Nutrients Recovery from Dairy Wastewater by Struvite Precipitation Combined with Ammonium Sorption on Clinoptilolite
Abstract
:1. Introduction
2. Materials and Methods
2.1. Chemicals, Reagents and Basic Equipment
2.2. Sample Preparation
2.3. Preparation of Zeolite Material
2.4. Ammonium Sorption Experiment
2.5. Struvite Precipitation Experiments
2.6. Effect of Zeolite on Precipitation Process
2.6.1. Gradient Batch Experiments
2.6.2. Combining Sorption and Desirability Approach
2.7. Germination Tests
3. Results
3.1. Characteristics of Zeolite Material
3.2. Sorption and Precipitation Results
3.3. Thermodynamic Aspect
3.4. Characterization of Recovered P Products
3.4.1. XRD and SEM Results
3.4.2. Evaluation of Fertilizer Properties
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Appendix A
Batch no | Mg:P | NH4+:P | Mg | P | NH4+ |
---|---|---|---|---|---|
1 | 1.21 | 2.69 | 150 | 5.819 | 1278 |
2 | 1.81 | 1.0 | 311 | 0.792 | 320.5 |
1.21 | 1.0 | 179 | 2.057 | 338.7 | |
1.51 | 1.0 | 281 | 1.479 | 316.5 | |
3 | 1.81 | 1.0 | 251 | 5 | 149.51 |
1.21 | 1.0 | 108 | 15 | 170.27 | |
1.51 | 1.0 | 194 | 5 | 143.28 | |
4 | 1.81 | 1.0 | 261 | 4 | 118.61 |
1.21 | 1.0 | 132 | 66 | 112.25 | |
1.51 | 1.0 | 231 | 8 | 103.78 | |
5 | 1.81 | 1.0 | 281 | 5 | 82.60 |
1.21 | 1.0 | 80 | 63 | 78.37 | |
1.51 | 1.0 | 238 | 12 | 61.42 | |
f(x) | y = 80.54 + 5908.25exp(−1.597x) | ||||
f’(x) | Y’ = 11453.44exp(−1.597x) | ||||
#iteration | CNH4+ | C’NH4+ | nNH4+ | nP | nMg |
0.104* | 0.039* | 0.044* | |||
1 | 1276.455 | 2318.328 | 0.071 | 0.071 | 0.107 |
2 | 322.613 | 469.260 | 0.018 | 0.018 | 0.027 |
3 | 129.543 | 94.984 | 0.007 | 0.007 | 0.011 |
4 | 90.463 | 19.226 | 0.005 | 0.005 | 0.008 |
5 | 82.552 | 3.892 | 0.005 | 0.005 | 0.007 |
6 | 80.951 | 0.159 | 0.004 | 0.004 | 0.007 |
7 | 80.627 | 0.032 | 0.004 | 0.004 | 0.007 |
8 | 80.562 | 0.007 | 0.004 | 0.004 | 0.007 |
9 | 80.548 | 0.001 | 0.004 | 0.004 | 0.007 |
10 | 80.546 | 0.000 | 0.004 | 0.004 | 0.007 |
11 | 3 × 10−4 |
Appendix B
Run no | Factors | Effluent | Inflow | Outflow | Yields | |||||
---|---|---|---|---|---|---|---|---|---|---|
Mg:P | N:P | Eff (g) | Pi | NH4+(i) | Pout | NH4+(out) | RecN | NH4+ | RecP | |
[%] | ||||||||||
1 | 1.21 | 0.8 | 87.5 | 1252 | 581.76 | 7.28 | 162.68 | 72.8 | 4.8 | 98.6 |
2 | 1.81 | 0.8 | 90 | 1252 | 1054.44 | 7.06 | 521.32 | 70 | 5.72 | 99.2 |
3 | 1.51 | 0.8 | 77.5 | 1252 | 109.08 | 19.48 | 10.01 | 68 | 6.1 | 99.3 |
4 | 1.21 | 1.45 | 81.5 | 1252 | 1054.44 | 4.50 | 815.63 | 45.1 | 5.43 | 99.4 |
5 | 1.21 | 0.15 | 90 | 1252 | 581.76 | 9.13 | 157.04 | 92.4 | 1.21 | 97.3 |
