QATAR UNIVERSITY

Graduate Studies

College of Engineering

CHARACTERIZATION OF PRODUCED WATER FROM TWO OFFSHORE OIL

FIELDS IN QATAR

A Thesis in

Environmental Engineering

By

Jumana Ahmad Ahan

© 2014 Jumana Ahmad Ahan

Submitted in Partial Fulfillment

Of the Requirements

For the Degree of

Master of Science in Environmental Engineering

December 2014
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Copyright © 2014 Jumana Ahan

I
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II
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III
 Abstract

In this study the produced water generated from two different offshore oil production fields

in Qatar was characterized to investigate their variations at different locations, and to

evaluate the efficiency of technologies used. One site located at filed A uses two stages of

two phase separation tanks coupled with filtration unit and chemical injection followed by

large gravitational separation tanks. The other site located at field B starts with two stage

separation with chemical injection, two phase followed by three phase separation tanks

coupled with hydrocyclone which is followed by surge drum. Produced water is

characterized based on pH, conductivity, total amount of hydrocarbon present in the sample,

BTEX and Phenol concentration, total COD, readily biodegradable COD, total solids, totals

dissolved solids, solids composition by weight, concentration of heavy metals, concentration

of total Kjeldahl nitrogen, ammonia nitrogen, phosphate, concentration of ions, dissolved

CO2, total sulfide, and oil droplet size distribution. These characteristics were chosen to

evaluate the efficiency of each unit. This was determined by comparing the characteristics

of samples collected before and after the unit operation based on the results. Results indicate

that the production station at Field A might requires an improvement in the filtration unit

and an additional treatment unit in the future. Treatment method that minimizes hazardous

pollutant in produced water was proposed for Field A. Results indicate that hydrocyeclone is

the most efficient equipment to remove oil from produced water in an offshore production

station. Hydrocyclone could remove 92.6% of total oil for an average oil droplet size of 11

microns and have a total capacity by volume of 312 h-1. The biodegradable COD percentage

IV
exceeds 50% for both fields with more than 60% of readily biodegradable COD. Biological

treatment might be suggested for future enhancements.

V
 Executive Summary

Studies have been conducted to characterize produced water and compare the characteristics

from two different fields that use different production, separation and treatment methods.

Two oil production offshore stations were investigated. A brief study was provided to

improve the treatability of produced water by suggesting design modification and additional

units to meet future requirement of produced water quality and to bring the produced water

quality to a level that would allow the produced water to be re-utilized in the process

without having future operation turbulence.

The characterization of produced water showed presence of high amount of total

hydrocarbon that is ranging from 3491 ppm to 40 ppm in different operation and treatment

units from the first stage of separation up to the produced water discharge stage. The

discharged produced water from field B recorded an average concentration of 40 ppm of the

total hydrocarbon while the discharged produced water from field A recorded an average

concentration of 52.6 ppm.

The chemical oxygen demand COD is divided into biodegradable COD and non-

biodegradable COD each could be soluble or suspended COD. Total COD, total soluble

COD and soluble biodegradable COD were measured in the lab. Total biodegradable and

total non-biodegradable were derived from the measurements. Results shows that more than

50% of the COD concentration is biodegradable and more than 60% of the biodegradable

COD is soluble which can be referred as readily biodegradable COD. The concentration of

VI
COD was decreasing from stage to stage in both fields but both streams required further

treatment to remove the COD. field A started with average initial COD concentration of

8594 ppm and reduced to 3764 ppm while, field B started with average initial COD

concentration of 16822 ppm and reduced to 7250 ppm.

During oil extraction process salts are considered as a major constituent. Some elements of

salts were observed with very high concentration, e.g. chloride (Cl-), which has a

concentration ranging from 73,330 ppm to 124,900 ppm in field A. While observed chloride

(Cl-) in field B has a concentration ranging from 163,980 ppm to 229,360 ppm. Other ions

were observed as well such as sulfate, bromide, fluoride and traces of nitrate.

The average total suspended solids are ranging from 38 ppm to 4 ppm both fields have

similar efficiency in removing suspended solids. Field A end up with last stage discharge of

The results also showed the presence of traces of toxic heavy metals such as mercury (Hg),

lead (pb), arsenic (As) and iron (Fe). The concentration of mercury in produced water ranges

between 0.83 ppb to 1.77 ppb , the concentration of lead ranges between 2.42 ppb to 12.64

ppb, the concentration of arsenic ranges between 1.84 ppb to 4.8 ppb while the

concentration of iron ranges from 140.8 ppb to 599.6 ppb. Other heavy metals are also

present in larger quantities in produced water samples such as strontium (Sr).

VII
Table of Contents
Abstract .................................................................................................................................. IV

Executive Summary ............................................................................................................... VI

List of Tables ...................................................................................................................... XIV

List of Figures .................................................................................................................... XVII

Chapter 1: Introduction ............................................................................................................ 1

1.1 History of Offshore Facilities in Qatar: ......................................................................... 1

1.2 Offshore Production Station Structure: .......................................................................... 2

1.3 Oil Production Process Description of the Studied Fields ............................................. 3

1.3.1 Field A process description and disposal method: .................................................. 3

1.3.2 Field B Process Description and Disposal Method: ................................................ 6

1.4 Production of Produced Water ....................................................................................... 8

1.5 Characteristics of the produced water ............................................................................ 9

1.5.1 Historical Constitutes of Qatar’s Produced Water .................................................. 9

Chapter 2: Literature Review................................................................................................. 12

2.1 Introduction to Produced Water: .................................................................................. 12

2.2 Sources of Produced Water: ......................................................................................... 14

VIII
 2.2.1 Formation Water: .................................................................................................. 15

2.2.2 Aquifers: ................................................................................................................ 15

2.2.3 Injection Water: ..................................................................................................... 16

2.3 Produced Water Generation: ........................................................................................ 16

2.3.1 Countries Generating Produced Water: ................................................................. 19

2.4 Characteristics of produced water: ............................................................................... 20

2.4.1 Suspended solids: .................................................................................................. 21

2.4.2 Dissolved solids:.................................................................................................... 22

2.4.3 Total petroleum Hydrocarbon: .............................................................................. 22

2.4.4 Chemical Oxygen Demand COD: ......................................................................... 28

2.4.5 Readily Biodegradable Chemical Oxygen Demand:............................................. 29

2.4.6 Total Kjedahl Nitrogen TKN: ............................................................................... 30

2.4.7 Heavy metal:.......................................................................................................... 32

2.4.8 Oil droplet size distribution: .................................................................................. 32

2.4.9 Ions and inorganic constituents: ............................................................................ 34

2.4.10 Alkalinity: ............................................................................................................ 36

2.4.11 Dissolved gases: .................................................................................................. 38

2.5 Chemical Additives: ..................................................................................................... 39

IX
2.6 Aquatic Chemistry: ...................................................................................................... 39

2.6.1 pH characteristic of the aquatic chemistry: ........................................................... 40

2.7 Effects of produced water on Aquatic Chemistry: ....................................................... 40

2.7.1 Hydrocarbon: ......................................................................................................... 41

2.7.2 Heavy metal:.......................................................................................................... 41

2.7.3 Suspended solids and dissolved gases: .................................................................. 41

2.8 Hazard and Risk of Produced Water: ........................................................................... 43

2.8.1 Environmental Risks: ............................................................................................ 44

2.8.2 Groundwater Pollution: ......................................................................................... 44

2.8.3 Health Risks: ......................................................................................................... 45

2.8.4 Industry Risk: ........................................................................................................ 46

2.9 Standards and Regulation: ........................................................................................... 47

2.9.1 Standards for Heavy Metal in Produced Water: .................................................... 47

2.9.2 Total Petroleum Hydrocarbon in Produced Water: ............................................... 49

2.9.3 Standards for COD in Produced Water: ................................................................ 50

2.9.4 Standards for Suspended Solids: ........................................................................... 50

2.9.5 Standards for Dissolved Gases in Produced Water: .............................................. 51

2.10 Previous studies on produced water: .......................................................................... 51

X
Chapter 3: Research Methodology ........................................................................................ 57

3.1 Total chemical oxygen demand (COD) ....................................................................... 57

3.1.1 Determination of Dissolved chemical oxygen demand ......................................... 58

3.1.2 .Materials ............................................................................................................... 58

3.1.3 Method................................................................................................................... 59

3.2 Determination of total petroleum hydrocarbons .......................................................... 60

3.2.1 Materials ................................................................................................................ 60

3.2.2 Method................................................................................................................... 60

3.3 Determination of heavy metals .................................................................................... 61

3.3.1 Materials ................................................................................................................ 61

3.3.2 Method................................................................................................................... 61

3.4 Determination of ions................................................................................................... 62

3.4.1 Materials ................................................................................................................ 62

3.4.2 Method................................................................................................................... 62

3.5 Total Suspended Solids and Total Dissolved Solids .................................................... 62

3.5.1 Materials ................................................................................................................ 63

3.5.2 Method................................................................................................................... 63

3.6 Determination of total sulfides dissolved in produced water ....................................... 63

XI
 3.6.1 Materials ................................................................................................................ 64

3.6.2 Method................................................................................................................... 64

3.7 Determination of Total carbon dioxide dissolved in produced water .......................... 65

3.7.1 Materials ................................................................................................................ 65

3.7.2 Method................................................................................................................... 66

3.8 Sampling and Sample preparation: .............................................................................. 66

3.9 Analysis:....................................................................................................................... 68

Chapter 4: Results and discussion: ........................................................................................ 71

