International Journal of Civil Engineering and Technology (IJCIET)

Volume 6, Issue 9, Sep 2015, pp. 139-146, Article ID: IJCIET_06_09_013

Available online at
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ISSN Print: 0976-6308 and ISSN Online: 0976-6316
IAEME Publication

NAPHTHA REMOVAL FROM PETROLEUM

INDUSTRIAL EFFLUENT
Sherif A. Moustafa
Assistant Professor of Public Work Engineering, Construction and Building
Department, Faculty of Engineering, October 6th.University, EGYPT,
Mohamed H. Al Awady
Water Pollution Research Department,
National Research Centre, Dokki, Cairo, Egypt
M. A. Ashmawy
Assistant Professor of Sanitation and environmental
Department faculty of engineering Helwan University
ABSTRACT
The Purpose of this research is treat the industrial wastewater flow
generated from El Nasr Petroleum Company to the accepted quality before
discharging it into Suez Gulf. A series of bench scale experiments, were
conducted in order to determine the best treatment process for such kind of
industrial flow. This research succeeded to remove the phenolic compounds
(naphtha) from the industrial effluent to the level stated in Law 4/1994.
The optimum doses of both Fe2+ and H2O2 were determined using jar
test to remove color, odor and COD constituents from the industrial effluent.
The experimental results indicated that the optimum doses of 0.8 and 20
ml/l for Fe2+ and H2O2 respectively reduced COD concentration from 8200
to 500 mg/l in 30 minutes reaction time
Key words: Petroleum Refinery and Petrochemical Waste; Electrolysis,
Naphtha Removal
Cite this Article: Sherif A. Moustafa, Mohamed H. Al Awady and
M.A.Ashmawy. Naphtha Removal from Petroleum Industrial Effluent.
International Journal of Civil Engineering and Technology, 6(9), 2015, pp.
139-146.
http://www.iaeme.com/IJCIET/issues.asp?JTypeIJCIET&VType=6&IType=9

1. INTRODUCTION
Large amounts of water are used in a petroleum refinery and, consequently,
significant volumes of wastewater are generated (0.4-1.6 times the volume of
processed oil) (Fica-Piras 2000). Petroleum refinery wastewater and its major

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Sherif A. Moustafa, Mohamed H. Al Awady and M.A.Ashmawy

components such as phenols and Benzene, Toluene, ethylbenzene and Xylene
(BTEX) and Naphtha has been studied to investigate the treatment efficiency by
using aerobic, anaerobic and anoxic or a combinations of two or more biological
conditions (1, 2,3,6.)
El-Nasr Petroleum Company is one of two refineries located at Suez governorate,
Egypt. The refinery is Egypt's largest with a capacity of 146,300 barrels per day
(bpd). It processes more than 30 percent of the petroleum produced in Egypt and
comprises of three crude distillation units, an accompanying asphalt production unit
and a power generation plant.
The company is discharging 16,800 m3/day of treated industrial wastewater
mixed with 216,000 m3/day cooling water with total wastewater flow of 233,000
m3/day into Suez Gulf. The quality of effluent from El Nasr Company is not
complying with Egyptian Environmental regulation in Egypt.
El Nasr Petroleum Company is specialized crude distillation and asphalt. The
industrial effluent of the company is discharged after passes through the existing
treatment units into Suez Gulf. The effluent does not comply with the parameters
stated in law No 4/1994 regarding the discharge into Sea. Therefore, the NPC
requested to study this situation and modify / upgrade the existing treatment process
to produce effluent complying with the parameters stated in law 4/1994.
The existing treatment process consists of API oil separator to remove oil and
grease. The total industrial wastewater is passed to Skim Basin where the 9000 m3
per hour cooling water is thoroughly mixed with the industrial wastewater coming
from Naphtha section. Naphtha represents the main source of organic pollutants, with
the maximum phenolic concentration, high alkalinity and chemical oxygen demand
which exceeding the trigger levels in Law 4/1994 for discharging the water onto the
sea shore.
Samples were collected from Naphtha department outlet, effluent water from
cooling process, influent waste to the API separator, effluent waste from API
separator and final wastewater discharged onto Suez Gulf. Table No. 1 presents the
characteristics of the industrial wastewater effluent from Naphtha department in the
El Nasr Petroleum Company.
Table 1 Characteristics of Industrial Wastewater flow from Naphtha Department
Parameters
pH
Chemical Oxygen Demand
Biological Oxygen Demand
Total Suspended Solids
Total Dissolved Solids
Phosphate
Chlorides
Phenol
Total Kjeldahl Nitrogen

Unit

Value

mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L

13.6
8200
3286
438
55600
0.4
420
160
17

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Maximum Limits
of Parameters in
Law 4/1994
69
100
60
60

Not Comply
Not Comply
Not Comply
Not Comply

5
10
0.01
10

Comply
Not Comply
Not Comply
Not Comply

Status

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Naphtha Removal From Petroleum Industrial Effluent

2. MATERIALS AND METHODS

Jar test was applied to the collected samples in order to determine the optimum doses
of Fe2+ and H2O2, the optimum pH and reaction time to achieve maximum color, odor
and COD removal efficiencies.
The effect of different variables was studied by changing each in turn while
keeping the other constant.

