H2O2 Based Oxidation Processes for the Treatment of Real High Strength Aqueous Wastes
Abstract
:1. Introduction
2. Materials and Methods
2.1. Aqueous Wastes
2.2. Pilot Scale Plants
- Plant A consists of a 2 L glass reactor; the cover is welded and a discharge valve is placed on the bottom. An external jacket connected to a cryostat is used for cooling the system. On the central cone a stirring device is applied. In the lateral cone two medium-high-pressure UV lamps are placed: each lamp has a power of 125 W (emission spectrum: 280–400 nm).
- Plant B consists of AISI 316L stainless steel photo-reactor (8 L volume), containing one UV lamp. During the experimental work, two different kinds of lamp were used: the first is a low-pressure lamp with a power of 36 W (emission spectrum: 254 nm); the second is similar but with a power of 120 W. The following advantages may be ascribed to the use of low-pressure lamps: low surface temperature (40–50 °C), high power conversion efficiency (35%–40% of electric energy is converted into useful UV energy) and long duration (8000–10,000 h).
- Plant C consists of: an AISI 316L stainless steel photo-reactor (10 L volume), a high-pressure UV lamp (power: 10–30 kW; emission spectrum: 200–700 nm), a feeding pump (with flowrate adjustable from 2 to 10 L·min−1), a pump for H2O2 dosage (flowrate adjustable up to 8 mL·min−1), probes for the measurement of flowrate, electrical conductivity, pH, redox potential, and temperature. The UV lamp used in this plant simulates solar radiation.
2.3. Experimental Tests
2.4. Analytical Methods
3. Results and Discussion
3.1. Phase I: COD Removal
3.1.1. H2O2/UV Process
3.1.2. Photo-Fenton Process
3.1.3. Fenton Process
3.2. Phase II: Anionic and Non-Ionic Surfactant Removal
Fenton Process
4. Conclusions
- The H2O2/UV process was very effective, yielding a COD removal efficiency higher than 70% in 120 min reaction, with a dosage of hydrogen peroxide lower than the stoichiometric value (the optimal H2O2/CODinitial dosage ratio being 1/2). The decrease of the UV power caused a significant reduction in the removal of COD, but the radiation intensity (up to 2000 W·L−1 in our experimentation) revealed to be a crucial factor especially in the earlier stage of the process (about for 40 min): this aspect can be exploited to reduce the costs related to energy consumption.
- The results of the photo-Fenton process were comparable to those obtained with the H2O2/UV treatment in terms of COD removal, at a reaction time of 240 min. No significant catalytic effect was observed by the addition of iron (an Fe2+/H2O2 ratio of 1/30 was finally chosen). The specific power input was 125 W·L−1 (medium-high pressure Hg lamp) and the H2O2/CODinitial ratio was 1/2. Photolytic reactions and the presence of dissolved oxygen (activated by UV radiation), either inflated or transferred by strong mixing conditions, revealed to be crucial factors for COD removal, which occurred even after the complete disappearance of hydrogen peroxide.
- The COD removal efficiency obtained with the Fenton process (phase I) was lower than 25%. The organic matter, present at very high concentration, exerted an inhibitory effect on the Fe2+ regeneration process, thus leading to the accumulation of H2O2.
- On the contrary, Fenton oxidation exerted very good performance in the treatment of aqueous wastes with high concentrations of surfactants (phase II). In this case, the results showed that the optimal treatment conditions for surfactants removal are the following: Fe2+/H2O2 = 1/4, H2O2/CODinitial ratio = 1, and contact time = 30 min. These process conditions allowed to obtain an average removal yield of 70% for TAS and 95% for MBAS.