4.1 Total Petroleum hydrocarbon....................................................................................... 73

4.1.1 Equipment efficiency in TPH removal .................................................................. 74

4.1.2 Field efficiency in TPH removal ........................................................................... 78

4.2 Oil droplet size distribution.......................................................................................... 79

4.2.1 Field A gravity separation tank upstream: ............................................................ 81

4.2.2 Field A gravity separation tank discharge : ........................................................... 82

4.2.3 Field B hydrocyclon upstream: ............................................................................. 84

4.2.4 Field B surge drum discharge :.............................................................................. 85

4.3 Solids in produced water .............................................................................................. 86

4.3.1 Solids composition: ............................................................................................... 88

XII
 4.4 Dissolved oxygen and oxygen demand:....................................................................... 89

4.4.1 Biochemical oxygen demand: ............................................................................... 89

4.4.2 Chemical oxygen demand: .................................................................................... 90

4.5 Extraneous and intrinsic conductivity ........................................................................ 100

4.6 The relation between ions and dissolved CO2 ........................................................... 105

4.7 Heavy metals concentration ....................................................................................... 107

4.8 Sulfides in produced water ......................................................................................... 109

Chapter 5: Suggested method for produced water treatment ............................................... 110

5.1 Typical methods of produced water treatment ........................................................... 110

5.2 Modifying Field A treatment method ........................................................................ 114

5.2.1 Designed produced water process ....................................................................... 114

Chapter 6: Conclusions and Recommendations .................................................................. 122

APPINDIX A ....................................................................................................................... 125

References: .......................................................................................................................... 143

XIII
List of Tables
Table 1: Typical produced water measurements in produced in Qatar ................................. 10

Table 2: hydrocarbons associating the oil mixture ............................................................... 23

Table 3: Solubility of BETX and other single ring aromatic hydrocarbons (Frintrop, et al.,

2011) ...................................................................................................................................... 27

Table 4: Common inorganic constituents in conventional produced water (Rice & Nuccio,

2000) ...................................................................................................................................... 34

Table 5: Conventional and Unconventional Constituent List (FakhrulRazi, et al., 2009) ... 35

Table 6: Important compounds for Alkalinity ...................................................................... 37

Table 7: Typical Alkalinity Range (Stewart & Arnold, 2011) ............................................. 38

Table 8: Hazardous chemical effects on health (OSHA, 2014)............................................. 45

Table 9: Max and min allowable concentration of some heavy metals and Comparison with

seawater (EPA, 2011) ............................................................................................................ 48

Table 10: Comparison of seawater metal concentration ..................................................... 53

Table 11: Comparison of oilfield produced water metal concentration ............................... 55

Table 12 Comparison of produced water characteristics ....................................................... 56

Table 13: Analytical techniques ............................................................................................ 69

Table 14: Characterization of produced water from Field A and Field B ............................. 72

XIV
Table 15: Percentage removal of oil by unit process ............................................................. 75

Table 16: Total Petroleum hydrocarbon comparison with earlier studies ............................. 79

Table 17: Oil droplet size analysis......................................................................................... 80

Table 18: Total solids across treatment stages ...................................................................... 87

Table 19: Element of solid content by wt%........................................................................... 88

Table 20: average COD concentration and % recovery across treatment stages .................. 93

Table 21: COD fractions and biodegradability rates ............................................................. 96

Table 22: RBCOD/COD ration for Field A and Field B ....................................................... 99

Table 23: Total ions present in produced water................................................................... 102

Table 24: comparison of Field A and Field B ions concentration and conductivity with other

oil fields ............................................................................................................................... 104

Table 25: Heavy metals concentration for Field A and Field B discharge .......................... 108

Table 26: Methods used to separate oil from water (Stewart & Arnold, 2011) .................. 111

Table 27: Produced water disposal standards (Stewart & Arnold, 2011) ............................ 114

Table 28: Trails for produced water characteristics from Field A 1st stage separation ....... 125

Table 29: Uncertainty in characteristics analysis for Field A 1st stage separation samples 126

Table 30: Trails for produced water characteristics from Field A 2nd stage separation ...... 127

Table 31: Uncertainty in characteristics analysis for Field A 2nd stage separation samples 128

XV
Table 32: Trails for produced water characteristics from Field A gravity separation tank

upstream ............................................................................................................................... 129

Table 33: Uncertainty in characteristics analysis for Field A gravity separation tank

upstream samples ................................................................................................................. 130

Table 34: Trails for produced water characteristics from Field A gravity separation tank

discharge .............................................................................................................................. 131

Table 35: Uncertainty in characteristics analysis for Field A gravity separation tank

discharge samples ................................................................................................................ 132

Table 36: Trails for produced water characteristics from Field B 1st stage separation ....... 133

Table 37: Uncertainty in characteristics analysis for Field B 1st stage separation samples 134

Table 38: Trails for produced water characteristics from Field B Hydrocyclone A ........... 135

Table 39: Uncertainty in characteristics analysis for Field B Hydrocyclone A samples .... 136

Table 40: Trails for produced water characteristics from Field B Hydrocyclone B ........... 137

Table 41: Uncertainty in characteristics analysis for Field B Hydrocyclone B samples ..... 138

Table 42: Trails for produced water characteristics from periods for Field B Hydrocyclone C

............................................................................................................................................. 139

Table 43: Uncertainty in characteristics analysis for Field B Hydrocyclone C samples ..... 140

Table 44: Trails for produced water characteristics from Field B surge drum .................... 141

Table 45: Uncertainty in characteristics analysis for Field B surge drum samples ............. 142

XVI
List of Figures
Figure 1: Some offshore oil fields location in Qatar ............................................................... 2

Figure 2: Field A process block diagram ................................................................................. 5

Figure 3: Field B process block diagram ................................................................................. 7

Figure 4: world Produced Water Production (Ferro & Smith, 2009) ................................... 17

Figure 5: Yearly Discharge of Produced Water (OSPAR, 2014) ......................................... 18

Figure 6: Disposal techniques for produced water (OSPAR, 2014) ..................................... 19

Figure 7: Oil and Gas Generation (UK Oil and Gas, 2014) ................................................. 20

Figure 8: Hydrocarbon chemistry of total petroleum hydrocarbons (TPHs) ........................ 25

Figure 9: Chemical oxygen demand fractions (Iowa state university, 2011) ....................... 29

Figure 10: Total kjedahl nitrogen TKN fractions (Metcalf & Eddy, et al., 2013) ............... 31

Figure 11: Major aquatic chemical processes ....................................................................... 42

Figure 12: Field A sample points........................................................................................... 67

Figure 13: Field B sample points ........................................................................................... 68

Figure 14: Hydrocyclone performance compression ............................................................. 76

Figure 15: Gravity separation tank compression ................................................................... 77

Figure 16: Field A sample point for oil size distribution...................................................... 80

XVII
Figure 17: Field B sample point for oil size distribution ....................................................... 80

Figure 18: Oil droplet size distribution for Field A 1st stage separation .............................. 82

Figure 19: Oil droplet size distribution for Field A last stage of treatment ........................... 83

Figure 20: Oil droplet size distribution for Field B hydrocyclone inlet unit ......................... 84

Figure 21: Oil droplet size distribution for Field B last stage of treatment ........................... 85

Figure 22: COD changes across treatment stages in Field A ................................................ 91

Figure 23: COD changes across separation and treatment stages in Field B ........................ 92

Figure 24: The relation of conductivity and total existing ions for Field A and Field B .... 103

Figure 25: The relation between CO2 and dissolved ions in produced water ...................... 106

Figure 26: Typical produced water treatment process ......................................................... 113

Figure 27: Field A fluid production forecast ....................................................................... 116

Figure 28: bases of separator selection (Shell Group, 2008) ............................................... 121

Figure 29: suggested process flow diagram for Field A ...................................................... 121

XVIII
Chapter 1: Introduction

1.1 History of Offshore Facilities in Qatar:

There are seven main offshore production stations in Qatar which operate on eight oil

production fields. Production Station 1 (PS1), Production Station 2 (PS2), Production

Station 3 (PS3) and other production stations. Below are the seven offshore production

stations: PS1 is located in the north east of Qatar in a 45 km distance from Al-Rayyan city

and it operates on two fields Idd- El Shargi north dome and Idd- El Shargi south dome. Idd-

El Shargi oil field had the first discovered oil well in 1960. PS2 and PS3 are operated by

Qatar petroleum. The two fields are also located in the north east of Qatar and these two

production platforms operate in two fields Maydan Mahzam (MM) and Bul Hanine (BH).

High quality crudes and associated gas are produced from the offshore Maydan Mahzam and

Bul Hanine fields which began production in 1965 and 1972, respectively. There are other

oil field operations in Qatar as well, Al-Shaheen field, Al-Khalij field, Al- Karkara and Al-

Rayyan. Al- Shaheen field is operated by Maersk Oil Qatar while Al-Khalij is operated by

TOTAL Exploration & Production Qatar. Al-Rayyan and Idd-El Shargi fields are operated

by Occidental Petroleum of Qatar Ltd. (QP, 2014). Al-Karkara field is operated by Qatar

Petroleum Development Company; the field had a full development plan, including drilling

of 1 production well and 1 water injection well in Aril 2011 (QPD-Jaban, 2014). El-Bunduq

field is shared with UAE and is operated by Bunduq Company Ltd. In 2008 the total oil

production in Qatar from offshore fields at PS1, PS2, PS3, Al-Khalij and AL-Karkara is

88.5 million barrels which is equivalent to 241868 barrels/day (QP, 2014). The produced

1
water is more than double the amount of extracted oil, which would lead to total of 177

million barrels/ year (483736 barrels/day).

