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TI Journals International Journal of Engineering Sciences www.tijournals.com
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International Journal of Engineering Sciences
www.tijournals.com

Int. j. eng. sci., Vol(3), No (12), December, 2014. pp. 120-129

ISSN:

2306-6474

Copyright © 2014. All rights reserved for TI Journals.

Coagulation and Dissolved Air Floatation for Treatment of Oil-Water Emulsion

Mohamed Hussein Abdel Megid

Alexandria University, Faculty of Engineering, Chemical Engineering Department, Alexandria, Egypt.

Amer Abdel Razek Amer

Alexandria petroleum company, Alexandria, Egypt.

Khaled Hassan Elsayed *

Alexandria petroleum company, Alexandria, Egypt.

*Corresponding author: kh_hassan1988@yahoo.com

Keywords

Dissolved air floatation coagulation wastewater treatment oil in water emulsion refinery wastewater

Abstract

Petroleum refineries generate significant amounts of wastewater which have to be treated and processed before their discharge into water streams. The refinery wastewater treatment plants employ physico- chemical processes (Usually API separator as a primary treatment and dissolved air flotation technique as a secondary treatment) to achieve effluents of satisfactory oil content to be further treated by biological processes. In the present study, coagulation and flotation processes are optimized to reduce the concentrations of oil, grease and other contaminants using different coagulants, this will provide different choices to the designer of a newly built wastewater treatment unit or to the operator of an already built unit that wasn't designed for a recently changed characteristics of wastewater stream, due to modifications or major changes in the crude oil processing variables. Alum, ferrous sulphate, ferric chloride and other chemicals are chosen for affecting coagulation. Treatment efficiency is evaluated in terms of effluent oil in water concentration. The experiments are conducted in discontinuous mode to assess the feasibility of the process. Flotation is investigated as a post-treatment process for the removal of emulsified hydrocarbons and satisfactory results are obtained. However different responses to the coagulant treatment were observed within the tested samples, Ferrous sulphate at PH = 10 removed 67% oil, Alum at PH =10 removed 73% oil, Ferric chloride at PH = 8 removed 74 % oil, other combinations with manufactured chemicals removed up to

87 % oil while normal DAF operations with no additives removed only 61 % oil from the oily wastewater.

1.

Introduction

The effluent of oil-water (o-w) emulsions is found in the petroleum industry during the producing, refining, and marketing processes [1].Oil presence in water even in small quantities is harmful to the environment; therefore, there is a great need to develop efficient methods for oil removal. There are several treatment processes applied, e.g. the API (American Petroleum institute) separator method, which is used for large oil droplets (greater than 150 µM). And the floatation method, which is used for relatively smaller droplets. The floatation method includes several techniques such as dissolved air, induced air, and electro floatation [1]. The process of floatation consists of four basic steps summarized as follows: (1) air bubble generation, (2) contact between gas bubble and oil droplets, (3) attachment of gas bubbles to oil droplets, and (4) rising up of air-oil combination [2]. For a successful floatation process the oil droplets must attach to gas bubbles and must remain in good contact until the bubbles reach the surface of floatation cell. The process is complex because it involves the hydrodynamics and surface chemistry. Dissolved air floatation is an effective method for removing low density particles from suspension and clarifying low turbidity [3]. In addition, dissolved air floatation has been used for treating wastewater to separate oil from aqueous dispersion, chemically treated wastewater, and refinery wastewater [4] however, these conventional floatation techniques are not satisfactory for removing emulsified oils without chemical pre-treatment [4,5] chemical pre-treatment of oil-water, by PH adjustment and coagulation [6], is based on the addition of chemicals that destroy the protective action of the emulsifying agent, overcoming the repulsive effects of the electrical double layers to allow finely-sized oil droplets to form larger droplets through coalescence [7]. El-Gohary et al. [8] found that ferric chloride, ferrous sulphate, and alum were highly effective coagulants in reducing Chemical oxygen demand. Chemical treatment is also very important as a pre-treatment process for DAF and an essential requirement for efficient treatment. It requires certain conditions of pre-treatment for reducing suspended solids, Greases & oil and separating Greases & oil sludge from water [9]. Therefore, the enhanced efficiency of oily wastewater treatment using DAF needs optimum conditions for chemical pre-treatment. Coagulation-dissolved air floatation is a preferable technique for treatment of oily wastewater [10] and refineries [11]. The process variables, which control the DAF system, namely the saturation pressure and hydraulic surface loading rate, depend on wastewater characteristics and the effluent quality requirements [12]. It is worth mentioning that, an adequate aggregation of the particulate matter represents an essential requirement for efficient floatation technique [13]. The objective of the experiments is to investigate chemical coagulation followed by dissolved air floatation using alum, ferric chloride, ferrous sulphate, and LC-9590 (polymer coagulant obtained from kurita company GmbH) for pretreatment of oily wastewater. The optimum PH values and coagulant dose were determined for each coagulant. Emphasis will be afforded to the removal efficiency of oil and grease.

