural Properties and Porosity
3.1.2. Elemental Analysis, Carbon Yield, Raman Spectroscopy, Zeta-Potential, and FTIR
3.1.3. Water Vapor Adsorption Isotherms, Hydrophilicity Index (HI)
3.2. Dye Adsorption Analysis
Adsorption Kinetics
3.3. Equilibrium of Adsorption
3.4. Mechanism of Adsorption
3.5. Adsorbent Performance: Comparison with Literature
3.6. Treatment of Synthetic Dye Effluents
4. Possible Application of Used BBC after Adsorption of Dyes
5. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Compounds | Concentration (mg L−1) | λmax (nm) | |
---|---|---|---|
Effluent | A | B | |
RO-16 | 50 | 50 | 494 |
RB- 4 | 50 | 50 | 595 |
Methylene Blue | 50 | 50 | 668 |
Bismarck Brown | 50 | - | 468 |
Crystal Violet | 50 | - | 590 |
Methyl Red | - | 50 | 507 |
Methyl Orange | - | 50 | 522 |
Phenol Red | - | 50 | 550 |
Sodium Dodecyl | 25 | 25 | - |
Sodium sulfate | 25 | 25 | - |
Ammonium chloride | 20 | 25 | - |
Sodium acetate | 20 | 25 | - |
pH | 5.1 | 4.9 | - |
Samples | ZnCl2-BBC | KOH-BBC |
---|---|---|
Parameters | ||
SBET (m2 g−1) | 754 | 1067 |
External surface area (m2 g−1) | 328 | 526 |
% of mesopore area (%) | 43.51 | 49.29 |
t-plot Micropore area (m2 g−1) | 425.8 | 541.2 |
% of micropore area (%) | 56.49 | 50.71 |
Total pore volume (cm3 g−1) | 0.4205 | 0.5585 |
t-plot micropore volume (cm3 g−1) | 0.2172 | 0.2776 |
% of micropore volume (%) | 51.65 | 49.70 |
Volume of mesopores (cm3 g−1) | 0.2033 | 0.2809 |
Average pore size (nm) | 2.231 | 2.093 |
Adsorbent | Activation Reagent | Preparation Conditions | SBET (m2 g−1) | Ref. |
---|---|---|---|---|
Scots pine bark | Steam + N2 | Firstly, the biomass was carbonized using slow pyrolysis at 475 °C for 3 h. Afterward, heated at 800 °C for 3.5 h under steam activation [steam (30 and 40%) + N2 (66 and 300 L/h)]. | 539–603 | [8] |
Norway spruce bark | Steam + N2 | Firstly, the biomass was carbonized using slow pyrolysis at 475 °C for 3 h. Afterward, heated at 800 °C for 3.5 h under steam activation [steam (30 and 40%) + N2 (66 and 300 L/h)]. | 187– 369 | [8] |
Norway spruce bark | Steam + N2 | The biomass was heated at 600 °C for 2 h under steam activation (steam + N2). | 351 | [9] |
Norway spruce bark | ZnCl2 | A mixture of ZnCl2 and biomass powder at ratio 2.0:1.0 (ZnCl2:biomass) and pyrolyzed at 600 °C for 2 h. Afterward, it was washed with HCl to remove the inorganic compounds. | 1495 | [9] |
Tea leave residue | KOH | A mixture of KOH and tea powder (2:1) and pyrolyzed at 900 °C for 60 min. Afterward, it was washed with HCl to remove the potassium compounds and further pyrolyzed at 1200 °C. | 912 | [28] |
Palm shell | KOH+ ZnCl2 | Pre-carbonization of biomass at 400 °C for 2 h. Afterward, a mixture of biomass and both KOH (75%) and ZnCl2 (25%) at the final ratio of biomass: chemical activator 1:4. The mixture was then pyrolyzed at 850 °C for 1 h and washed with HCl. | 1295 | [29] |
Garlic peel | KOH | First, it was hydro-carbonized and then chemically activated by KOH (ratio 2:1, KOH: biomass) and pyrolyzed at 600 °C at 4 °C/min under N2 flow for 2 h. | 947 | [30] |
Rice plants | KOH | The biomass was Pre-carbonized at 500 °C for 1 h, followed by NaOH washing. Afterward, the pyrolyzed BBC was mixed with KOH at ratio 1:4. The mixture was then pyrolyzed at 800 °C for 30 min and then washed with HCl. | 2330 | [31] |