AL-Khalij Field

ALkarkar

Figure 1: Some offshore oil fields location in Qatar

1.2 Offshore Production Station Structure:

Offshore production and operation depends on the size and water depth. A whole range of

different structure is being used in different offshore production stations all around the

world. In the last few years, a technology was found which pure sea bottom installations

with multiphase piping to shore and no offshore topside structure at all. Replacing outlying

2
wellhead towers, deviation drilling is used to reach different parts of the reservoir from a

few wellhead cluster locations(Stewart & Arnold, 2011). The gulf sea is a very shallow sea

with an average depth of 30 m (QP, 2014). Therefore, the most common structures used in

the region are offshore, fixed multi platforms, offshore fixed self contained platforms and

offshore self contained concrete gravity platforms (Stewart & Arnold, 2011).

1.3 Oil Production Process Description of the Studied Fields

1.3.1 Field A process description and disposal method:

Field A production station is located 85 kilometers east of Doha in approximately 30 m of

water depth. The structure of the field started before 1964. The original oil station was

installed to American and British standards, in accordance with shell’s design and

engineering practices of that period. In 1979 NGL production facilities were added, where it

had three small platforms, accommodation platform and flare. In 1995, Field A has been

developed in to new phase where 6 more platforms were added and connected. New

platforms were installed for different purposes such as oil production, gas compression, fluid

rising, water injection and glycol utility units. By that time extensive developments to the

production station and oil field have occurred, including advanced technology exploration

and drilling programs, and the commissioning of gas lift and water injection system. In

2004, an additional major platform was added and connected to Field A to increase the

production. The added platform includes all the individual services. Field A is connected to

remote wellhead jackets that are located in Field A south dome and Field A north dome.

Remote jackets can be of 5 types in broad tripod-three leg jacket, tripod with helideck, four

3
leg jacket, four leg jacket with helideck and minimum facility platform which can be

referred to as minimum facilities platform. Field A production station facility receives fluids

from one of the oil fields located at the state of Qatar. The field is a multiple jacket field

with multiple flow lines flowing into Field A production station. The production platforms

in field A production station separates the gas from the liquid phase (oil and water) through

a two stage separation unit. The gas is primarily exported to Mesaieed. A portion of the gas

is used for fuel gas system, power generation, gas lift to increase fluid production and gas

injection to improve reservoir pressure. The separated oil and water are transported from

Field A production station to Halul Island in to the separation tanks via subsea flow lines.

Through the separation tanks the oil is separated from the water which is referred to as

produced water. Oil is exported to Qatar Petroleum and the water is currently disposed in to

the water disposal wells located in Umm-Erradhuma aquifer.

Produced water is decanted through a nozzle in the lower part of Halul separation tank .

The function of the tanks, each equipped with degassing boot, is to remove gas from crude

oil and water at a continuous throughput basis. Water quality is the governing requirement.

The duty tank provides approximately 6 hours of gross liquid residence time, as the water

cut increase the residence time might increase to provide a sufficient separation. The

position of the oil/ water interface is measured using a nucleonic differential absorption

meter. The interface level is maintained at the selected position under automatic set point

control by modulating a level control valve in the discharge piping of the produced water

pumps.

4
The produced water flow is filtered downstream of the booster pumps to remove 95% of

particles greater than 150 μm before being piped approximately 4 km to the offshore

disposal wellhead platform. Produced water is pumped through a filtration package for

disposal offshore into Umm Erradhuma aquifer. Peak produced water throughput 350,000

barrels/day. Peak produced water output to the aquifer 410,000 barrels/day. The production

of produced water is expected to reach 500,000 barrels/day in 2015.

Figure 2: Field A process block diagram

1.3.1.1 Field A Process Block Diagram Description

After reservoirs drilling and fluid extraction process, fluid is collected via subsea pipelines

and collected in the oil manifold. At this stage, the fluid is associated with gas oil and water.

The fluid then will be sent to first stage separation unit were it is operated at high pressure.

The separation unit derived from the physical principle of change in momentum. The gas

5
will be separated from the liquid phase (oil and water). Then fluid will be sent to second

stage of separation were the separator operate at low pressure the aim of this stage is to

remove any gas carryover by the liquid droplet and it also uses the same physical principle

of the first stage. During first and second stage there will be chemical injection such as

antifoam, emulation breaker, anticorrosion, scale inhibitors. The scale inhibitors and

anticorrosion will be injected in the pipelines as well. After the second stage the liquid (oil

and water) will be sent to the last stage which is large tanks that are derived by the physical

principle of gravitational separation. Separation tanks will provide 6 hr as a residual time.

The fluid will be passing through filtration unit which removes only large suspended solids.

Produced water will be then discharged in to saline aquifer.

1.3.2 Field B Process Description and Disposal Method:

Field B is located above the Qatar Arch, about 85 km off the northern coast of Qatar. The

field was discovered by Wintershall’s 1976. Field B initiated oil production in November

1996 from four horizontal production wells. Over the next thirteen years, another twelve

horizontal production wells were added to bring the well count to sixteen horizontal

production wells. Oil Field B is a marginal field producing sour crude with very low gas oil

ratio (GOR) and very high water cut. Because of low field pressures, production from the

reservoir is supported through the utilization of electrical submersible pumps (ESPs). The

production station at Field B is a refurbished six-leg jack up rig permanent production

facilities (PPF), which supports a new modularized process facility together with utilities,

and an accommodation unit. The extracted fluid is transported to the permanent production

6
facilities through a subsea multi-phase flow lines. At the surface of the facilities the oil,

produced water and gas are separated through a high pressure three phase separation tanks.

The produced water is then sent to the produced water treatment system. The system

consists of three parallel Hydrocyclone and a surge drum. The purpose of the system is to

reduce the oil content of produced water from the high pressure separators to the minimum

state constitutional requirement prior to re-injection. The produced water system also

provides sufficient residence time in the surge drum to enable degassing of the water.

Dissolved gas in the produced water is degassed in the surge drum by venting to the flare

header. The surge drum also provides surge volume for water disposal pumps and removes

oil from the produced water by skimming. Produced water is removed from the surge drum

and routed to two disposal wells.

Figure 3: Field B process block diagram

7
1.3.2.1 Field B Process Block Diagram Discretion

After reservoirs drilling and fluid extraction process. fluid is collected via subsea pipelines

and collected in the oil manifold. Fluid will be diverted in first stage separation unit were

oil, water and gas is separated into three phase separation unit. The separation unit is derived

by two physical principles, change in momentum and density deference of oil and water.

There will be some chemical injection at this stage. After the produced water separation it

will still contain some traces of oil so, it will be sent to three stages of Hydrocyclones which

are working in parallel to handle the capacity of produced water. Finally, the produced water

will be collected into a surge drum to eliminate any chances of gas presence and oil content.

Produced water will be the discharged in to saline aquifer.

1.4 Production of Produced Water

Produced water is a term used in the oil and gas industries. This term refers to the water that

associates the oil in the extraction process. Produced water is the largest waste stream

generated in oil and gas industries. It is a mixture of different organic and inorganic

compounds. Oil extraction process is a physical process that is divided into steps. First the

oil reservoir is drilled and then the oil is extracted from the reservoir using subsea pipe-lines.

The extracted fluid contains oil, gases and water. The source of the water at this stage will

be from the sea water that is surrounding the reservoir as the reservoir will be located in the

bottom area of the sea. To enhance the oil extraction and to maintain the pressure of the

reservoir, two techniques are generally used. These techniques are water injection and gas

injection. The purpose of this technique is to add extra pressure in the reservoir, squeeze the

8
rocks to produce more oil and to replace the lost pressure in the reservoir due to oil

extraction. The third step is the gas lift, where gas is used to enhance the lifting of the fluid

from the reservoir to the manifolds, this technique works on lowering the density of the

extracted fluid.

1.5 Characteristics of the produced water

The characteristic of produced water may change with different locations of the reservoir or

different location of separation or even with different technique of the water oil separation.

Water cut is the ratio of the water present in the extracted fluid compared to the oil. The

water cut show a discrepancy in oil production fields in Qatar and from 2:1 to 4:1. The

higher ratio means that produced water will be in more quantities. Based on the historical

information of the operating company on Field A and Field B. Field A operates with almost

2:1 which indicate that the extracted fluid consist of 50% produced water and 50% of

hydrocarbons, while Field B field operates with 8:1 which indicate that the extracted fluids

consists of 80% produced water and 20% of hydrocarbons.

1.5.1 Historical Constitutes of Qatar’s Produced Water

Constitutes of the produced water will vary according to location and nature of reservoir and

type of fields. Produced water contains sand, suspended solids, dissolved gases and

dissolved solids. Dissolved solids will vary from 100 mg/l to 300,000 mg/l. Inorganic

dissolved solids might include sodium cations (Na+) and chloride anions ( Cl -) which are the

most predominantly, other common cations are Calcium (Ca2+), Magnesium (Mg2+), Iron

(Fe2+) and might include some traces of Barium ( Ba2+) Potassium (K+), Strontium (Sr+),

9
Aluminum (Al3+), Lithium (Li+). There are also some anions present like Bicarbonate

(HCO3), Carbonate (CO3) and Sulfate (SO4).The precipitated solids might include calcium

carbonate (CaCO3), calcium sulfate (CaSO4), and iron sulfide (FeS2) scale, along with oil

coated solids. The dissolved gases in the produced water include Natural gas (methane,

ethane, propane and butane), Hydrogen sulfide and Carbon dioxide (Stewart & Arnold,

2011).