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Coagulation and Dissolved Air Floatation for Treatment of OilWater Emulsion

International Journal of Engineering Sciences Vol(3), No (12), December, 2014.

  • 2. Methodology

    • 2.1. Wastewater and analytical methods

Emulsions were prepared from petroleum crude oil (Marine Balaim oil). Table (1) indicates the physical properties of oil used. The emulsifier

used was Tween 80. The proper amount of emulsifier was added according to the Critical Micelle Concentration. The coagulants used were ferric chloride, alum, ferrous sulphate, and LC-9590.

Table 1. Physical properties of Marine Balaim crude oil

Characteristics

value

Specific gravity at 60/60 (ASTM D1298)

0.8730

API gravity

29

Pour point (max ºC) (ASTM D79)

1

Viscosity RI at 70 ºF (ASTM D445)

136 SUS

At 100 ºF

71 SUS

Sulfur content wt % (ASTM D129)

2.30

Salt Content wt % (IP 77)

0.005

Carbon residue conrasdon wt % (ASTM D189)

5.2

Wax content vol % (ASTM D95)

4.2

Water content vol % (ASTM D85)

Nile

Asphaltenes wt % (IP 143)

1.96

Ash content wt % (ASTM D482)

0.004

The oil in water emulsion was prepared as follows; ten cubic centimeters of crude oil were added to one Liter of water in a metallic container. The proper amount of emulsifier (Tween 80) was added according to the Critical Micelle Concentration, and then a high speed mixer of 2500 rpm was applied for 20 minutes. This highly concentrated emulsion was filled up to 10 liters, Then mixed roughly for another 30 minutes at 2000 rpm. After that the emulsion is ready for processing and is introduced to the dissolved air flotation unit first step which is the pressurizing tank.

  • 2.2. Treatment procedure

The coagulation-floatation experiments were performed using a flotation unit, the schematic diagram of which is presented in figure (1). The main components of the floatation unit are: air compressor, a pressure retention tank, and a floatation cell. The pressure tank is designed to withstand a pressure up to 10 kg/cm2. The pressure within the tank was regulated via a pressure gauge mounted on the tank. The floatation unit is made of a calibrated plexi-glass column, 85 cm in length and 5 cm in diameter. The pressurized air/water mixture was released from the retention tank to the floatation cell unit through a valve located at the bottom of the tank. Oil in water emulsion (wastewater) in the pressure tank was saturated with air at a pressure of 6 kg/cm2. The required amount of air pressurized water was released gradually to the floatation cell. Coagulants were injected using graduated syringes. The treated wastewater samples were then collected for analysis from a 10 cm high nozzle after times of 5, 10, 15, 20, 25, and 30 minutes.

121 Coagulation and Dissolved Air Floatation for Treatment of OilWater Emulsion International Journal of Engineering Sciences

Figure 1. Dissolved air flotation unit [DAF]

  • 2.3. Oil Concentration Determination

The concentration of emulsified oil was determined by the extraction colorimetric technique. Hexane was used as a solvent to extract the oil

from the oil in water emulsion. The oil concentration in Hexane was measured with UNICO spectrophotometer model 2000 [1, 14].

  • 3. Results and discussion

    • 3.1. Estimating Optimum PH Values of Each Additive Using Jar Test

Different kinds of Chemical additives were investigated using the Jar test in order to find the optimum conditions to apply at the Dissolved air flotation unit. In order to study the performance of these additives optimum PH value and coagulant dose are needed, that’s why JAR test was used at 2 steps. The first step was to find the optimum PH value at a fixed dose. So 1000 mg/l of each additive were used and PH values of 3, 5,6,7,8 and 10 were tested.

Mohamed Hussein Abdel Megid, Amer Abdel Razek Amer, Khaled Hassan Elsayed *

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International Journal of Engineering Sciences Vol(3), No (12), December, 2014.

