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

120-129

TI Journals

ISSN:

International Journal of Engineering Sciences

2306-6474

www.tijournals.com

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

Abstract

Dissolved air floatation

coagulation
wastewater
treatment
oil in water emulsion
refinery wastewater

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 physicochemical 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 M). 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
Specific gravity at 60/60 (ASTM D1298)
API gravity
Pour point (max C) (ASTM D79)
Viscosity RI at 70 F (ASTM D445)
At 100 F
Sulfur content wt % (ASTM D129)
Salt Content wt % (IP 77)
Carbon residue conrasdon wt % (ASTM D189)
Wax content vol % (ASTM D95)
Water content vol % (ASTM D85)
Asphaltenes wt % (IP 143)
Ash content wt % (ASTM D482)

value
0.8730
29
1
136 SUS
71 SUS
2.30
0.005
5.2
4.2
Nile
1.96
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.

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, thats 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
mg/L

80

100

78
76

50

Conc

74

% removal

72
0

10

12

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

140

92

120

91

100

oil Conc
mg/L

90 % oil removal

80
89
60
88

40
20

87

Conc
% removal

0
0

200

400

600

800

1000

86
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
mg/L

150

50
40

100

30
20

50

Conc

10

% removal

0
0

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

60
oil Conc
mg/L

150

50
40

100

30
20

50

Conc

10

% removal

0
0

200

400

600

800

1000

0
1200

Conc of Ferrous sulphate mg/l

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

% oil removal

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:
FeSO4+2 HCO 3Fe (OH) 2 + SO4 -2 + 2CO2
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 thats 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
mg/L

88
60
87.5

40

87

20

Conc
% removal

0
0

86.5
6

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

160

90

140

89
88

120
oil Conc
mg/L

% oil removal

87

100

86
80

85

60

84

40

83
Conc

20

82

% removal

0
0

200

400

600

800

1000

81
1200

Conc of Feric chloride mg/l

Figure 7. Effect of ferric chloride concentration on oil removal at constant PH = 5

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].

160

93

140

92
91

120

oil Conc
mg/L

90

100

89

80

88

60

87
86

40

85

20

Conc

84

% removal

83
0

10

12

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

% oil removal

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

126

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

300

100
90

250

80
70

200

% oil removal

60
oil Conc
mg/L

150

50
40

100

30
20

50

10

Conc
% removal

0
0

200

400

600

800

1000

0
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

300

70
60

250

50

% oil removal

200
oil Conc
mg/L

40
150
30
100

20

50

Conc

10

% removal

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

300

70
60

250

50

% oil removal

200
oil Conc
mg/L

40
150
30
100

20

50

10

Conc
% removal

0
0

10

0
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

300

70
60

250

50

% oil removal

200
oil Conc
mg/L

40
150
30
100

20

50

10

Conc
% removal

0
0

10

0
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
LC 9590
Ferric chloride
Alum
Ferrous sulphate
No Additives

Optimum PH
6
8
10
10
-

Optimum dose
100 mg/L
100 mg/L
100 mg/L
100 mg/L
-

Oil removal efficiency

87.4 %
74%
72.7%
67.3%
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
mg/L

300

50
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 PH10

20
FeSo4 PH 10

10
No Addittives

0
0

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 %).

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