Produced water production arises from a number of separate reservoirs with different water

to oil ratio, but similar, produced water compositions. As total production can be across a

wide range of reservoir ratios there is a range of possible produced water compositions that

can form the feed to the produced water handling facilities. The given composition is an

average of a number of samples of similar composition and is a mixture of water from

various reservoirs, primarily done by the operating company of Field A.

Table 1: Typical produced water measurements in produced in Qatar

Component name Method Concentration ( mg/L )

Calcium API 45 (1968) 17240
Magnesium API RP 45 (1968) 3315
Sodium APHA 3111 66219
Potassium APHA 3111 3370
Silica APHA 3111 67
Soluble iron APHA 3111 0.9
Total iron APHA 3111 1
Boron APHA 4500 B 15.4
Barium APHA 3111 30
Strontium APHA 3111 1560

10
 Copper APHA 3111 < 0.01
Nickel APHA 3111 < 0.01
Zinc APHA 3111 < 0.01
Cobalt APHA 3111 < 0.01
Chromium APHA 3111 0.02
Aluminum APHA 3111 < 0.01
Lead APHA 3111 < 0.01
Manganese APHA 3111 0.24
Cadmium APHA 3111 < 0.01
Cyanide APHA 3111 < 0.001
Selenium APHA 3111 < 0.001
Arsenic APHA 3111 < 0.001
Mercury APHA 3111 < 0.0001
Ammoniacal nitrogen APHA 4500 NH3 1.2
Total phosphates as p APHA 4500 P D 0.2
Chlorides APHA 4500 Cl-B 139310
Sulphates APHA 4500 SO4 2-C 560
Sulphides APHA 4500 S- 7
Carbonates APHA 2320 B 0
Bicarbonates APHA 2320 B 248
Free CO2 APHA 4500 CO2 C 128
Salinity as NaCl Calculation 229860
Total oil content ppm range Historical 5.4 x 104 - 39
Total dissolved solids at 105 oC APHA 2540 B 232020
Total hardness as CaCO3 APHA 2340 B 57530

11
Chapter 2: Literature Review
This chapter presents the review of related literature, researches and studies which have

bearing to the present research study. The theoretical and conceptual frameworks of the

study are presented. To facilitate further understanding, the conceptual and operational

definitions of the key terms are also included in this chapter.

2.1 Introduction to Produced Water:

Produced water is produced as a by-product of drilling and extraction process of oil and gas.

Produced water is certainly not the product of interest of the drilling process. But water is

naturally present in any geographical area under the ground, no matter how sophisticated a

machinery of drilling is used to avoid produced water it will still exist in the extracted fluid.

The hydrocarbons are separated from produced water at the initial stage of the treatment of

produced water.

Water by its nature is a normal solvable product. It has a tendency to dissolve some

hydrocarbons in it under the ground were the pressure is very high. Produced water have

amount dissolved salt also in it and it is said to have nearly 5-6 times more salt than sea

water (Hayes & Aurther, 2004). Produced water can become an environmental hazard if it is

disposed directly into wells or sea. Water level of wells and surrounding area can become

low if produced water is not recycled and re-injected into that particular area of drilling.

Therefore if the facilities of oil and gas drilling and extraction purify produced water, it can

be reused by re-injection into injection wells next to the production wells and that particular

12
geological zone. This helps in keeping the water level and required pressure of that

particular geological area up to the required level (Veil, M.G, & Redwick, 2004). Presently

the most famous method of removing hydrocarbons from produced water is based on using

the gravitational force to separate the hydrocarbons. Oil has a tendency to float above the

water due to its difference in density compared to water. The gravity method doesn’t

separate the dissolved hydrocarbons from water. So, for that purpose different methods are

used like biological methods that is used to remove these hydrocarbons which are fully

dissolved into produced water. Another method is the membrane technology which can

remove the suspended particles. A conventional method like gravity separation, gas flotation

and filtration can be used to remove larger particles from the produced water, these particles

of size larger than 5 µ𝑚 (Frankiewiwicz, 2001). Many standards have been set to measure

the contamination levels of produced water and only 90% or more purified water is allowed

to be discharged. One of the regulatory bodies regulating European Union, has set the

standard of 5mg/L or less hydrocarbons and 10mg/L or less suspended solids contamination

in produced water is mandatory to discharge it to any source like sea or earth (Ashagi, et al.,

2007) .

Zaidi, Simms and Nelson showed in their study that micro or ultrafiltration membranes can

be used to purify the produced water to a level that is very reasonable. It is acceptable by all

regulatory authorities of the world. They observed that this process is sufficient to remove

suspended particles and oil droplets from the produced water. They also clarified that only

one technology is never sufficient for the required level treatment of produced water. It is

always a combination of different technologies which are integrated to process produced

13
water to a level that is acceptable to the present environmental standards set by regulatory

bodies. So to maintain the appropriate purification standards multistage processing processes

must be incorporated (Ray & Engelhardt, 1993). After a reasonable treatment this produced

water is a resource within itself. So the investment in purifying this produced water can be

recovered from its use. It can be used by reinjection the oil and gas wells. It can also be used

as a coolant in power generation plants and geothermal power generation. Areas where there

is a dust problem, produced water can be used to suppress the dust to improve the

environment.

2.2 Sources of Produced Water:

There are three main sources of produced water formation water, aquifer and injection

water. The latest technology of drilling for oil and gas detects the sources of produced water

in the geographical area, trying to perform drilling in area where the possibility of produced

water generation is low. There are some factors that affect the extracted volume of produced

water. Method of drilling plays an essential role; a horizontal well can produce at a higher

rate than a vertical well at similar drawdown. The location of the well whether it was located

within homogeneous or heterogeneous reservoirs is also another factor that affects the

volume of produced water. There are some relations between vertical and horizontal wells

along with homogeneous and heterogeneous reservoirs. For homogeneous reservoirs, use of

horizontal wells reduces water production. The volume of water injection for oil recovery

enhancing, also have an effect on the volume of produced water. Poor mechanical integrity

of drilling may increase the production of produced water (FakhrulRazi, et al., 2009).

14
2.2.1 Formation Water:

Subsurface formations are generally saturated by different underground fluids such as oil,

gas, and sea water. The rocks are saturated with sea water before trapping the hydrocarbon

compounds. The total amount of water that is present in any geographical reservoir that has

the hydrocarbon content is said to be formation water. Formation water is simply the flow

within the hydrocarbon zone. Water saturation is a measure of formation water in any

reservoir. A well of pure water is said to have 100% water saturation. For the measure of

different concentration levels formation water is given different names. Underground

reservoirs under few hundred meters always have certain amount of hydrocarbons

contamination in water. Even the purest of all oil and gas reservoirs have certain amount of

water (FakhrulRazi, et al., 2009).

2.2.2 Aquifers:

Aquifer water could by another source of sea water either above the hydrocarbon zone or

below. Aquifers are another important source of produced water. Aquifers are formation of

ground in which water is enclosed. There are two main types of aquifers

 Confined Aquifer

 Unconfined aquifer

Confined aquifers are source of produced water which are underwater reservoirs containing

high pressure water reservoirs, more than atmospheric pressure. This is the reason why it

doesn’t have free water table. It contains material with a confining layer.

15
Unconfined aquifers are contained in underwater reservoirs without any confining layer over

it. In unconfined aquifer the pressure is equal to atmospheric pressure. (Liu & Liptak, 1999).

Hydrocarbons are contained in aquifers due to water flooding in the aquifers.

2.2.3 Injection Water:

Injection water is another important source of produced water. Before drilling a reservoir

has even pressure within it. So, a reservoir is injected with water, in the beginning the water

is injected and it flows through high permeability areas of the reservoir and it faces

relatively less resistance. Gradually it starts facing relatively greater pressure in different

zones, so the water flow is decreased. As a result, it makes the water to flow towards low

permeability regions. Finally the pressure difference in high and low permeability regions is

reduced. This happens because the flow of water towards low permeability regions is

increased and the overall pressure comes to a balance. This increases the overall efficiency

of the reservoir and more amounts of oil and gas can be drilled out (Xinquan, 2013).

2.3 Produced Water Generation:

Produced water generation is increasing in the world by the passage of time. This is

happening because energy requirement of the world is increasing rapidly. So for this reason

produced water generation is increasing. Figure 4 shows produced water generation for last

decades.

16
 Figure 4: world Produced Water Production (Ferro & Smith, 2009)

The amounts of produced water generated from onshore sources are much higher than the

amount of produced water generated from offshore sources. The production of produced

water rabidly increased from 2002 to 2004 and since then it has been increasing gradually.

Globally in 2009 produced water production is estimated to be 250 million barrels per day

that is produced along with 80 million barrels per day. Where the world water to oil ratio is

3:1 which represent 70% water cut (FakhrulRazi, et al., 2009). Time passes, and the

production of the produced water increases however, the treatment of produced water is

becoming safe and better. This is due to strict regulation that is set by regulatory institution.

So, the environmental hazards caused by produced water are decreasing certainly with time

and the environmental threats are also decreasing. Discharge of produced water is shown in

the following graph:

17
 Figure 5: Yearly Discharge of Produced Water (OSPAR, 2014)

As shown in figure 5, the amount of oil that being discharged into the sea either in the form

of spillage or produced water discharge is being observed in the period of 1998 up to 2007.