The second step was to find the optimum coagulant dose of additive at the optimum PH value obtained from the previous step each chemical additive was tested at concentrations of 50, 100, 200, 400, 600, 800 and 1000 mg/L and at the optimum PH value previously obtained. JAR TEST experiments were made as follows: Three liters of emulsion were taken and divided equally to six different Beakers each given hydrochloric acid or caustic soda treatment till the desired PH value obtained with error of ± 0.2 then stirred at 250 rpm for 3 minutes to promote coagulation then at 30 rpm for 20 minutes to promote flocculation then left to settle for One hour, test samples are drawn from the point in the center of beaker and half the height of the liquid in the beaker to apply same conditions for each experiment.

3.2. Use of Alum

3.2.1. Effect of ph

For determination of the optimum pH value of Alum, different pH values covering a range from 3 to 10 were tested. The Alum dose was kept constant at 1000 mg/l. Data presented in Figure (2) shows that the optimum pH values is 10 at which oil removal reaches value of 86.9% .

3.2.2 Effect of alum dose

Changing the alum dose from 50 to 100 mg/l, at a pH value of 10 gave the results presented in Figure (3).Available data indicates that the oil

removal efficiency increased from 87 to 88% by increasing the alum dose from 50 to 1000 mg/l respectively. The predominant removal mechanism at low doses of alum is adsorption and charge neutralization. However, at high doses of coagulant is sweep floc coagulation by enmeshment in the aluminum hydroxide precipitate. Further increase of the alum dose from 100 to 1000 mg/l exerted slight improvement in oil removal i.e. by a value of 3.5%.Therefore, the optimum dose of alum that enhanced maximum removal of oil was taken as 100 mg/l [8, 15, 16].

250 88 86 200 84 82 150 % oil removal oil Conc 80 mg/L 100 78
250
88
86
200
84
82
150
% oil removal
oil Conc
80
mg/L
100
78
76
50
Conc
74
% removal
0
72
0
2
4
6
8
10
12
PH

Figure 2. Effect of PH on oil removal at constant alum concentration of 1000mg/l

140 92 120 91 100 90 % oil removal 80 oil Conc 89 mg/L 60 88
140
92
120
91
100
90
% oil removal
80
oil Conc
89
mg/L
60
88
40
87
20
Conc
% removal
0
86
0
200
400
600
800
1000
1200
Conc of alum mg/l

Figure 3. Effect of alum concentration on oil removal at constant PH = 10

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Coagulation and Dissolved Air Floatation for Treatment of OilWater Emulsion

International Journal of Engineering Sciences Vol(3), No (12), December, 2014.

3.3. Studies on Ferrous Sulphate behavior

  • 3.3.1. Effect of PH

To determine the optimum pH-value for ferrous sulfate, a fixed dose equivalent to 1000 mg/l was used. The pH was changed from 3 to 10. It can be seen from Figure (4) that percentage removal of oil was increased from 59 to 87% by increasing the pH of the reaction from 6 to 10 respectively. Therefore, pH 10 is recommended as the optimum pH for this experimental run. The minimum value at PH 6 is due to the low oxidation rate at pH 6.0. [8]

  • 3.3.2. Effect of ferrous sulfate dose

To find out the optimum ferrous sulfate dose, different doses ranging from 50 to 1000 mg/l were tested. The effect of coagulant dose on oil

reduction is presented in Figure (5). Resulted data indicates that the oil removal efficiency increased from 75 to 90.7% by increasing the ferrous sulphate dose from 100 to 1000 mg/l respectively. So optimum ferrous sulphate dose was taken as 100 mg/l.

300 100 90 250 80 70 200 % oil removal 60 oil Conc 150 50 mg/L
300
100
90
250
80
70
200
% oil removal
60
oil Conc
150
50
mg/L
40
100
30
20
50
Conc
10
% removal
0
0
0
2
4
6
8
10
12
PH

Figure 4. Effect of PH on oil removal at constant ferrous sulphate concentration of 1000mg/l

300 100 90 250 80 70 200 % oil removal 60 oil Conc 150 50 mg/L
300
100
90
250
80
70
200
% oil removal
60
oil Conc
150
50
mg/L
40
100
30
20
50
Conc
10
% removal
0
0
0
200
400
600
800
1000
1200
Conc of Ferrous sulphate mg/l

Figure 5. Effect of ferrous sulphate concentration on oil removal at constant PH = 10

Mohamed Hussein Abdel Megid, Amer Abdel Razek Amer, Khaled Hassan Elsayed *

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International Journal of Engineering Sciences Vol(3), No (12), December, 2014.

