The Use of Exoskeletons and Molts of Farmed Mealworm (Tenebrio molitor) for the Removal of Reactive Dyes from Aqueous Solutions
Abstract
:1. Introduction
2. Materials and Methods
2.1. Sorbents
2.2. Sorbates (Dyes)
2.3. Chemical Reagents
- Hydrochloric acid (HCl)—37%—(solution pH correction);
- Sodium hydroxide (NaOH) > 99.9%-micropellets—(solution pH correction);
- Petroleum ether (40–60 °C)—dewaxing of molts and exoskeletons.
2.4. Laboratory Equipment
- HI 110 pH meter (HANNA Instruments, Olsztyn, Poland)—for measurement and correction of solution pH;
- An 11 basic laboratory grinder (IKA, Willmington, NC, USA)—for grinding exoskeletons and molts biomass;
- SK-71 laboratory shaker (JEIO TECH, Daejeon, Republic of Korea)—for the sorption process;
- MS-53M multi-channel stirrer (JEIO TECH, Daejeon, Republic of Korea)—for the sorption process;
- UV-3100 PC spectrophotometer (VWR Spectrophotometers, Mississauga, ON, Canada)—for quantifying dye in solutions;
- FT/IR-4700LE FT-IR Spectrometer with single reflection ATR attachment (JASCO International, Tokyo, Japan)—for determining the FTIR spectra of the sorbents;
- Gemini VI (Micromeritics, Norcross, GA, USA)—for the measurements of porosity and surface area of the sorbent.
2.5. Sorbent Preparation
2.6. Determination of pH Effect on Dye Sorption Efficiency
2.7. Determination of Dye Sorption Kinetics
2.8. Determination of pH Effect on Dye Sorption Efficiency
2.9. Computation Methods
- QS—the mass of sorbed dye [mg/g];
- C0—the initial concentration of the dye [mg/L];
- CS—concentration of the dye after sorption [mg/L];
- V—the volume of the solution [L];
- m—sorbent mass [g].
- Q—the instantaneous value of sorbed dye [mg/g];
- qe—the amount of dye sorbed at equilibrium state [mg/g];
- t—time of sorption [min];
- k1—pseudo-first-order adsorption rate constant [1/min];
- k2—pseudo-second-order adsorption rate constant [g/(mg·min)];
- kid—intraparticle diffusion model adsorption rate constant [mg/(g·min0.5)].
- Q—the mass of sorbed dye [mg/g];
- C—concentration of the dye left in the solution [mg/L];
- Qmax—maximum sorption capacity from the Langmuir equation [mg/g];
- b1—maximum sorption capacity of the sorbent (type I active sites) [mg/g];
- b2—maximum sorption capacity of the sorbent (type II active sites) [mg/g];
- KC—constant from the Langmuir equation [L/mg];
- K1 and K2—constants from the Langmuir 2 equation [L/mg];
- K—the sorption equilibrium constant in the Freundlich model;
- n—constant in the Freundlich model;
- B—constant in the Dubinin–Radushkevich model [mol2/J2];
- R—universal gas constant—8.314 [J/mol∗K];
- T—absolute temperature (K).
3. Results and Discussion
3.1. Characteristics of Tested Sorbents (FTIR, Surface)
3.2. Influence of pH on the Dye Sorption Efficiency on MES and MMS
3.3. Kinetics of Dye Sorption on MES and MMS
3.4. Maximum Sorption Capacity of MES and MMS
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Sorbent | Dye | Dye Conc. | Pseudo-First Order Model | Pseudo-Second-Order Model | Exp. Data | ||||||
---|---|---|---|---|---|---|---|---|---|---|---|