The amount of oil discharged from the produced water can reach double to triple the amount

of oil that is discharged to the sea due to oil spillage. The following figure represents the

disposal capacity of produced water for various techniques and the expected range of oil

concentration for various produced water volume.

Figure 6 indicates that the produced water injected directly into the sea water reservoirs has

an oil concentration of 2 to 5 mg/l while the produced water that are being discharged into

the disposal wells has an oil concentration of 25 to 27 mg/l.

18
 Figure 6: Disposal techniques for produced water (OSPAR, 2014)

2.3.1 Countries Generating Produced Water:

Produced water production varies with different geographical location and different capacity

production of oil and gas. The volume of produced water produced from oil and gas wells

changes with time, the water to hydrocarbon ratio increase over the time. The share of these

countries in generating oil and gas is shown in figure 7. Figure 7 shows worldwide top

countries for oil and gas production. Qatar is considered one of the top ten oil and gas

production countries, so a massive amount of produced water is expected.

19
 Figure 7: Oil and Gas Generation (UK Oil and Gas, 2014)

USA is considered as second largest country for oil and gas production, the produced water

estimated in 2007 is about 21 billion barillas which is equivalent to 57.4 million barillas per

day. The average of offshore and onshore water to oil ratio is estimated to be 5.3 (Veil &

Clark, 2009). Based on the Norwegian oil and gas association in 2012 about 819 million

barillas of produced water were discharged in the Norwegian continental shelf (Torgeir, et

al., 2013). Although Norway has high capacity of produced water generation it is not

considered as the world top 20 oil and gas producers. Produced water production is not the

same for all countries, it depends on the water to oil ratio.

2.4 Characteristics of produced water:

Physical and chemical properties of produced water vary with different geographical

location of the field, the geologic formation of the production well, the hydrocarbon type

that is being produced and lifetime of the reservoirs (FakhrulRazi, et al., 2009). Produced

20
water contains organic and inorganic materials, dissolved and dispersed oil compounds,

dissolved gases, solids, heavy metals and production chemical compounds. Characteristics

of produced water are discussed discretely in the following headings:

2.4.1 Suspended solids:

Suspended Solids are very often present in the extracted fluid. Suspended solids are found as

small particles from the reservoir rock such as clays and quarts or from hydraulic fracture in

the rock due to the hydraulic pressure replacement such as proppant, or it can precipitate

from the produced water re-injection such as iron sulfide. Produced water may surely be

having various kinds of solid or dissolved impurities. If we quantify these impurities

suspended solids is a term used to indicate small particles in the water column. The size of

these particles varies. In the hydraulic-fracture case, the proppant size may be 1 mm or

larger, while iron sulfide precipitate can be < 0.1 µm. Usually solids are ignored until the

problems are onerous that action is required. Because the solids are denser than either the oil

or the produced water, it tends to sink to the bottom of the pipes, vessels, or tanks which

causes lots of operational issues (Blumer, 2007).

Earlier studies carried out using X-ray photoelectron spectroscopy(XPS) and X-ray

fluorescence revealed that some organic compounds along with crude oil were present in the

suspended solids samples, some crystal inorganic substances like SiO2, Fe2O3, Fe3O4,

BaSO4 in suspended solid samples was also observed (Leiknes & Semmens, 2000) .

21
2.4.2 Dissolved solids:

Produced water dissolved solids mostly are sodium, anions of chloride and bicarbonates.

The Sodium Adsorption Ratio (SAR) is scale to measure of the sodicity of water (Healy, et

al., 2011). About 70% of the world petroleum reserves have water containing more than

100,000 mg/l of dissolved solids. Waters associated with the other 30% of petroleum

reserves contain less than 100,000 mg/l. Water containing dissolved solids in excess of

100,000 mg/l can be classified as brine (Blumer, 2007). A regular upper limit of the

concentration of TDS in sweater is almost 40,000mg/L but it can be only in few extreme

situations Brine may also have the TDS concentration of up to 300,000mg/L (FakhrulRazi,

et al., 2009). Brackish produced water is in less existence. Previous literature survey in

United States indicates that less than 3% of studied produced water was brackish to hyper

saline (Alley, et al., 2011). High concentrations of TDS detected at the surface of water body

due to evaporation (Batley, & Kookana, 2012).

2.4.3 Total petroleum Hydrocarbon:

Hydrocarbons are measured as Total Petroleum Hydrocarbons (TPHs). These are molecules

that have carbon and hydrogen. Petroleum hydrocarbon can be ether in the form of dissolved

or suspended petroleum hydrocarbon. Petroleum hydrocarbon is a mixture of hydrocarbon

including mainly four groups BTEX, NPD, PAHs and phenols. The following table

represents the hydrocarbons that associate the oil compound

22
 Table 2: hydrocarbons associating the oil mixture

BTEX NPD PAHs Phenols

Polyaromatic
Benzene Naphthalene C1-phenol
hydrocarbon

Toluene Phenantherene Benzo(a)pyrene C2-phenol

Ethylbenzene C3-phenol
Dibenzothiophene Benzo(ghi)perylene
Xylenes C4-phenol

There are many factors that affect the concentration of oil in produced water factors such as

the extracted oil composition, pH, salinity, TDS, temperature, water to oil ratio, type and

quantity of the oilfield chemicals and type and quantity of various stability compounds such

as waxes, asphaltenes, fine solids. The hydrocarbons are usually grouped into three

categories:

1. Saturated 2. Unsaturated 3. Aromatics

2.4.3.1 Saturated:

Saturated hydrocarbons are characterized by the single C-C bonds while all other available

bonds are saturated by H atoms. This group can further be divided into two more sub

categories that are:

1. Aliphatic: Aliphatic hydrocarbons are directly branched with a general molecular

Formula: CnH2n+2.

23
 The general names for these kinds of compounds are alkanes and Isoalkanes which

are usually highlighted by the petroleum industry as paraffin’s and isoparaffins

respectively.

2. Alicyclic: Alicyclic hydrocarbons are saturated hydrocarbons which contain one or

more rings with a general molecular formula: CnH2n.

They are also known as cycloalkanes or naphthenic or cycloparaffins by the

petroleum industry.

2.4.3.2 Unsaturated:

Unsaturated hydrocarbons are simply characterized by two or more bonds (C=C for alkynes

or C≡C for alkynes) between two carbon atoms. They are not usually found in crude oils,

but are produced in cracking processes converting large molecular hydrocarbon to small

molecule hydrocarbon.

Alkenes/olefins are those which contain two carbon bonds with a general molecular

Formula: CnH2n.

Alkynes/acetylenes are those which contain three carbon bonds with a general molecular

Formula: CnH2n−2.

24
 Figure 8: Hydrocarbon chemistry of total petroleum hydrocarbons (TPHs)

Figure 8 shows the categories and the groups of the petroleum hydrocarbons. Alkynes and

Alkenes are example of unsaturated hydrocarbon while, cycloalkanes are example of

saturated hydrocarbons.

2.4.3.3 Aromatic hydrocarbons:

Aromatic hydrocarbons are grouped by a benzene ring structure. The benzene ring have six

carbons, each carbon in the ring attaches with one hydrogen. It depends on the number of

rings that aromatic hydrocarbon molecule having in it. Aromatic carbons are often further

25
subcategorized into single ring aromatics and polycyclic aromatics containing two rings or

more.

Understanding the composition of oil will help to realize the basic hydrocarbon chemistry.

Oil in produced water is a common term, but the result of oil content in produced water

depends on the methods used for this purpose. Different appropriate methods can be used to

determine the oil concentration.

2.4.3.3.1 Dispersed oil:

Commonly it is the oil content in produced water in the form of small droplets of oil

suspended in the produced water, which may lie from sub-microns to hundreds of microns.

Dispersed oil will contain PAHs and some of the heavier alkyl phenols which are less

soluble in produced water. There are some factors that affect the amount of dispersed oil

such as density of the oil, the shear history of the droplet and the interfacial tension between

the water and the oil (FakhrulRazi, et al., 2009).

2.4.3.3.2 Dissolved oil:

Commonly it is the oil in produced water in a soluble form. The water soluble organic

compounds in produced water are polar constituents which could be in low or medium

carbon range. Organic acid such as formic acid and propionic acid are normally present in

produced water. Phenols and BTEX are the most soluble compounds in produced water.

Aliphatic hydrocarbons in general have very low solubility in water but, aromatic

hydrocarbons; combination of compounds such as organic acid forms the huge amount of

dissolved oil. There are factors that affect the volume of dissolved oil in produced water.

26
Temperature and pH have a directly proportional relationship with soluble organics in

produced water. Pressure enhances the solubility of organics (FakhrulRazi, et al., 2009). If

the sample of produced water are taken and acidified many of the organics acids and phenols

are converted from the water soluble to oil soluble(dispersed), which are taken out of the

solvent.

Table 3: Solubility of BETX and other single ring aromatic hydrocarbons (Frintrop, et al., 2011)

Compound Molecular Formula Solubility at25 ◦C (mg/l)

Benzene C6H6 1790
(mg/L)
Toluene C7H8 526
Ethylbenzene C8H10 169
o-xylene C8H10 178
p-xylene C8H10 162
m-xylene C8H10 161
1,2,3- C9H12 75
1,2,4- C9H12 57
Trimethylbenzene
1,3,5- C9H12 48
Trimethylbenzene
p-Ethyl toluene C9H12 95
Trimethylbenzene
o-Ethyl toluene C9H12 75
m-Ethyl toluene C9H12 40
Iso-propyl C9H12 61
n-Propy
benzene benzene C9H12 52
n-Butyl benzene C10H14 12

27
2.4.4 Chemical Oxygen Demand COD:

COD are defined as the milligrams of O2 which consumed by the chemical demand per liter

of the sample under the terms of the procedure used. COD is considered toxic to the

environment if it was present at high concentrations. It also contributes in decreasing the

amount of dissolved oxygen in the water body, which will affect the living organisms.