Basic equations occurring during the coagulation process for ferrous sulfate is given in the following equation:

FeSO 4 +2 HCO 3 Fe (OH) 2 + SO 4 -2 + 2CO 2

Hydrolysis of FeSO4 during coagulation results in the formation of corresponding gel like hydroxides and some positively charged mononuclear and poly-nuclear species so the reaction favors the alkaline solutions as they produce negatively charged hydroxide ions. These positively charged compounds combine with negatively charged colloidal particles present in the wastewater by charge neutralization mechanism and at the time of settling under gravity these hydroxides and complexed hydroxides sweep away remaining uncharged/charged colloidal particles of the wastewater with them and precipitates out. [17]

3.4. Studies on Ferric chloride behavior

  • 3.4.1. Effect of PH

For determination of the optimum pH value of ferric chloride, different pH values covering a range from 3 to 10 were tested. The ferric chloride dose was kept constant at 1000 mg/l. Data presented in Figure (6) shows that the optimum pH values is 5 at which oil removal reaches value of 89.3%, then a reduction in oil removal percentage occurs till a value of 86.6 %at PH 7 the raises again till 88 % at PH 8 that’s due to at pH 5, the main iron ions species present in solution is Fe(OH)2+, while at pH around 8, it is Fe(OH)3. Fe(OH)2+ can neutralize negatively charged materials like organic substances and suspended particles. On the other hand, Fe(OH)3, a hydrophobic compound, can adsorb contaminants in particulate form by surface interactions, which in some cases can lead to polymeric entities.

  • 3.4.2. Effect of ferric chloride dose

The use of different doses of ferric chloride ranging from 50 to 1000 mg/l was examined at the predetermined optimum pH value (5). The removal of oil increased with increasing dose of ferric chloride as shown in Figure (7) the oil percentage removal increased from 83.5 to 90% when the dose of the ferric chloride was increased from 100 to 900 mg/l, respectively. Thus the optimum dose of ferric chloride that enhanced oil removal will not exceed 100 mg/l. This will allow coagulant saving and consequently lower sludge production.

The principle removal mechanism at low concentration of Ferric chloride is adsorption [15].And by Increasing the dose of the ferric chloride would increase the super saturation of the Fe (OH)3 which increased the nucleation rate and hence the floc growth rate. As a result, suspension of greater number of flocs was enhanced, and subsequently, removal of larger amounts of COD was achieved, due to the availability of larger surface area on which adsorption of the organic matter took place. On the contrary, low doses of ferric chloride led to the formation of larger but fewer flocs as a result of faster growth rate relative to nucleation rate, which resulted in a smaller surface area on which adsorption of organic matter occurred [8].

140 89.5 120 89 100 88.5 % oil removal 80 oil Conc 88 mg/L 60 87.5
140
89.5
120
89
100
88.5
% oil removal
80
oil Conc
88
mg/L
60
87.5
40
87
20
Conc
% removal
0
86.5
0
2
4
6
8
10
12
PH

Figure 6. Effect of PH on oil removal at constant ferric chloride concentration of 1000mg/l

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Coagulation and Dissolved Air Floatation for Treatment of OilWater Emulsion

International Journal of Engineering Sciences Vol(3), No (12), December, 2014.

180 91 90 160 89 140 88 120 % oil removal 87 100 oil Conc 86
180
91
90
160
89
140
88
120
% oil removal
87
100
oil Conc
86
mg/L
80
85
60
84
40
83
Conc
20
82
% removal
0
81
0
200
400
600
800
1000
1200
Conc of Feric chloride mg/l
Figure 7. Effect of ferric chloride concentration on oil removal at constant PH = 5
160
93
92
140
91
120
90
% oil removal
100
89
oil Conc
80
88
mg/L
87
60
86
40
85
20
Conc
84
% removal
0
83
0
2
4
6
8
10
12
PH

3.5. Studies on LC 9590 behavior

3.5.1. Effect of ph

The pH of the wastewater was changed from 3 to 10 at a fixed LC 9590 dose of 1000 mg/l. From the available results presented in Figure (8), it

can be seen that the optimum pH value is 6 which achieved 92% oil removal.