Brazil nutshells | ZnCl2 | A mixture of ZnCl2 and biomass powder at ratio 1.5:1.0 (ZnCl2:biomass) and pyrolyzed at 600 °C for 30 min. Afterward, it was washed with 6.0 M HCl to remove the inorganic compounds. | 1457 | [32] |
Sewage sludge | ZnCl2 | A mixture of ZnCl2 and biomass powder at ratio 0.5:1.0 (ZnCl2:biomass) and pyrolyzed at 500 °C for 15 min. Afterward, it was washed with HCl to remove the inorganic compounds. | 679 | [33] |
Coconut shell | ZnCl2 | Blending coconut shell powder and ZnCl2 at ratio 1:3 in 50 mL of 3 M FeCl3 solution. Afterward, heated at 900 °C for 1 h under an inert atmosphere. Afterward, it was washed with HCl to remove the inorganic compounds. | 1874 | [34] |
Norway spruce bark | ZnCl2 | ZnCl2 and biomass powder mixture at ratio 1.0:1.0 (ZnCl2:biomass) and pyrolyzed at 800 °C for 60 min. Afterward, it was washed with 6.0 M HCl to remove the inorganic compounds. | 754 | This work |
Norway spruce bark | KOH | A mixture of KOH and biomass powder at ratio 1.0:1.0 (KOH: biomass) and pyrolyzed at 800 °C for 60 min. Afterward, it was washed with 1.0 M HCl to remove the inorganic compounds. | 1067 | This work |
Samples | ZnCl2-BBC | KOH-BBC |
---|---|---|
Parameters | ||
HI (H2O/n-heptane) | 1.19 | 1.29 |
Zeta potential (mV) | −19.4 | −20.5 |
pH | 5.1 | 6.0 |
Carbon content (%) | 94.8 | 91.6 |
Nitrogen content (%) | 0.51 | 0.29 |
Hydrogen (%) | 1.2 | 1.6 |
Oxygen (%) | 2.5 | 5.3 |
Ash (%) | 0.99 | 1.21 |
BBC yield (%) | 38.1 | 14.2 |
Model | RO-16 Initial Concentration (1000 mg L−1) | RB-4 Initial Concentration (1000 mg L−1) | ||
---|---|---|---|---|
ZnCl2-BBC | KOH-BBC | ZnCl2-BBC | KOH-BBC | |
Pseudo-first order | ||||
q1 (mg g−1) | 74.71 | 307.5 | 84.01 | 301.7 |
k1 (min−1) | 0.4529 | 3.502 | 0.7381 | 2.489 |
R2 | 0.9639 | 0.9606 | 0.8502 | 0.8182 |
R2adj | 0.9614 | 0.9573 | 0.8408 | 0.8068 |
SD (mg g−1) | 5.107 | 20.22 | 11.79 | 46.03 |
Pseudo-second order | ||||
q2 (mg g−1) | 89.96 | 332.7 | 92.62 | 329.1 |
k2 (g mg−1 min−1) | 0.00566 | 0.01539 | 0.01277 | 0.009700 |
R2 | 0.9783 | 0.9963 | 0.9102 | 0.9019 |
R2adj | 0.9768 | 0.9960 | 0.9046 | 0.8958 |
SD (mg g−1) | 3.957 | 6.217 | 9.126 | 33.81 |
General order | ||||
qn (mg g−1) | 78.98 | 356.3 | 136.6 | 355.2 |
kn (min−1 (g mg−1)n−1) | 1.114 × 10−6 | 4.140 × 10−4 | 4.964 × 10−7 | 2.595 × 10−5 |
n (-) | 22.69 | 2.6270 | 33.08 | 40.08 |
R2 | 0.9852 | 0.9985 | 0.9629 | 0.9799 |
R2adj | 0.9838 | 0.9983 | 0.9580 | 0.9831 |
t0.5 (hour) | 1.46 | 0.24 | 1.57 | 0.43 |
T0.95 (hour) | 6.00 | 2.98 | 6.95 | 3.21 |
SD (mg g−1) | 3.311 | 4.049 | 8.861 | 10.22 |
Model | Samples | |||
---|---|---|---|---|
ZnCl2-BBC | KOH-BBC | ZnCl2-BBC | KOH-BBC | |
Langmuir | RO-16 | RB-4 | ||
Qmax (mg g−1) | 90.04 | 358.2 | 59.00 | 339.15 |
kL (L mg−1) | 0.05004 | 2.579 | 0.02698 | 0.005491 |
R2 | 0.8386 | 0.8614 | 0.9534 | 0.9905 |
R2adj | 0.8225 | 0.8488 | 0.9488 | 0.9896 |
SD (mg g−1)2 | 13.77 | 57.72 | 4.794 | 13.93 |
Freundlich | ||||
kF ((mg g−1) (mg L−1)−1/nF) | 34.37 | 257.1 | 11.10 | 14.25 |
nF (dimensionless) | 6.7123 | 16.24 | 3.906 | 1.859 |
R2 | 0.8480 | 0.8467 | 0.9889 | 0.9818 |
R2adj | 0.8328 | 0.8328 | 0.9878 | 0.9799 |
SD (mg g−1)2 | 13.36 | 60.71 | 2.399 | 19.31 |
Liu | ||||
Qmax (mg g−1) | 123.1 | 354.9 | 332.9 | 582.5 |