2.1. Analytical Measurements

The materials used in the experiments were Fe2SO47H2O solution and lime slurry
and H2O2 solution of (30%) (H2SO4 30%) and [Ca (OH)2] of 50% were prepared
daily.
All experiments were carried out in the jar test. Mixing speed of the apparatus was
adjustable between 0 and 250 rpm. The pH-measurement was carried out using a pHmeter. The measured parameters of wastewater during the experiments were
Chemical Oxygen Demand (mg/l), Total Suspended Solids (TSS, mg/l), total Kjeldahl
Nitrogen, Nitrite, Nitrate, Ammonia, pH and Oil & Grease. All parameters have been
measured according to procedures given in the American Standard Methods, APHA
(2008). The Naphtha industrial wastewater samples were obtained from the effluent
from the Naphtha Department. The experiments were carried out at the laboratory of
water pollution in NRC.

3. RESULTS AND DISCUSSION

The optimal reaction conditions determined by following up the removal of COD and
phenol, respectively. The effect of Fenton's reagent dosages on Fenton oxidation are
summarized as follows:

3.1. Optimum pH
The experiments were carried out using Jar tests to determine the optimum pH versus
removal of both COD and Phenol. It is found that the optimum pH value to achieve
the maximum removal of both COD and Phenol ranges from 9.5 to 10.5.

3.2. Optimum Detention Time

Figure 1 COD Removal versus Detention Time

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Sherif A. Moustafa, Mohamed H. Al Awady and M.A.Ashmawy

Figure 2 Phenol Removal versus Detention Time

Figures 1 and 2 show that the optimum detention time for removal of both COD
and Phenol is 30 minutes. It is found that 10 minutes detention time can achieve
removal efficiency of COD and Phenol reaches up to 95% but in order to achieve the
limits stated in law 4/1994, the detention time shall be increased to be 30 minutes.

3.3. Hydrogen Perxide (30%) Dose

Figure 3 COD Removal versus Hydrogen Perxide (30%) Dose

Figures 3 and 4 show that the optimum dose of hydrogen peroxide (30%) can
reduce the concentration of COD and phenol to the limits stated in law 4/1994 at dose
equal 65 ml/l.

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Naphtha Removal From Petroleum Industrial Effluent

Figure 4 Phenol Removal versus Hydrogen Perxide (30%) Dose

3.4. Optimum Dose of Fe2+ versus COD

Figure 5 COD Removal versus Fe2+ Dose

Figure 6 Phenol Removal versus Fe2+ Dose

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Sherif A. Moustafa, Mohamed H. Al Awady and M.A.Ashmawy

Figures 5 and6 show that the optimum dose of Fe2+can reduce the concentration of
COD and phenol to the limits stated in law 4/1994 at dose equal 5 and 8 mg/l
respectively.

3.5. Proposed Industrial Wastewater Treatment Units

3.5.1. Naphtha Effluent
Spent caustic from Naphtha Treatment Unit will be treated according to the Fenton
reaction. The collected spent caustic is treated with Acid, Ferrous Sulfate, and
Peroxide. This treatment will reduce the phenol, COD and associated TKN content
prior to discharge in the main oily water stream.

Spent
Caustic

pH
adjustment

Fe2SO4
Addition

Discharge
to Oily
Water
Stream

H2O2
Addition

3.5.2. API separator Effluent

Effluent from API separator will be treated by flocculation and Dissolved air
floatation. This treatment will reduce the Total Suspended Solids, COD, and
associated TKN before discharge to the skim basin for dilution.

Alum

From API
Separator

Addition

Flocculation

Dissolved
Air
Floatation

Discharge
to Skim
Basin

The following process flow diagram shows the proposed treatment process.

Proposed Industrial Wastewater Treatment Process for Portion 1 (from

Naphtha Department- Phenol Removal) Flow 12.5 m3/hr
Fe2+

H2O2

Caustic
Soda

Flow 12.5 m3/hr

pH
Fe2+
Adjustment

To Existing API

Fe2+

pH Adjustment

Temperature Reduction
(Cooling)

Schematic Flow Diagram for Industrial Wastewater from Naphtha Department

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Naphtha Removal From Petroleum Industrial Effluent

Proposed Industrial Wastewater Treatment Process for Portion 2 (from

Other Departments - COD and TSS Removal) Flow 725 m3/hr
Alum dose
100 mg/liter
Flow 725 m3/hr

Flash
Fe2+tank
Mixing
1 min

Flocculation
Fe2+
Tank 15 min

Dissolved
Flotation Tanks

To Existing API

Schematic Flow Diagram for Industrial Wastewater from Other Departments

4. CONCLUSION OF THE TREATABILITY STUDY

From the previous results the following are concluded that the optimal operating
conditions are as follows:
1.

Reaction time is 30 minutes to complete the reaction.

2.

The Fe2+ dose is 0.8 g/l.

3.

The (30 %) H2O2 dose is 65 ml/l.

4.

The starting pH value up to 10, reduced to the level of optimal value of the
reaction.

5.

The reduction in COD reaches up the required level in law 4/1994

6.

The reduction in phenol reaches up the required level in law 4/1994

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