Chemical oxygen demand can be classified into sub categories as listed below in figure 9.

A detailed characterization of the produced water organic matter can be achieved by

dividing the total COD into fractions with different microbiological properties (Vollertsen &

Jacobsen, 2002).

These parameters determine the quantity of the organic matter present. composition of the

fractions of biodegradable organic matter can be obtained by referring to COD fractions

information. Some more information on the Produced water biodegradability can be gained

comparing different measures of COD fractions, information such as the nature of the COD

and weather if it is in the form of soluble COD or particulate COD. One of the COD

fractions is the active agent in the microbial transformations; it is the heterotrophic microbial

biomass. Other fractions are substrate for this biomass. Some of the substrate is readily

biodegradable and some is more slowly biodegradable in a way that it must be hydrolyzed

before it can be utilized by the heterotrophic biomass. Another part of the organic matter is

not biodegradable at all (Vollertsen & Jacobsen, 2002).

28
 Total COD
(COD or tCOD)
Carbonaceous materials in wastewater

Biodegradable COD Nonbiodegradable COD

(bCOD) (nbCOD, uCOD)
Carbonaceous materials which can be degraded Carbonaceous materials which are inert and not
biologically Typically 50 – 70% processed biologically Typically 30 – 50%

Readily Biodegradable Slowly Biodegradable Nonbiodegradable Nonbiodegradable

(soluble) (particulate)
rbCOD sbCOD
Carbonaceous materials Usually the main
of low molecular size, biodegradable
important in high rate carbonaceous fraction,
denitrification and P require enzymatic or
removal Typically 8 – hydrolytic conversion, effluent soluble COD
25% important in slow rate
denitrification
Typically 75 – 90%
(soluble) (particulate)
nbsCOD nbpCOD, upCOD
Always present in Inert particulate material
influent, passes assumed entrapped by
through plant activated sludge flocs,
unchanged, become removed by wasting of
sludge Analogous to
(sCODe, usCODe) nbVSS

Figure 9: Chemical oxygen demand fractions (Iowa state university, 2011)

2.4.5 Readily Biodegradable Chemical Oxygen Demand:

When produced water is generated as a byproduct, then along with many other impurities

harmful and hazardous constituents it also contains carbonaceous constituents. This section

will discuss readily degradable chemical oxygen demand (rbCOD) concentrations in the

produced water. Before designing any method to process the produced water, the fraction of

rbCOD must be known because it define the oxygen demand for the reduction of the

carbonaceous impurities. It is also a key factor and consideration in the nitrogen removal

29
process in produced water. Produced water having more rbCOD, will be quicker in reducing

nitrogen from produced water and vice versa. There are different methods of reduction and

removal of rbCOD from produced water before injecting it back to earth aquifers or to

discharge it in sea. When phosphorus is removed from water, rbCOD is converted to acetate

which can further be removed. rbCOD is actually complex form of COD which is soluble in

nature as discussed previously. During the processing it is converted to or can be converted

to fatty acids. It can be measured in produced water during its biological testing. Oxygen is

required to process rbCOD content. So it is another consideration, because oxygen is

consumed as a main product for the processing of rbCOD content in produced water

(Metcalf & Eddy, et al., 2013).

2.4.6 Total Kjedahl Nitrogen TKN:

Most scientists believe that the hypoxic zone which is an area of low dissolved oxygen is

caused by the presence of nutrients such as nitrogen and phosphorus (Veil, et al.,

2005).TKN is the measure of total nitrogen in water. TKN is mainly a composition of

Ammonia Nitrogen and Organic Nitrogen. Figure 10 represent diagram in which Nitrogen

constituents and their relationship is shown. It is certainly easier to process the

biodegradable part of organic nitrogen while non-biodegradable part of organic nitrogen is

more difficult to treat and is more harmful for the environment. However there is a certain

cost involved in the processing for even biodegradable part of organic nitrogen. Particulate

is easier to separate than the soluble but as far as they are biodegradable they can be

30
 processed. So it is very important to get rid of TKN as much as possible before injecting the

water back to the environment whether it is sea or aquifers (Metcalf & Eddy, et al., 2013).

TKN

Ammonia Nitrogen Organic Nitrogen

Biodegradable Non-

biodegradable

Particulate Soluble
Soluble Particulate

Figure 10: Total kjedahl nitrogen TKN fractions (Metcalf & Eddy, et al., 2013)

31
2.4.7 Heavy metal:

Heavy metal concentration in produced water depends on age of the wells and formation

geology (FakhrulRazi, et al., 2009). Metals are simply available in produced water in the

form of dissolved ions or particles. Some researchers have shown that produced water tend

to contain zinc (Zn), lead (Pb), manganese (Mn) and iron (Fe) at concentrations widely

exceeding the normal specified in regulations. Other famous heavy metal pollutants like

cadmium, chromium, nickel, vanadium and copper exhibit only less amounts, which are

lower than the identified standards. the most studied metals in produced water are barium

(Ba), cadmium (Cd), chromium (Cr), lead (Pb), mercury (Hg), copper (cu), nickel (Ni), and

zinc (Zn). Produced water have so many other trace metals which includes iron (Fe), lithium

(Li), manganese (Mn), Selenium (Se), strontium (Sr), Some of the metals are atmosphere

dependent because their concentrations may be high to cause bioaccumulation and toxicity.

2.4.8 Oil droplet size distribution:

Produced water is removed from an inherently organic system, where carbon sources have

been converted to hydrocarbons over geologic time. Organic matter in produced water is

present in two forms:

1. dispersed oil

2. non-hydrocarbon organic material

Dispersed oil is small, discrete droplets suspended in the water. The amount of oil droplets

in produced water depends on the density of oil and the amount of oil precipitation and

32
interfacial tension between the water and oil. PAHs and few heavier alkyl phenols are less

soluble in produced water and exist as dispersed oil. The concentration of PAHs and C6–C9

alkylated phenols is strongly correlated to disperse oil content of produced water. Suspended

carbon may contain oil or high carbon mass particles that possible be removed by the

filtration (Tibbetts & Buchanan, 1992). The behavior of emulsions is important, it is

considered as the primary factor to determine the treatment method of produced water from

the total petroleum hydrocarbon. Full characterization is needed most importantly the

droplet size distribution. There are so many techniques may be used to get the droplet size

distribution. Microscope is a popular technique that is being used very often.

2.4.8.1 Droplet Size Distribution from Microscope:

When measuring the droplet size distribution by using the microscope method it is needed to

dilute the emulsions. The dilution include 0.2𝑔 emulsion drop to 2 𝑔 of the crude oil and

slightly mix it. The oil droplet size distribution can be obtained by putting a little portion of

the dilute emulsion on the glass lid the drop would be flattened by placing a smaller glass

slide on the top of the droplet. Several pictures would be taken to get the credible impression

of the droplet size distribution more than the 800 droplets would be counted in distribution

population (Chakraborty, et al., 2003). It is very important to know the droplet size. By

knowing the droplet size the most appropriate treatment method or produced water can be

identified.

33
2.4.9 Ions and inorganic constituents:

Ions are charged particles, for instance NaCl salt dissolves in water forming a solution which

contains Na(+) and Cl(-). Based on the salt composition study from the previous sections

sodium is strongly present in produced water. The ranges of SAR are unique for each

produced water source. SAR represents the ration of particular cations to one another it

represents direct focus on the relationship of the sodium with calcium and magnesium.

When concentrations of sodium the calcium and magnesium get higher value of SAR

becomes lower. High TDS concentration are related to high SAR even when sodium is

strongly present. Major inorganic constituents are indicating in produced water include

sodium, bicarbonate, magnesium, potassium, calcium, chloride, and sulfate. The following

table represents concentration of the inorganic constituents in produced water by the United

State Geological Survey institution (Rice & Nuccio, 2000).

Table 4: Common inorganic constituents in conventional produced water (Rice & Nuccio, 2000)

Concentration Range
Constituent Units Reference
Low High Median
USGS
TDS Mg/L 400,000 50,000
USGS
Sodium Mg/L 0 150,000 9,400
produced
100 USGS
Chloride Mg/L 0 250,000 29,000 produced
water
USGS
Sulfate Mg/L 0 15,000 500 produced
water
database
USGS
Bicarbonate Mg/L 0 15,000 400 produced
water
database
USGS
Calcium Mg/L 0 74,000 1,500 produced
water
database
produced
atwater
Minor ions present in product water containing inorganic constituents like metal database
different
water
database
range of concentrations as well as a nonmetal likely fluoride and boron. These minor ions
database

34
are found comparatively lower concentration than the major ions. Table 5 contains the

comprehensive list of inorganic constituents and Minor ions concentration being provided

from countless studies sources in association with USGS database value (FakhrulRazi, et al.,

2009).

