Thesis: “Chemical and microbial treatment of toxic wastes from Fertilizers industry“ Biological Treatment of Waste and Bio remediation) Environmental Biotechnology Department, Genetic Engineering and Biotechnology Research institute, University of Sadat City, Egypt

2. “Chemical and microbial treatment of toxic wastes
from the phosphate Fertilizers industry”
M.Sc
By
Omar Ali Omar Elkashef
In
Genetic Engineering and Biotechnology
Environmental Biotechnology
(Biological treatment of waste and Bioremediation)

3. 3
Prof Dr. Hamdy A. Hassen
Prof. of Microbiology
Institute of Genetic Engineering and Biotechnology Research
University of Sadat City
Dr. Ibrahim El-Sayed Ibrahim Mousa
Ass. Prof. of Environmental science
Institute of Genetic Engineering and Biotechnology Research
University of Sadat City
Dr. Ayman Said Abdel-Aziz
Ass. Prof. of Environmental science
Institute of Genetic Engineering and Biotechnology Research
University of Sadat City
SUPERVISORS

4. Introduction

5. Introduction
• Fresh water resource is becoming day-by-day at
the faster rate of deterioration.
• Also, Ground water will be an important source of
future water supply and will play a crucial role in
any kind of development.
• Water quality is now a global problem
(Mahananda et al., 2005).

6. Introduction
• Phosphates are necessary elements in the
fertilizers used to supply food and feed human
beings.
• It is important to note that healthy animals and
human beings also require adequate amounts of
phosphorus in their food for normal metabolic
processes (FAO, 1984, 1995).
• Phosphate rocks contain about 4% fluoride.

7. Introduction
• Phosphate ores are divided into three groups
according to their P2O5 content:
• Low-grade ores (12–16% P2O5),
• Intermediate grade ores (17–25% P2O5),
• High-grade ores (26–35% P2O5).
• Deposits that could be mined and processed
economically to give about 28–38% P2O5 are
considered commercial phosphate deposits
(Sengul et al., 2006).

8. Introduction
• Some wastewater resources such as live-stock wastes
and manure have high concentrations of phosphate
(Nancharaiah et al., 2016; Tao et al., 2016).
• Moreover, the use of the fluorine-containing fertilizer
could cause the pollution to ecosystems.
• With the grade declining of phosphate rock in recent
years, manufacturing enterprise will have to utilize
mid-and low-grade phosphate rock in production
process of nitro-phosphate [Liu et al., 2014].

9. Introduction
• Normally, the objective of wastewater treatment
is to remove phosphate and Fluoride rather than
recover.
• However, researchers has increasingly recognized
the importance of phosphate recovery from
wastewater as wastewater provides rich sources
for phosphate recovery (TNN, 2011).
• Recovering phosphate from wastewater can
eliminate eutrophication to some extent and
produce fertilizers as a supplementary source.

10. Introduction
• Furthermore, the problem of global warming
can also be alleviated through phosphate and
Fluoride recovery (Bradford-Hartke et al.,
2015).
• In order to meet the needs of a regulations
and to decrease pollutants releasing to sewer
system from fertilizer industries, the removal
conditions has been improved.

11. The aim of this work
• The aim of this work was to optimize the removal
efficiency of phosphate and fluoride loads by
changing chemical forms.
• Studying the factors affecting treatment though
many indictors was investigated.
• A comparison between different bases on the
basis of increasing pH by addition of Ca(OH)2 and
CaCl2 and the effluent quality was run under
different operation indicators.