k1 | qe,cal. | R2 | χ2 | k2 | qe,cal. | R2 | χ2 | qe,exp. | |||
[mg/L] | [1/min] | [mg/g] | - | - | [g/mg·min] | [mg/g] | - | - | [mg/g] | ||
MES | RB5 | 50 | 0.0829 | 20.78 | 0.9917 | 0.265 | 0.0059 | 22.57 | 0.9974 | 0.071 | 21.55 |
250 | 0.0743 | 58.84 | 0.9581 | 3.469 | 0.0018 | 64.36 | 0.9914 | 0.635 | 61.97 | ||
RY84 | 50 | 0.0742 | 20.16 | 0.9758 | 0.680 | 0.0050 | 22.16 | 0.9961 | 0.085 | 21.38 | |
250 | 0.0606 | 51.08 | 0.9499 | 4.117 | 0.0016 | 56.53 | 0.9867 | 0.949 | 53.23 | ||
MMS | RB5 | 50 | 0.0847 | 19.92 | 0.9989 | 0.029 | 0.0062 | 21.72 | 0.9991 | 0.027 | 20.29 |
250 | 0.0706 | 43.72 | 0.9800 | 1.169 | 0.0022 | 48.02 | 0.9980 | 0.113 | 45.44 | ||
RY84 | 50 | 0.0675 | 16.00 | 0.9944 | 0.413 | 0.0053 | 17.85 | 0.9988 | 0.322 | 16.48 | |
250 | 0.0553 | 34.92 | 0.9690 | 1.648 | 0.0022 | 38.16 | 0.9952 | 0.210 | 35.98 |
Sorbent | Dye | Dye Conc. | Phase 1 | Phase 2 | ||||
---|---|---|---|---|---|---|---|---|
kd1 * | Duration | R2 | kd2 | Duration | R2 | |||
[mg/L] | [*] | [min] | - | [*] | [min] | - | ||
MES | RB5 | 50 | 3.807 | 20 | 0.9998 | 0.537 | 130 | 0.9252 |
250 | 11.993 | 10 | 0.(9) | 3.057 | 110 | 0.9775 | ||
RY84 | 50 | 3.592 | 20 | 0.9997 | 0.689 | 130 | 0.9852 | |
250 | 9.687 | 10 | 0.(9) | 2.980 | 110 | 0.9843 | ||
MMS | RB5 | 50 | 3.443 | 30 | 0.9952 | 0.239 | 120 | 0.9005 |
250 | 7.647 | 20 | 0.9996 | 1.838 | 100 | 0.9734 | ||
RY84 | 50 | 2.626 | 30 | 0.9928 | 0.349 | 120 | 0.9746 | |
250 | 5.545 | 20 | 0.9989 | 1.793 | 100 | 0.9926 |
Sorbent | Dye | Langmuir 1 Model | Freundlich Model | Dubinin–Radushkevich Model | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Qmax | Kc | R2 | χ2 | k | n | R2 | χ2 | Qmax | B | R2 | χ2 | ||
[mg/g] | [L/mg] | - | - | - | - | - | - | [mg/g] | [mol2/J2] | - | - | ||
MES | RB5 | 71.65 | 0.084 | 0.986 | 2.822 | 16.3 | 0.27 | 0.899 | 21.18 | 63.68 | 0.0168 | 0.923 | 35.56 |
RY84 | 57.75 | 0.076 | 0.998 | 0.297 | 13.5 | 0.26 | 0.902 | 717.89 | 51.39 | 0.0211 | 0.910 | 24.95 | |
MMS | RB5 | 49.38 | 0.063 | 0.998 | 0.101 | 11.1 | 0.26 | 0.895 | 11.56 | 43.88 | 0.0346 | 0.914 | 28.44 |
RY84 | 41.82 | 0.031 | 0.993 | 0.979 | 6.5 | 0.31 | 0.946 | 4.88 | 34.88 | 0.1104 | 0.871 | 641.5 | |
Sorbent | Dye | Langmuir 2 Model | |||||||||||
Qmax | b1 | K1 | b2 | K2 | R2 | χ2 | |||||||
[mg/g] | [mg/g] | [L/mg] | [mg/g] | [L/mg] | - | - | |||||||
MES | RB5 | 78.70 | 45.84 | 0.099 | 32.86 | 0.002 | 0.990 | 2.433 | |||||
RY84 | 60.49 | 51.95 | 0.091 | 8.54 | 0.004 | 0.999 | 0.279 | ||||||
MMS | RB5 | 55.72 | 48.86 | 0.095 | 6.86 | 0.002 | 0.999 | 0.098 | |||||
RY84 | 44.25 | 30.08 | 0.104 | 14.17 | 0.006 | 0.997 | 0.204 |
Dye | Sorbent | Sorption Capacity [mg/g] | pH of Sorption | Time of Sorption [min] | Source |
---|---|---|---|---|---|
RB5 | Coconut shells | 0.82 | 2.0 | 60 | [39] |
Pumpkin seed husks | 1.00 | 3.0 | 60 | [40] | |
Sunflower biomass | 1.10 | 2.0 | 210 | [41] | |
Macadamia seed husks | 1.21 | 3.0 | 510 | [42] | |
Cotton fibers | 2.74 | 3.0 | 240 | [30] | |
Sunflower seed shells | 2.89 | 3.0 | 210 | [31] | |
Buckwheat hulls | 4.43 | 3.0 | 300 | [43] | |
Hen feathers | 5.19 | 2.0 | 210 | [28] | |
Cotton seed husks | 12.90 | 2.0 | 30 | [44] | |