6 | 1.51 | 0.15 | 77.5 | 1252 | 109.08 | 25.81 | 6.45 | 92.3 | 1.25 | 98 |
7 | 1.51 | 1.45 | 98 | 1252 | 1054.44 | 5.28 | 534.85 | 48.2 | 7.3 | 99.6 |
8 | 1.81 | 0.15 | 77.5 | 1252 | 109.08 | 19.84 | 6.50 | 88.2 | 0.0778 | 98 |
9 | 1.81 | 1.45 | 85.5 | 1252 | 581.76 | 14.97 | 135.50 | 33.1 | 7.35 | 99.6 |
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Concentration [mg∙kg−1] | |||||
---|---|---|---|---|---|
Elements | Wastewater | Artificial | Elements | Wastewater | Artificial |
pH | 4.35 | 8.9 | N [%] | 0.14 | - |
C [%] | 3.07 | - | Na | 485 | - |
Cl− [mol·kg−1] | 0.16 | P | 445 | 1203 | |
B | 10.3 | - | S | 132 | - |
Ca | 526 | 404 | Si | 99.94 | - |
K | 1654 | 4524 | NH4+ | 364 | 1876 |
z-Mg | Raw | after NH4+ Contact | |
---|---|---|---|
Compound | m/m% | m/m% | m/m% |
SiO2 | 64.22 | 68.30 | 59.53 |
Al2O3 | 8.39 | 14.28 | 8.01 |
K2O | 8.33 | 4.77 | 11.45 |
CaO | 7.65 | 6.33 | 9.94 |
Fe2O3 | 4.96 | 2.70 | 4.90 |
Effluent Concentration | Product Nutrient Content | ||||||||
---|---|---|---|---|---|---|---|---|---|
[mg·kg−1] | % | ||||||||
Sample | Ca | Mg | P | NH4+ | N | P2O5 | K | Ca | Mg |
GA | 45.2 | 1322 | 4.21 | 84.6 ± 7.63 | 3.42 | 29.5 | 3.05 | 0.65 | 12.8 |
GAZ | 62.4 | 1348 | 4.32 | 48.6 ± 7.61 | 2.02 | 20.7 | 2.53 | 0.85 | 8.81 |
GW | 78.2 | 1048 | 5.81 | 73.8 ± 2.55 | 2.21 | 24.7 | 1.95 | 0.25 | 10.1 |
GWZ | 68.8 | 1235 | 5.54 | 63.0 ± 2.50 | 1.47 | 18.1 | 1.22 | 0.50 | 6.38 |
DA | 45.2 | 282 | 5.41 | 184 ± 2.10 | 5.49 | 30.3 | 0.76 | 4.27 | 9.80 |
DAZ | 62.4 | 293 | 4.80 | 176 ± 1.70 | 2.74 | 26.0 | 0.32 | 1.58 | 10.6 |
DW | 56.7 | 248 | - | 228 ± 2.20 | 3.30 | 25.0 | 0.29 | 2.27 | 9.76 |
DWZ | 63.5 | 279 | - | 212 ± 1.70 | 1.09 | 12.9 | 0.51 | 1.85 | 2.94 |
Component | Species | Mg2+ | NH4+ | PO43− | Na+ | K+ | Ca2+ | H+ | CO32− | H2O | Cl− | GA | GAZ αi (%) | DA | DAZ |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Mg2+ | Mg2+ | 1 | 46.72 | 50.43 | 51.53 | 51.52 | |||||||||
Mg2CO32+ | 2 | 1 | 5.08 | 5.32 | 1.39 | 1.39 | |||||||||
MgOH+ | −1 | 0.05 | 0.06 | 0.06 | 0.06 | ||||||||||
MgCl+ | 1 | 1 | 14.74 | 15.87 | 16.59 | 16.60 | |||||||||
MgHPO4 (aq) | 1 | 0.02 | 0.05 | 0.20 | 0.18 | ||||||||||
MgCO3 (aq) | 1 | 23.38 | 19.81 | 21.23 | 21.25 | ||||||||||
MgHCO3+ | 1 | 1 | 1 | 10.01 | 8.47 | 8.99 | 9.00 | ||||||||
PO43− | PO43− | 1 | 0.07 | 0.06 | 0.09 | 0.09 | |||||||||
HPO42− | 1 | 1 | 36.20 | 31.59 | 48.06 | 48.13 | |||||||||
H2PO4− | 1 | 2 | 0.23 | 0.20 | 0.30 | 0.30 | |||||||||
MgPO4− | 1 | 1.41 | 1.52 | 0.57 | 0.57 | ||||||||||
MgHPO4 (aq) | 1 | 1 | 1 | 33.56 | 36.34 | 13.81 | 13.84 | ||||||||