12. Introduction
1. Oxidation/filtration method :
a. Oxidation
b. Filtration
2. Activated carbon (AC) filtration process
3. BIRM media
4. Anthracite
5. Greensand
6. Pebbles and sand
7. By Subsurface iron removal

13. Fertilizers industry
Wastewater treatment plant

15. Analyses Methods
• 1- Phosphate content
• 2- Fluoride content
• 3- pH of wastewater
• 4- Total suspended solids
• 5- Total dissolved solids (TDS)

16. • Wastewater samples:
• Wastewater samples were supplied by Evergrow
company, Sadat city, Egypt.
• The real water that collected for used as plant
influent has characters and then a daily sample
was collected until the final of the experiments.
• Water sampling was also done at the beginning
of monitoring and survey program. Table 1
shows the details of the chemical composition of
soluble species of influent.

17. 1.4. Removal efficacies
It is important to calculate the rate at which
contaminants are removed in order to design the full
scale application of the technology (Rajic et al., 2016).
Phosphate and fluoride removal were calculated by the
following equation:
removal % =
W0− Wt
∗ 100 (1)
W0

18. • 1.5. Statistical analysis
• The data were analyzed by using a statistical
software (SPSS Version 17, SPSS INC, Chicago,
IL, USA). Initially, the descriptive statistics
were computed. One-way ANOVA was used
followed by Duncan's post hoc test (α 0.05). In
all tests, p values smaller than 5% were
considered statistically significant.

19. Results

20. 3.1. Characteristics of the Wastewater

21. Parameters Unite
Value
Average ± SD Minimum Maximum
pH (site 1) 8.30±0.29 7.04 9.29
pH (site 3-1) 6.33±1.70 1.71 11.7
General pH (site 3-2) 7.37±0.88 2.86 11.00
Indicators pH (site 4) 6.59±2.00 1.46 11.94
TDS (site 1) mg/l 565.7±149.7 375 1912
TDS (site 4) mg/l 6051±4983 285 29370
Phosphate
(PO4) mg/l 148.25 103 211
Anions Fluoride (Fl) mg/l 17.25±5.6 12 25
Total alkalinity mg/l 377±486 33 4724
Table 1: Composition of influent was used in all experiments.

22. 5.00
5.50
6.00
6.50
7.00
7.50
8.00
8.50
9.00
9.50
10.00
1
8
15
22
29
36
43
50
57
64
71
78
85
92
99
106
113
120
127
134
141
148
155
162
169
176
183
190
197
204
211
218
225
232
239
246
253
260
267
274
281
288
295
302
309
316
323
330
pH of the site(sulforic acid cooling tour)

23. 0.00
2.00
4.00
6.00
8.00
10.00
12.00
1
8
15
22
29
36
43
50
57
64
71
78
85
92
99
106
113
120
127
134
141
148
155
162
169
176
183
190
197
204
211
218
225
232
239
246
253
260
267
274
281
288
295
302
309
316
323
330
pH of the site # 2

24. 0.00
2.00
4.00
6.00
8.00
10.00
12.00
1
8
15
22
29
36
43
50
57
64
71
78
85
92
99
106
113
120
127
134
141
148
155
162
169
176
183
190
197
204
211
218
225
232
239
246
253
260
267
274
281
288
295
302
309
316
323
330
pH of the site (calcium chloride liquid plant)

25. 0.00
2.00
4.00
6.00
8.00
10.00
12.00
14.00
1
8
15
22
29
36
43
50
57
64
71
78
85
92
99
106
113
120
127
134
141
148
155
162
169
176
183
190
197
204
211
218
225
232
239
246
253
260
267
274
281
288
295
302
309
316
323
330
pH of the site (potassium sulfate acid liquefaction plant)

26. Characterization of pH collected from influent and effluent of
industrial treatment plant (Evargrow) and Egyptian law
(44/2000) from studying period March 2014 to Feb 2016.
0
2
4
6
8
10
12
14
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59 61 63 65 67 69 71 73 75 77 79 81 83 85 87 89 91
pH characterization
pH Influent pH Effluent pH Law 44/2000 pH Law 44/2000