kS (mg L−1) | 0.02017 | 1.943 | 0.007468 | 0.004040 |
nL (dimensionless) | 0.3850 | 1.780 | 0.2913 | 0.8848 |
R2 | 0.8498 | 0.8646 | 0.9891 | 0.9911 |
R2adj | 0.8164 | 0.8375 | 0.9899 | 0.9891 |
SD (mg g−1)2 | 13.99 | 59.84 | 2.344 | 14.21 |
Adsorbent | pH | Dosage (g L−1) | T (°C) | Qmax (mg g–1) | Ref. |
---|---|---|---|---|---|
RO-16 | |||||
BBC-KOH-800 | 5.5 | 1.5 | 22 | 354.8 | This study |
BBC-ZnCl2-800 | 5.5 | 1.5 | 22 | 90.1 | This study |
Chitosan/sepiolite composite | 6.5 | 2.0 | 30 | 190.96 | [46] |
Fish scales Mesoporous BBC | 6.0 | 1.0 | 50 | 114.2 | [47] |
BBC Brazilian-pine fruit shell | 2.5 | 2.5 | 50 | 314.0 | [48] |
BBC Brazilian-pine fruit shell | 2.5 | 2.5 | 50 | 470.0 | [48] |
BBC from rice husk ash | 11 | 2.5 | 30 | 13.32 | [49] |
Phosphoric BBC from biomass | 6.2 | 0.4 | 30 | 58.54 | [50] |
Psyllium seed powder biosorbent | 4.0 | 2.0 | 30 | 206.6 | [51] |
Paper sludge activated carbon | 2.0 | 1.0 | 30 | 178.0 | [52] |
Ananas Comosus leaves BBC | 2–3 | 1.0 | 30 | 147.05 | [53] |
Sewage sludge BBC | 2.0 | 10.0 | 25 | 114.7 | [54] |
Coffee husk-based BBC | 4.0 | 2.0 | 30 | 66.76 | [55] |
Coffee husk-based BBC | 4.0 | 2.0 | 50 | 76.57 | [55] |
RB-4 | |||||
BBC-KOH-800 | 4.0 | 1.5 | 22 | 582.5 | This study |
BBC-ZnCl2-800 | 4.0 | 1.5 | 22 | 332.9 | This study |
Multi-walled carbon nanotubes | 2.0 | 1.5 | 25 | 502.5 | [42] |
Single-walled carbon nanotubes | 2.0 | 1.5 | 25 | 567.7 | [42] |
Chitosan hydrogel beads (CHB) | 4.0 | 1.0 | 30 | 317 | [43] |
CHB modified with hexadecylamine | 4.0 | 1.0 | 30 | 454 | [43] |
Enteromorpha prolifera BBC | 6.0 | - | 27 | 131 | [56] |
Mg–Al layered double hydroxide | 2.0 | 0.75 | 22 | 328 | [57] |
Cotton grafted with chitosan | 4.0 | 10 | 25 | 180 | [58] |
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dos Reis, G.S.; Larsson, S.H.; Thyrel, M.; Pham, T.N.; Claudio Lima, E.; de Oliveira, H.P.; Dotto, G.L. Preparation and Application of Efficient Biobased Carbon Adsorbents Prepared from Spruce Bark Residues for Efficient Removal of Reactive Dyes and Colors from Synthetic Effluents. Coatings 2021, 11, 772. https://doi.org/10.3390/coatings11070772
dos Reis GS, Larsson SH, Thyrel M, Pham TN, Claudio Lima E, de Oliveira HP, Dotto GL. Preparation and Application of Efficient Biobased Carbon Adsorbents Prepared from Spruce Bark Residues for Efficient Removal of Reactive Dyes and Colors from Synthetic Effluents. Coatings. 2021; 11(7):772. https://doi.org/10.3390/coatings11070772
Chicago/Turabian Styledos Reis, Glaydson Simões, Sylvia H. Larsson, Mikael Thyrel, Tung Ngoc Pham, Eder Claudio Lima, Helinando Pequeno de Oliveira, and Guilherme L. Dotto. 2021. "Preparation and Application of Efficient Biobased Carbon Adsorbents Prepared from Spruce Bark Residues for Efficient Removal of Reactive Dyes and Colors from Synthetic Effluents" Coatings 11, no. 7: 772. https://doi.org/10.3390/coatings11070772
APA Styledos Reis, G. S., Larsson, S. H., Thyrel, M., Pham, T. N., Claudio Lima, E., de Oliveira, H. P., & Dotto, G. L. (2021). Preparation and Application of Efficient Biobased Carbon Adsorbents Prepared from Spruce Bark Residues for Efficient Removal of Reactive Dyes and Colors from Synthetic Effluents. Coatings, 11(7), 772. https://doi.org/10.3390/coatings11070772