Table 5: Conventional and Unconventional Constituent List (FakhrulRazi, et al., 2009)

Constituent List Units Conventional Unconventional

Antimony mg/L n/a ND – 0.005
Aluminum mg/L < 0.50 – 410 0.005 – 1.52
Beryllium mg/L < 0.001 – 0.004
Arsenic mg/L 0.004 – 151 a,b,d ND –n/a0.158 e
Bicarbonate mg/L ND – 14,750 4.53 – 49,03
Barium mg/L ND – 1740 a,b,d 0.445 – 125 e, g
Boron mg/L ND – 95 0.05 – 30.6
Bromide mg/L 150 – 1,149 ND – 41.1
Cadmium mg/L < 0.005 – 1.21 ND – 0.076
Calcium mg/L ND – 74,185 ND – 5,530
Chloride mg/L 2 – 254,923 ND – 52,364

– 1.1–a,d
Copper mg/L < 0.002 5 0.001 – 1.448
Chromium mg/L ND ND – 3.71 e, g
Fluoride mg/L n/a 0.57 – 20
Cobalt mg/L n/a ND – 0.010 e
Iron mg/L ND – 1,100 0.001 – 258
Lead mg/L 0.002 – 10.2 ND – 0.098
Lithium mg/L 3 – 235 ND – 1.50
Magnesium mg/L ND – 46,656 1.2 – 918.9
Nickel mg/L 0.08––175 ND– –3.11
<< 9.2 d 0.082
Manganese mg/L 0.004 ND e, g
Nitrogen, ammoniacal (N- mg/L 10 – 300 n/a
Mercury mg/L < 0.001 – 0.002 d ND – 0.014 e
Nitrate ND – 26.1
NH3) (N-N03) mg/L n/a
Molybdenum
Potassium mg/L
mg/L n/a
0 – 14,840 ND––0.448
ND 1,100e
Selenium mg/L n/a ND – 1.27

35
Silver mg/L < 0.001 – 7 ND – 0.14
Tin mg/L – 1.1 h
Sodium mg/L 1 –ND
149,836 97.3 –n/a
32,013 e
Titanium mg/L < 0.01 – 0.7 n/a
Strontium mg/L 0.02 – 6,200 a,d ND – 47.9 g
Uranium mg/L n/a ND – 2.5
Vanadium mg/L n/a ND – 0.290
Zinc mg/L 0.01 – 35 0.005 – 5.639

2.4.10 Alkalinity:

Produced water is usually alkaline. If alkalinity needs to be reduced, it is necessary to

remove bicarbonate ions or reduce pH by adding an acid. Alkalinity is a measure of the

capability of water or any other solution to neutralize or buffer acids. This measure of acid-

neutralizing capability plays an important part in figuring out how “buffered” the water is

against sudden changes in pH. Actually the pH is a measure of hydrogen ion (H+)

concentration and the scale pH indicates the intensity of acidic or fundamental character of

the solution at a assigned temperature. Carbonate (CO32-) and bicarbonate (HCO3-) ions are

very important complex in water they define alkalinity in water. Carbonate ions are able to

react with the neutralize hydrogen ions (H+) and the bicarbonate ions can also neutralize H+

or hydroxide ions (OH-). The capability to reverse the changes in pH by neutralizing acids is

called buffering. Alkalinity is very important to the aquatic organism because it defend the

aquatic organism from the fast changes in pH. Alkalinity is very important in those places

where acid rain is an issue. Table 6 represent the compounds that affects the produced water

alkalinity.

36
 Table 6: Important compounds for Alkalinity

H+ Hydrogen ion (acid)

OH- Hydroxide ion (base)
H2CO3 Carbonic acid
HCO3- Bicarbonate ions
CO32- Carbonate ion
CaCO3 Calcium carbonates(calcite
CaMg(CO3)2 Dolomite Lime

In many ways, many sources are travelling for alkalinity. One of these sources is calcium

carbonate CaCO3 or the dolomite (CaMg(CO3)2), little amount of other minerals are also

included. Alkalinity may increase the pH when it would be coming from mineral source

such as calcium carbonate (CaCO3). If we dissolve CaCO3 in the water the carbonate (CO32-)

would react with water to form bicarbonate (HCO3-) it would produce hydroxide (OH-):

CaCO3 (s) ↔ Ca2+ + CO32-

CO32- + H2O ↔ HCO3- +OH-

Rate of alkalinity is higher because it typically have high concentration of nutrients and ions.

Some have acid buffering feature like silicate and phosphates. Carbon dioxide and water are

converted to carbonic acid through the following reaction:

CO2 + H2O ↔ H2CO3 (carbonic acid)

37
Table 7 shows the alkalinity range for different sources of water. Produced water have a

lower range of alkalinity than Seawater.

Table 7: Typical Alkalinity Range (Stewart & Arnold, 2011)

Water source (mg/L CaCO3)

Rainwater <10
Typical surface water 20-200
Ground water 100-500
Seawater 50-1000
Produced water 100-500

2.4.11 Dissolved gases:

The major dissolved gases in produced water are carbon dioxide, oxygen and hydrogen

sulfide. They are formed naturally, by the activities of bacterial or by chemical reactions in

the water. There are dissolved hydrocarbon gases as well. The solubility of the gases in

water usually decreases with increased water salinity and temperature and increases with

pressure. Hundreds of drill stem samples of brine from water-bearing subsurface formations

in the US Gulf Coast area were analyzed to determine the amounts and types of

hydrocarbons. The main constituent of the dissolved gases was methane; also measurable

amounts of ethane, propane, and butane were observed. The concentration of the dissolved

hydrocarbons generally increased with depth in a given formation. In close proximity to

some oilfields, the waters were enhanced in dissolved hydrocarbons. Up to 14 scf dissolved

gas/bbl water was distinguished in some locations (Blumer, 2007).

38
According to Henry’s law the solubility of gasses depends on temperature and the partial

pressure of the gas over the liquid which is the produced water in this case. The pressure

down the production reservoir is very high. When pressure increases the amount of

dissolved gasses also increases.

2.5 Chemical Additives:

In addition to the naturally present components in produced water produced from oil

extraction process and the produced water that is re-injected to maintain the reservoir

pressure. They may also contain chemical additives, used in drilling and production

operation for different purposes. The used chemicals are typically complex mixture of

various molecular compounds. These chemicals can affect the water/oil ratio, toxicity and

biodegradability (Veil, M.G, & Redwick, 2004). This mixture could be anti-foams to

prevent the formation of foams in the separation vessels, or could be demulsifiers which

helps to break the emulsion layer between oil and water, it could also be corrosion inhibitor

to help in reducing the corrosion rate in pipelines and equipments. There are other chemicals

as well like scale inhibitor and solvents to reduce paraffin deposits.

2.6 Aquatic Chemistry:

When water chemistry is analyzed it is needed to identify the quantity of chemical contents

and characteristic of specific water. It may be containing pH, isotopes, major cations and

anions and trace elements. It is known that H2O is a polar molecule with a meager positive

39
charge near the hydrogen and a minor negative charge near the oxygen. These exact charges

are a way to understand the aquatic chemistry.

2.6.1 pH characteristic of the aquatic chemistry:

Extreme pH values >11.0 or <4.5 are lethal for the aquatic environment. Acids play vital

role to decrease the pH of a solution it chop up the water molecules. Acid react with the OH-

hydroxide ion and separate from H+ hydrogen ion. The hydrogen and hydroxide ions also

have important role in water reactions lots of reactions depends upon pH and make pH

more independent. So, pH is often known as master variable in aquatics system. It is said

that pH represent the hydrogen ion, one may find out hydroxide ion concentration by pH

since protons and the hydroxide concentrations are relating each other by the connection of

water

2.7 Effects of produced water on Aquatic Chemistry:

The main physical factors affecting aquatic chemistry are temperature, transparency,

dissolved oxygen, chemical oxygen demand, CO2 concentration, salinity and presence of

impurities. Many of the chemical processes are influenced by the action of algae and

bacteria. The algae and bacteria are very dependents on the presence of dissolved CO2 and

O2. The aquatic chemistry would be affected by the produced water chemistry due to the

large volume discharge of the produced water in to the sea as a reservoir injection or

disposal. The presence of ions in produced water would affect the chemistry of produced

water in term of buffering capacity, salinity, and scale potential (FakhrulRazi, et al., 2009).

40
2.7.1 Hydrocarbon:

The mechanisms of poisonous impacts of aromatic hydrocarbons like PAH are the subject to

the reasonable discussion. Few PAHs can be having their impact on hormones regulations

however it is also said endocrine disruption. There are some limited particle are available for

the disturbance of hormone regulation. Produced water from oil production field is different

than the gas production field. Produced water from oil production fields always contains

lower level of low molecular weight aromatic hydrocarbon than the produced water from

gas field. BTEX (benzene, toluene, ethyl benzene and xylene) is an example of low

molecular weight aromatic hydrocarbon.

2.7.2 Heavy metal:

Heavy metal is being a reason of the aquatics pollution. the main heavy metals that affect the

aquatic chemistry are Lead, Cadmium, Arsenic, Chromium, Mercury and Thallium. Little

amount of heavy metals like copper, zinc emerge into our bodies are helpful in maintaining

human metabolism. If the concentrations of these metals increases, surely it will tend to

poisoning effect.

2.7.3 Suspended solids and dissolved gases:

Calcium carbonate CaCO3(s) represent one of the major suspended solids in water. Calcium

carbonate is formed due to the presence of calcium in the discharged produced water were

the calcium ion Ca+2 react with carbonate ion CO3-2 to produce calcium carbonate. The

carbonate ion naturally presence in the water is due to algal photosynthesis which is

41
supported by the presence of dissolved CO2 gas. Part of the calcium carbonate will react

with the hydrogen ions present in the water to dissolve in to Ca2+, CO2 and H2O as the

following equation

CaCO3 + 2H+ → Ca2+ + CO2 + H 2O

Calcium carbonate might also react with CO2 and H2O to produce Ca2+ and HCO3-. In

general the presence of calcium and bicarbonate will cause the temporary hardness in the

water. Due to the microbial action of the biomass present from the photosynthesis of algae

and the presence of dissolved oxygen in the water body and in the discharged produced

water which also contains the sulfur ions the harmful H2S gas is produced. Figure 11 shows

the main chemical cycle in the aquatic chemistry.