3.5.2 Effect of LC 9590 dose

Changing the LC 9590 dose from 50 to 100 mg/l, at a pH value of 6 gave the results presented in Figure (9).resulted data indicates that the

optimum dose concentration is 100 mg/L oil. The decrease in the removal efficiency after the optimum value in all the tested chemicals is due to higher concentrations were more than necessary the efficiency of oil removal decreased because the flocs formed by coagulation were smaller and less compact and were not favorable for sludge .the addition of coagulant aids could overcome this disadvantage [15].

Figure 8. Effect of PH on oil removal at constant LC9590 concentration of 1000mg/l

Mohamed Hussein Abdel Megid, Amer Abdel Razek Amer, Khaled Hassan Elsayed *

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International Journal of Engineering Sciences Vol(3), No (12), December, 2014.

300 100 90 250 80 70 200 % oil removal 60 oil Conc 150 50 mg/L
300
100
90
250
80
70
200
% oil removal
60
oil Conc
150
50
mg/L
40
100
30
20
50
Conc
10
% removal
0
0
0
200
400
600
800
1000
1200
Conc of LC9590 mg/l

Figure 9. Effect of LC9590 concentration on oil removal at constant PH = 6

3.6. Application of coagulation treatment on the DAF unit

The previous results were obtained using JAR tests, so the most promising optimum results obtained with both optimum PH values and least concentration with highest removal efficiency were applied to the DAF unit to simulate the actual working conditions and the results are shown in figures 10, 11, 12 & 13 of Alum, Ferric Chloride, Ferrous sulphate & LC 9590 respectively which obtained maximum values of oil removal percentages of 72.7% for alum, 74% for Ferric chloride, 67.3% for Ferrous sulphate and 87.4% for LC 9590 .

350 80 70 300 60 250 % oil removal 50 200 oil Conc 40 mg/L 150
350
80
70
300
60
250
% oil removal
50
200
oil Conc
40
mg/L
150
30
100
20
50
Conc
10
% removal
0
0
0
10
20
30
40
Time (min)

Figure 10. Results of DAF enhanced with alum at PH=10 & C=100 mg/L (optimum Values)

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Coagulation and Dissolved Air Floatation for Treatment of OilWater Emulsion

International Journal of Engineering Sciences Vol(3), No (12), December, 2014.

350 80 70 300 60 250 % oil removal 50 200 oil Conc 40 mg/L 150
350
80
70
300
60
250
% oil removal
50
200
oil Conc
40
mg/L
150
30
100
20
50
10
Conc
% removal
0
0
0
10
20
30
40
Time (min)

Figure 11. Results of DAF enhanced with ferric chloride at PH=5 & C=100 mg/L (optimum Values)

350 80 70 300 60 250 % oil removal 50 200 oil Conc 40 mg/L 150
350
80
70
300
60
250
% oil removal
50
200
oil Conc
40
mg/L
150
30
100
20
50
Conc
10
% removal
0
0
0
10
20
30
40
Time (min)

Figure 12. Results of DAF enhanced with ferrous sulphate at PH=10 & C=100 mg/L (optimum Values)

3.7. Comparison between the efficiency of the different coagulants at their optimum operating conditions

The results presented in Table (2) and figure (14) reveals that the four coagulants investigated along with no pre-treated DAF which were found to be more or less similar in their performance. Maximum oil removal obtained was by LC 9590 with 87.4 % oil removal efficiency while that with no additives at all only removed 60.9 %.

Table 2. Comparison between the efficiency of different coagulants at optimum operating conditions.

Coagulant used

Optimum PH

Optimum dose

Oil removal efficiency

LC 9590

6

100 mg/L

87.4 %

Ferric chloride

8

100 mg/L

74%

Alum

10

100 mg/L

72.7%

Ferrous sulphate

10

100 mg/L

67.3%

No Additives

-

-

60.9%

Mohamed Hussein Abdel Megid, Amer Abdel Razek Amer, Khaled Hassan Elsayed *

128

International Journal of Engineering Sciences Vol(3), No (12), December, 2014.

600 100 90 500 80 70 400 % Oil Removal 60 Conc 300 50 mg/L 40
600
100
90
500
80
70
400
% Oil Removal
60
Conc
300
50
mg/L
40
Conc
200
30
% removal
20
100
10
0
0
0
10
20
30
40
Time (min)

Figure 13. Results of DAF enhanced with LC9590 at PH=6 & C=100 mg/L (optimum Values)

100 90 80 70 60 % Oil Removal 50 LC9590 PH6 40 FeCl3 PH8 30 Alum
100
90
80
70
60
% Oil Removal
50
LC9590 PH6
40
FeCl3 PH8
30
Alum PH10
20
FeSo4 PH 10
10
No Addittives
0
0
5
10
15
20
25
30
35
Time (min)

Figure 14. Comparative chart between all different coagulants used with DAF

4.