CaHPO4 (aq) | 1 | 1 | 1 | 0.92 | 2.26 | 0.81 | 0.82 | ||||||||
CaPO4− | 1 | 1 | 3.40 | 8.37 | 2.98 | 2.98 | |||||||||
NaHPO4− | 1 | 1 | 1 | 18.09 | 14.46 | 25.12 | 25.02 | ||||||||
KHPO4− | 1 | 1 | 1 | 4.68 | 4.09 | 6.18 | 6.19 | ||||||||
K2HPO4 (aq) | 1 | 2 | 0.26 | 0.22 | 0.34 | 0.34 | |||||||||
KH2PO4 (aq) | 1 | 1 | 0.01 | 0.01 | 0.02 | 0.02 | |||||||||
KPO42− | 1 | 1 | 0.02 | 0.02 | 0.02 | 0.02 | |||||||||
Na2HPO4 (aq) | 1 | 2 | 1.06 | 0.77 | 1.54 | 1.53 | |||||||||
Na2PO4− | 1 | 2 | 0.03 | 0.02 | 0.04 | 0.04 | |||||||||
NaH2PO4 (aq) | 1 | 1 | 0.03 | 0.03 | 0.05 | 0.05 | |||||||||
NaPO42− | 1 | 1 | 0.04 | 0.04 | 0.06 | 0.06 | |||||||||
NH4+ | NH4+ | 1 | 76.31 | 76.23 | 76.12 | 76.12 | |||||||||
NH3 (aq) | 1 | 1 | 23.65 | 23.66 | 23.85 | 23.85 | |||||||||
CaNH32+ | 1 | 1 | 0.04 | 0.11 | 0.03 | 0.03 | |||||||||
I (M) | 0.36 | 0.35 | 0.32 | 0.32 | |||||||||||
∆G (Kj.mol−1) | −5.87 | −5.42 | −9.66 | −9.56 |
Sample | Element Content in Dry Biomass (mg·kg−1) | TF | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
N | P | K | Ca | Mg | N | P | K | Ca | Mg | |
Struvite (DA) | 4.42 | 16.59 | 48.19 | 20.71 | 8547 | 0.44 | 0.07 | 3.47 | 0.27 | 0.23 |
Str & zeolite (DAZ) | 3.04 | 14.98 | 39.91 | 19.49 | 8423 | 1.04 | 0.12 | 1.09 | 1.58 | 0.33 |
Control | 2.86 | 12.52 | 0.94 | 14.12 | 8.61 | - | - | - | - | - |
Group | Fresh Sprouts Mass | Dry Sprouts Mass | Root Area | Root Length | Steam Length | Root Volume |
---|---|---|---|---|---|---|
[g] | [g] | [cm2] | [g] | [g] | [cm3] | |
DA | 45.14 ± 4.62 | 5.62 ± 0.42 | 8.43 ± 0.34 | 6.06 ± 1.44 | 3.03 ± 1.10 | 0.77 ± 0.12 |
DAZ | 88.7 ± 8.46 | 8.83 ± 1.11 | 13.46 ± 1.15 | 8.32 ± 2.16 | 2.71 ± 0.73 | 1.51 ± 0.24 |
Control | 26.2 ± 4.61 | 4.56 ± 0.43 | 11.24 ± 0.94 | 4.66 ± 0.14 | 1.82 ± 0.46 | 7.18 ± 0.14 |
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Numviyimana, C.; Warchoł, J.; Ligas, B.; Chojnacka, K. Nutrients Recovery from Dairy Wastewater by Struvite Precipitation Combined with Ammonium Sorption on Clinoptilolite. Materials 2021, 14, 5822. https://doi.org/10.3390/ma14195822
Numviyimana C, Warchoł J, Ligas B, Chojnacka K. Nutrients Recovery from Dairy Wastewater by Struvite Precipitation Combined with Ammonium Sorption on Clinoptilolite. Materials. 2021; 14(19):5822. https://doi.org/10.3390/ma14195822
Chicago/Turabian StyleNumviyimana, Claver, Jolanta Warchoł, Bartosz Ligas, and Katarzyna Chojnacka. 2021. "Nutrients Recovery from Dairy Wastewater by Struvite Precipitation Combined with Ammonium Sorption on Clinoptilolite" Materials 14, no. 19: 5822. https://doi.org/10.3390/ma14195822