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Parameter | Phase I—COD Removal | Phase II—Surfactant Removal | |||||
---|---|---|---|---|---|---|---|
A.W.#1 | A.W.#2 | A.W.#3 | A.W.#4 | A.W.#5 | A.W.#6 | ||
pH | - | 5.2–5.4 | 5.6–5.7 | 6.5–6.7 | 5.6–5.9 | 5.2–5.5 | 8.1–8.6 |
COD | mg·L−1 | 200,000–220,000 | 95,000–100,000 | 18,000–20,000 | 55,000–56,600 | 48,000–50,000 | 98,000–104,000 |
BOD5/COD | - | 0.48–0.50 | 0.38–0.41 | 0.42–0.45 | 0.18–0.25 | n.a. | n.a. |
TN | mg·L−1 | <0.5 | 3800–4000 | 290–310 | <0.5 | <0.5 | <0.5 |
N-NH4+ | mg·L−1 | <0.5 | 20–25 | 35–40 | <0.5 | 7–10 | 60–70 |
N-NO3- | mg·L−1 | <0.5 | <0.5 | 15–20 | <0.5 | <0.5 | <0.5 |
N-NO2- | mg·L−1 | <0.1 | <0.1 | 0.15–0.2 | <0.1 | <0.1 | <0.1 |
TP | mg·L−1 | <0.5 | <0.5 | 380–420 | <0.5 | <0.5 | <0.5 |
TAS | mg·L−1 | n.a. | n.a. | 20–25 | 980–1020 | 850–950 | 15,000–17,000 |
MBAS | mg·L−1 | n.a. | n.a. | 95–110 | 1490 | 11,000–13,000 | 3500–3800 |
Process Tested | Contact Time (min) | H2O2 Dosage | Fe2+ Dosage | UV | Air Supply | Aqueous Waste Tested | |||||
---|---|---|---|---|---|---|---|---|---|---|---|
(mg·L−1) | H2O2/CODinitial | Dosing Mode | (mg·L−1) | Fe2+/H2O2 | Dosing Mode | UV Plant | Lamp Power (W·L−1) | ||||
H2O2/UV | 120 | 150 | 1/4 | Initial | - | - | - | A-MHP | 125 | No | A.W.#1 |
120 | 360 | 1/2 | Initial | 125 | |||||||
120 | 400 | 2/3 | Initial | 125 | |||||||
120 | 150 | 1/4 | Consecutive | 125 | |||||||
120 | 300 | 1/2 | Consecutive | 125 | |||||||
240 | 160 | 1/4 | Initial | 125 | |||||||
240 | 300 | 1/2 | Initial | 125 | |||||||
240 | 400 | 2/3 | Initial | 125 | |||||||
240 | 300 | 1/2 | Initial | 62.5 | |||||||
120 | 30 | 1/20 | Initial | - | - | - | B-LP | 4.5 | |||
60 | 1/10 | Initial | |||||||||
300 | 1/2 | Initial | |||||||||
120 | - | - | - | - | - | - | C-HP | 1500 | No | A.W.#2 | |
100 | 1/10 | Initial | 1500 | No | |||||||
200 | 1/5 | Initial | 1500 | No | |||||||
350 | 1/3 | Initial | 1500 | No | |||||||
500 | 1/2 | Initial | 1500 | No | |||||||
700 | 3/4 | Initial | 1500 | No | |||||||
700 | 3/4 | Continuous | 1500 | No | |||||||
1800 | 3/2 | Continuous | 1500 | No | |||||||
2250 | 5/2 | Continuous | 2000 | No | |||||||
700 | 3/4 | Initial | 1500 | Yes | |||||||
700 | 3/4 | Continuous | 1500 | Yes | |||||||
120 | - | - | - | - | - | - | B-LP | 15 | No | ||
350 | 1/3 | Initial | |||||||||
700 | 3/4 | Initial | |||||||||
350 | 1/3 | Initial | |||||||||
700 | 3/4 | Continuous | |||||||||
Photo-Fenton | 120 | 300 | 1/2 | Consecutive | 10 | 1/30 | Initial | A-MHP | 125 | No | A.W.#1 |
240 | 10 | 1/30 | |||||||||
120 | 15 | 1/20 | |||||||||
120 | 25 | 1/10 | |||||||||
120 | 50 | 1/6 | |||||||||
120 | 67 | 1/4 | |||||||||
120 | 100 | 1/3 | |||||||||
120 | 60 | 1/10 | Consecutive | 10 | 1/6 | Initial | B-LP | 4.5 | |||
300 | 1/2 | 50 | 1/6 | ||||||||
Fenton | 120 | 300 | 1/2 | Consecutive | 15 | 1/20 | Initial | - | - | No | A.W.#1 |
50 | 1/6 | ||||||||||
100 | 1/3 | ||||||||||
120 | 500 | 1/2 | Consecutive | 50 | 1/10 | Initial | - | - | No | A.W.#2 | |
Consecutive | 100 | 1/5 | Initial | No | |||||||
Continuous | 100 | 1/5 | Initial | No | |||||||
Consecutive | 100 | 1/5 | Initial | Yes | |||||||
Consecutive | 180 | 1/3 | Initial | No | |||||||
Consecutive | 250 | 1/2 | Initial | No | |||||||
Consecutive | 250 | 1/2 | Consecutive | No | |||||||
Consecutive | 500 | 1 | Consecutive | No |
Process Tested | Contact Time (min) | H2O2 Dosage | Fe2+ Dosage | Air Supply | Aqueous Waste Tested | ||||