Conclusion

Dissolved air flotation technique is very effective secondary treatment method for treating refinery wastewaters and it can be further improved by coupling it with chemical treatment methods like coagulation to improve its oil and grease removal. Dissolved air flotation process pretreated with coagulants showed that LC 9590 obtained highest oil removal (87.4 %) as compared to ferric chloride (74 %), Alum (72.7 %) and ferrous sulfate (67.3 %).

References

[1]

A.El-Kayar, M.Hussein, A.A.Zatout, A.Y.Hosny and A.A.Amer, Removal of oil from stable oil-water emulsion by induced air floatation technique.

[2]

Separation technology (3) (1993). S.Goududey and R.K.Kaushal, Fine Particle Separation by Floatation: A Review. VSRD International journal of technical & Non-Technical Research (4)

(2013).

[3]

R.Gregory, T.Zabel, in: F.W. Pontius (Ed.), Water Quality and Treatment, 4 th ed, McGraw-Hill, New York (1990) 367-453.

129

Coagulation and Dissolved Air Floatation for Treatment of OilWater Emulsion

International Journal of Engineering Sciences Vol(3), No (12), December, 2014.

[4]

A.A. Al-Shamrania, A. Jamesa, H. Xiao, Destabilization of oil-water emulsions and separation by dissolved air floatation, Water Research 36 (2002)

1503-1512.

[5]

A.S. Moursy, S.I. Abo-Elela, Treatment of oily refinery wastes using a dissolved air flotation process, Environmental international 7 (1982) 267-270.

[6]

W.W. Eckenfelder jr. (2000) .Industrial Water Pollution Control .3 rd ed, MAC Graw Hill,USA.

[7]

Y. Sato, Y. Murakami, T.Hirose, H. Yamamoto, Y. Uryu, Removal of Emulsified Oil Particles by Dissolved Air Floatation. Journal of Chemical

[8]

Engineering 12 (6) (1979), 454-459. F.El-Gohary , A.Tawfik & U. Mahmoud, Comparative study between chemical coagulation/precipitation (C/P) versus Coagulation/dissolved air floatation

[9]

(C/DAF) for pre-treatment of personal care products (PCPs) wastewater. Desalination 252 (2010) 106-112. S.Fujii, M.Okada, T.Furuzono, Hydroxyapatite nanoparticles as stimulusresponsive particulate emulsifiers and building block for porous materials.

[10]

Journal of colloid and interface Science 315 (2007) 287-296. R.Moosai, R.A.Dawe, GAS attachment of oil droplets for gas flotation for oily wastewater cleanup. Separation and Purification Technology 33 (2003)

303-314.

[11]

L.Malik, M.A.Hamia, M.M.Al-Hashimib, J.Al-Doori, J.Dosta, A.ARovira, S.Gali, J.Mace,M.A.Ivarez, Effect of activated carbon on BOD and COD

[12]

removal in a dissolved air floatation unit treating refinery wastewater. Desalination 216 (2007) 116-122. M.Krofta, B.Herath, D.Burgess, L.Lampman, An attempt to understand dissolved air flotation using multivariate data analysis. Water Science and

[13]

Technology 31 (3-4) (1995) 191-201. R.Klute, S.Langer, R.Pfeifer, Optimization of coagulation processes prior to DAF. Water Science and Technology 31 (59-62) (1995) 1-23.

[14]

J.Coca, G.Gutierrez & J.M. Benito, Treatment of oily wastewater. Springer Netherlands (2011) 1-55.

[15]

C.Rattanapan , A.Sawain, T.Suksaroj & C.Suksaroj, Enhanced efficiency of dissolved air flotation for biodiesel wastewater treatment by acidification and

[16]

coagulation processes. Desalination 280 (2011) 370-377. J.Gregory, J.Duan, Hydrolyzing metal salts as coagulants. Pure Appl.Chem.Vol. 73, nr. 12, 2001, 2017- 2026.

[17]

K.A. Parmar, S.Prajapati, R.Patel and Y.Dabhi, Effective use of ferrous sulphate and alum as a coagulant in treatment of dairy industry wastewater. Journal of Engineering and Applied Sciences (2011) Vol.6 (9) 42-45.