27. Characterization of phosphate as PO4 collected from influent and effluent of
industrial treatment plant (Evergrow) and Egyptian law (44/2000) from
studying period March 2014 to Feb 2016.
0.1
1
10
100
1000
10000
100000
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59 61 63 65 67 69 71 73 75 77 79
ppm
PO4 characterization
Influent Effluent Law 44/2000

28. Removal% of phosphate as PO4 for industrial treatment plant
(Evergrow) from studying period March 2014 to Feb 2016.
0
10
20
30
40
50
60
70
80
90
100
1 4 7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52 55 58 61 64 67 70 73 76 79 82 85 88 91
PO4 removal%

29. Characterization of Fluoride collected from influent and effluent
of industrial treatment plant (Evargrow) from studying period
March 2014 to Feb 2016.
0
10
20
30
40
50
60
70
80
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59 61 63 65 67 69 71 73 75 77 79
ppm
Fluoride characterization
Influent Effluent

30. Removal% of Fluoride for industrial treatment plant (Evergrow)
from studying period March 2014 to Feb 2016.
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
100.0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59 61 63 65 67 69 71 73 75 77
Fluoride Removal%

31. Characterization of TSS collected sample from influent and
effluent of industrial treatment plant (Evergrow) and Egyptian
law (44/2000) from studying period March 2014 to Feb 2016.
0.1
1
10
100
1000
10000
100000
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59 61 63 65 67 69 71 73 75 77 79
ppm
TSS characterization
Influent Effluent Law 44/2000

32. Removal% of TSS for industrial treatment plant (Evargrow) from
studying period March 2014 to Feb 2016.
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
100.0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59 61 63 65 67 69 71 73 75 77 79 81 83 85 87 89 91
TSS Removal%

33. Characterization of industrial wastewater treatment plant in average and SD
through different parameters (pH, phosphate, and total suspended solids)
through studying period.
0.1
1
10
100
1000
10000
Influent Effluent Influent Effluent Influent Effluent
pH PO4 T.S.S

34. phosphate concentration with different pH correction
by 100 ppm of Ca(OH)2.

35. Effect of treatment with different concentration of CaCl2 for
simulated water contains 25 ppm of phosphate and pH 8.

36. Comparison between alkali treatment with free of 100 ppm of
Ca(OH)2 and CaCl2 and mixture of 50 ppm Ca(OH)2 and 50 ppm
CaCl2) for simulated water contains 25 ppm phosphate and pH
8.

37. Optimization of specific pH and correlation with alkali
Ca(OH)2 and CaCl2 addition.

38. Removal% of phosphate and fluoride according treatment with
Ca(OH)2 and CaCl2 as a function of pH degree correction.

39. Chemical characterization (pH, fluoride, phosphate and
total dissolved solids) of real influent after treatment

40. Removal % of fluoride, phosphate and total dissolved solids of
real influent after treatment with 25 ppm of CaCl2.
82.0
97.1
78.2
0
10
20
30
40
50
60
70
80
90
100
TDS Phosphate Fluoride
Removal%

41. Conclusion
• Increases in pollutants loading adversely did
not impact on the precipitation capacity of the
alkali.
• The decline in precipitation was remarkably
after pH 7.4 for phosphate fertilizer
wastewater.
• The use of a pH dependent alkali technique
underestimated the development of CaCl2 or
Ca(OH)2 within the reaction condition;

42. Conclusion
• pH was found to be an important parameter for the reduction process, the
optimum pH ranged from 8 to 9.0 with using alkali. Small increase in
influent pH after 8.5 caused a slow increase in phosphate and fluoride
removal
• This was a unique finding that has not been reported for chemical
modification treating wastewater by self discharged wastewater to
improve our environment through limitation of one pollutant that could
be reacted with other.
• Further study to improve the efficiency of advanced degradation to
accelerate the removal efficiencies of TP and TF and its associated
microbial intermediate products is needed in case of fertilizers industry
wastewater.
• Further study to evaluate the impact of biofilter will prove to be valuable.