The seed scales of Eriobotrya japonica | 13.76 | 3.0 | 150 | [34] | |
Beech sawdust | 13.90 | 3.0 | 1440 | [45] | |
Wheat straw | 15.70 | 7.0 | 195 | [46] | |
Wheat straw (other research) | 16.72 | 3.0 | 210 | [47] | |
Wood (walnut) activated carbon | 19.30 | 5.0 | 400 | [48] | |
Activated carbon from palm shell | 25.10 | 2.0 | 300 | [49] | |
Banana peel (powder) | 26.90 | 3.0 | 60 | [50] | |
Rape stalks (waste) | 32.80 | 2.5 | 30 | [51] | |
Cotton stems | 35.70 | 1.0 | 360 | [52] | |
Activated carbon from Carob tree | 36.90 | 2.0 | 120 | [33] | |
Activated carbon from bamboo | 39.02 | 2.0 | 60 | [53] | |
Molts of mealworm (MMS) | 55.72 | 2.0 | 150 | This study | |
Powdered activated carbon | 58.82 | - | - | [54] | |
Chitin flakes from shrimp shells (produced by Sigma-Aldrich, Darmstadt, Germany) | 60.00 | 6.0 | 600 | [55] | |
Modified activated carbon (SPC) | 69.90 | 2.0 | <60 | [56] | |
Mealworm exoskeletons (MES) | 78.70 | 2.0 | 150 | This study | |
Chitin from the molts of mealworm (own study) (CH) | 121.15 | 3.0 | 300 | [15] | |
Powdered activated carbon | 125.79 | 2.0 | 240 | [29] | |
Chitin flakes from snow crab shells (produced by BioLog Heppe, Hayward, CA, USA) | 131.56 | 3.0 | 360 | [27] | |
RY84 | Compost | 2.20 | 3.0 | 180 | [57] |
Sunflower seed husks | 4.15 | 2.0 | 90 | [31] | |
Wool | 11.00 | 7.0 | 180 | [35] | |
Activated carbon from the Borassus flabellifer plant | 40.00 | No data | No data | [58] | |
Cotton fibers | 43.34 | 2.0 | 240 | [30] | |
Mealworm exoskeletons (MES) | 44.25 | 2.0 | 150 | This study | |
Hydroxyapatite | 50.25 | 5.0 | 180 | [59] | |
Molts of mealworm (MMS) | 60.49 | 2.0 | 150 | This study | |
Chitin from the molts of mealworms | 138.54 | 3.0 | 270 | [15] |
Sorbent | Quantity of Sorbent [g] | Quantity of RB5 Removable by 1 g Sorbent [mg] | Max. Content of Chitin in Sorbent | Quantity of RB5 Removable by Chitin in 1 g of Sorbent [mg] | Ratio of Sorption Capacity to Chitin in the Sorbent [%] | Increase of Sorption Capacity in Relation to Chitin in the Sorbent [%] |
---|---|---|---|---|---|---|
Chitin from Mealworm Molts (CH) | 1 | 121.15 | 100%—1.0 g | 121.15 | 100.0 | - |
Mealworm Exoskeletons (MES) | 1 | 78.70 | 10%—0.1 g | 12.12 | 649.3 | 549.3 |
Mealworm Molts (MMS) | 1 | 55.72 | 18%—0.18 g | 21.81 | 255.4 | 155.4 |
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Jóźwiak, T.; Filipkowska, U.; Bakuła, T. The Use of Exoskeletons and Molts of Farmed Mealworm (Tenebrio molitor) for the Removal of Reactive Dyes from Aqueous Solutions. Appl. Sci. 2023, 13, 7379. https://doi.org/10.3390/app13137379
Jóźwiak T, Filipkowska U, Bakuła T. The Use of Exoskeletons and Molts of Farmed Mealworm (Tenebrio molitor) for the Removal of Reactive Dyes from Aqueous Solutions. Applied Sciences. 2023; 13(13):7379. https://doi.org/10.3390/app13137379
Chicago/Turabian StyleJóźwiak, Tomasz, Urszula Filipkowska, and Tadeusz Bakuła. 2023. "The Use of Exoskeletons and Molts of Farmed Mealworm (Tenebrio molitor) for the Removal of Reactive Dyes from Aqueous Solutions" Applied Sciences 13, no. 13: 7379. https://doi.org/10.3390/app13137379