---|---|---|---|---|---|---|---|---|---|
(mg·L−1) | H2O2/CODinitial | Dosing Mode | (mg·L−1) | Fe2+/H2O2 | Dosing Mode | ||||
Fenton | 30 | 3600 | 1/3 | Initial | 1800 | 1/2 | Initial | No | A.W.#3 |
30 | 3600 | 1/3 | 900 | 1/4 | |||||
30 | 8200 | 3/4 | 1650 | 1/5 | |||||
60 | 11,000 | 1 | 5500 | 1/2 | |||||
60 | 8200 | 3/4 | 4100 | 1/2 | |||||
60 | 10,500 | 3/4 | 5200 | 1/2 | |||||
60 | 16,800 | 1.2 | 8400 | 1/2 | |||||
60 | 16,800 | 1.2 | 4200 | 1/4 | |||||
60 | 21,000 | 3/4 | Initial | 5200 | 1/4 | Initial | No | A.W.#4 | |
60 | 28,000 | 1 | 7000 | 1/4 | |||||
60 | 21,000 | 3/4 | 10,500 | 1/2 | |||||
30 | 21,000 | 3/4 | 5200 | 1/4 | |||||
60 | 42,000 | 3/2 | 10,500 | 1/4 | |||||
120 | 21,000 | 3/4 | 5200 | 1/4 | |||||
60 | 9400 | 3/4 | Initial | 2350 | 1/4 | Initial | No | A.W.#5 | |
60 | 12,500 | 1 | 3100 | 1/4 | |||||
60 | 18,700 | 3/2 | 4700 | 1/4 | |||||
30 | 9400 | 3/4 | 2350 | 1/4 | |||||
60 | 12,500 | 1 | 6250 | 1/2 | |||||
120 | 12,500 | 1 | 3100 | 1/4 | |||||
60 | 15,000 | 3/4 | Initial | 3750 | 1/4 | Initial | No | A.W.#6 | |
60 | 20,000 | 1 | 5000 | 1/4 | |||||
60 | 30,000 | 3/2 | 15,000 | 1/2 | |||||
30 | 15,000 | 3/4 | 3750 | 1/4 | |||||
60 | 20,000 | 1 | 5000 | 1/4 | |||||
120 | 20,000 | 1 | 5000 | 1/4 |
Time (min) | Photo-Fenton Test 1 (P-F1) | Photo-Fenton Test 2 (P-F2) | ||
---|---|---|---|---|
COD Removal Yield (%) | Residual H2O2 (mg·L−1) | COD Removal Yield (%) | Residual H2O2 (mg·L−1) | |
0 | - | - | - | - |
10 | 12 | 50 | 9 | 50 |
40 | 25 | 1 | 20 | 12.5 |
80 | 39 | 0 | 40 | 0 |
120 | 58 | 0 | 62 | 0 |
160 | - | - | 61 | 0 |
200 | - | - | 65 | 0 |
240 | - | - | 72 | 0 |
Fenton Test | Aqueous Waste Tested | Iron Dosage (Fe2+/H2O2) | COD Removal Yield (%) |
---|---|---|---|
F1 | A.W.#1 | 1/20 | 10 |
F2 | 1/6 | 11 | |
F3 | 1/3 | 17 | |
F4 | A.W.#2 | 1/10 | 3 |
F5 | 1/5 | 11 | |
F6 | 1/3 | 16 | |
F7 | 1/2 | 21 |
Aqueous Waste Tested | Iron Dosage (Fe2+/H2O2) | H2O2 Dosage (H2O2/CODinitial) | Contact Time (min) | Removal Yield (%) | ||
---|---|---|---|---|---|---|
TAS | MBAS | Total Surfactants | ||||
Mix#1 | 1/5 | 3/4 | 30 | 52 | 76 | 70 |
1/2 | 60 | 53 | 80 | 73 | ||
A.W.#4 | 1/4 | 3/4 | 30 | 44 | 90 | 71 |
60 | 62 | 95 | 81 | |||
120 | 83 | 99 | 92 | |||
A.W.#5 | 1/4 | 3/4 | 30 | 70 | 97 | 95 |
60 | 43 | 96 | 93 | |||
1 | 60 | 77 | 98 | 96 | ||
120 | 76 | 98 | 97 | |||
A.W.#6 | 1/4 | 3/4 | 30 | 89 | 94 | 90 |
60 | 80 | 95 | 83 | |||
1 | 60 | 91 | 99 | 93 | ||
120 | 91 | 98 | 92 |
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Collivignarelli, M.C.; Pedrazzani, R.; Sorlini, S.; Abbà, A.; Bertanza, G. H2O2 Based Oxidation Processes for the Treatment of Real High Strength Aqueous Wastes. Sustainability 2017, 9, 244. https://doi.org/10.3390/su9020244
Collivignarelli MC, Pedrazzani R, Sorlini S, Abbà A, Bertanza G. H2O2 Based Oxidation Processes for the Treatment of Real High Strength Aqueous Wastes. Sustainability. 2017; 9(2):244. https://doi.org/10.3390/su9020244
Chicago/Turabian StyleCollivignarelli, Maria Cristina, Roberta Pedrazzani, Sabrina Sorlini, Alessandro Abbà, and Giorgio Bertanza. 2017. "H2O2 Based Oxidation Processes for the Treatment of Real High Strength Aqueous Wastes" Sustainability 9, no. 2: 244. https://doi.org/10.3390/su9020244
APA StyleCollivignarelli, M. C., Pedrazzani, R., Sorlini, S., Abbà, A., & Bertanza, G. (2017). H2O2 Based Oxidation Processes for the Treatment of Real High Strength Aqueous Wastes. Sustainability, 9(2), 244. https://doi.org/10.3390/su9020244