Figure 11: Major aquatic chemical processes

42
2.8 Hazard and Risk of Produced Water:

Produced water is the largest waste flow discharged by the oil and gas industry. Produced

water is considered to be hazards waste because it contains the following components:

1. hydrocarbons

2. salts

3. toxic metals

4. radionuclides

5. toxic production chemicals

The damage or the risk due to produced water discharge is limited to a certain distance and

the exposure time. Hydrocarbons are the major sources of toxicant in produced water

specially the monocyclic aromatic hydrocarbons BTEX and the polycyclic aromatic

hydrocarbons PAH. Some PAH are known to be potent carcinogens for that reason PAH is

given high priority for environmental pollution regulation and in risk assessments of

industrial discharges. According to studies and investigation done to study the

ecotoxicological issues related to PAH, it may cause DNA damage, oxidative stress, cardiac

function defects or embryotoxicity (Torgeir, et al., 2013).

A general ratio of brine or salt to produced water associate oil produced from convectional

well sources is 2:1 however, the volume of brine to oil increases over the life span of the

well and produced water may approach 10:1. The disposal of the brine could cause ground

and surface water pollution, salt scaring and erosion (Farag & Harper, 2013).

43
2.8.1 Environmental Risks:

Leaks from pipes and containment structures are key risk for the area surrounding oil and

gas production stations. Environmental risk depends on its structure and locations plus

magnitude. Produced water spill near the cost have an influence on the soil and greatly

affect vegetation (Davies, 2013). Downstream aquatic system may be having ecological

impact if the spilled produced water enters in a water course. Eco toxic response may be the

result of high level of salt and metal concentration of produced water. Soil pollution my

intact for long time period it may take years for remediation, while water pollution may take

few months.

2.8.2 Groundwater Pollution:

Onshore production stations which are surrounded by groundwater supplies cause a real risk

to groundwater. New South Wales State did a study on one of the gas producer company in

the U.S. The study was done by Macquarie University and reported to NSW office of the

chief scientist and engineering. The result of the study indicated that some BTEX were

found in the surrounding aquifers (Davies, 2013).

If the groundwater aquifers polluted by produced water it takes many years before it is safe

to use. During such situation citizen should be facilitated with different supplies for

domestic and agricultural usage if their main source of water is groundwater. The drinking

water wells should be within 1 kilometer of the gas wells as the elevated methane escapee

gases exists in the area. Produced water is also some time used for irrigation in some areas

they are facing a great risk by the produced water. There is a huge risk of the

44
bioaccumulation of certain pollution in the crops and even stocked grains. That can directly

and badly affect the human health in a way (Jackson, et al., 2013)

2.8.3 Health Risks:

Produced water has a direct health affect if the pollutants presents in high quantities.

According to United States department of labor, hazardous Chemicals present in produced

water have an adverse health effects. Table 8 includes the hazardous chemical with the

corresponding affects (OSHA, 2014).

Over 300 various chemicals are being used in the United States as chemical additives. 75%

of them can directly affect human skin, eyes and other sensitive organs of human body

including their respiratory and gastrointestinal system. Nerves and brains, kidneys, immune

and cardiovascular system may also get affected 40 to 50%, endocrine system of human

body may also be affecting by 37% and there are 25%chance of cancer and mutations.

(Colborn, et al., 2011)

Table 8: Hazardous chemical effects on health (OSHA, 2014)

Hazardous Chemicals Adverse Health Effects

Benzene (crude oils high in BTEX,
benzene, toluene, ethylbenzene, and
xylene)
Benzo(a)pyrene (a polycyclic aromatic
hydrocarbon reproductive [see below],
formed when oil or gasoline burns)
Carbon dioxide (inerting atmosphere,
byproduct of combustion)
Carbon monoxide (byproduct of
Irritation to eyes, skin, and respiratory system;
dizziness; rapid heart rate; headaches; tremors;
confusion; unconsciousness; anemia; cancer
Irritation to eyes and skin, cancer, possible
effects
Dizziness, headaches, elevated blood pressure,
rapid heart rate, loss of consciousness
asphyxiation, coma
Dizziness, confusion, headaches, nausea,

45
combustion) Irritation to eyes, skin, and
respiratory
Ethyl benzene (high in gasoline)
Hydrogen sulfide (oils high in sulfur,
decaying plants and animals)
Methyl tert-butyl ether (MTBE) (octane
booster and clean air additive for
gasoline, or pure MTBE)
Polycyclic aromatic hydrocarbons
(PAHs) (occur in crude oil, and formed
during burning of oil)
Sulfuric acid (byproduct of combustion
of sour petroleum product)
Toluene (high BTEX crude oils)
Xylenes (high BTEX crude oils)
weakness, loss of consciousness, asphyxiation,
coma
Irritation to eyes, skin, and respiratory system;
loss of consciousness; asphyxiation; nervous
system effects
Irritation to eyes, skin, and respiratory system;
dizziness; drowsiness; cough; headaches; nervous
system effects
Irritation to eyes, skin, and respiratory system;
headaches; nausea; dizziness; confusion; fatigue;
weakness; nervous system, liver, and kidney
Irritation to eyes and skin, cancer, possible
reproductive effects, immune system effects
Irritation to eyes, skin, teeth, and upper
respiratory system; severe tissue burns; cancer
Irritation to eyes, skin, respiratory system;
fatigue; confusion; dizziness; headaches; memory
loss; nausea; nervous system, liver, and kidney
effects
Irritation to eyes, skin, respiratory system;
dizziness; confusion; change in sense of balance;
nervous system gastrointestinal system, liver,
kidney, and blood effects

2.8.4 Industry Risk:

An oil and gas production company faces industrial risks from constituents in produced

water. One of the most constituent that adds risk to operation is suspended solids. The

suspended solids my cause accumulation in pipelines which causes extra pressure or it may

cause fouling for some of the equipments that might be affected by the solids. Produced

water may contain hydrogen sulfide H2S and also have the tendency to generate H2S as

46
discussed in the previous chapters. Hydrogen sulfide can cause many operational issues due

to pipelines and equipment corrosion and failure.

2.9 Standards and Regulation:

There are different regulatory institution which are now inspecting and regulating the

produced water treatment process. Increasing demand of energy makes the oil and gas

companies extract more oil and gas. So it is important to provide a guide line to discharge

produced water after extracting the harmful component. Occupational Safety and Health

Administration (OSHA) and United States Environmental Protection Agency (EPA) are two

regulatory institution which have made critical regulations and laws for the extraction

process and disposing of produced water. These regulatory institution are authorities and

they can monitor and enforce penalties upon any mistreatment of produced water for the oil

and gas extraction companies. In each country, there are different institutions that set the

regulation of the country. For some countries like Qatar there is only one institution that sets

the regulations, and regulations must be followed by all companies and association. This

institution is the ministry of environment. Currently the only regulated characteristic for

disposal of produced water in term of reinjection is TPH.

2.9.1 Standards for Heavy Metal in Produced Water:

Clean Water Act is imposed in US by Environmental Protection Agency; section 402 covers

the quality of waters of US. Some detailed regulations are applied and enforced to maintain

the quality of waters of US. So, produced water is only allowed to be discharged after

47
standard operation of produced water. Any liquid or waste which can pollute the waters of

US is prohibited to be discharged in US waters. This mainly covers the onshore produced

water discharge. Under this act of EPA, all the oiling and drilling firms are allowed to

discharge only processed water into US oceans which is not harmful for the ocean species

and is not prone to cause any environmental hazards. (EPA, 2011).

As far as the concentration of heavy metals is concerned in produced water that is to be

discharged after extracting the harmful material, there are no certain regulations directly on

heavy metal discharge offshore under EPA regulations. However heavy metals are

sometimes toxic as well so certain toxicity regulations cover the quantity of heavy metals in

produced water to be discharged. As the standard metals is regulated to be toxicity so to

make it easily understandable the heavy metals dissolved in produced water are found in

different quantities from different geographical areas. The amount of heavy metals from

different geological places depends upon the geological nature of that area (Ray &

Engelhardt, 1993). Table 9 gives the concentration of heavy metals in produced water and

its maximum allowable limit according to EPA:

Table 9: Max and min allowable concentration of some heavy metals and Comparison with seawater (EPA, 2011)

Metal Average Standard Maximum Minimum Seawater

Cd (mg/l) 27 12 98 0 Trace
(µg/L) Deviation (µg/L) (µg/L) (µg/L)
Cr (mg/l) 186 68 390 0 Trace
(µg/L)
Cu (mg/l) 104 180 1455 0 45
Pb (mg/l) 315 670 5700 2 5
Ni (mg/l) 192 307 1674 0 0.5
Ag (mg/l) 63 17 152 12 0.3

48
 Zn (mg/l) 170 253 1600 17 14

2.9.2 Total Petroleum Hydrocarbon in Produced Water:

Total Petroleum hydrocarbons are a large family of chemicals contained in produced water.

EPA treats it as a combined unit of all petroleum hydrocarbons in the produced water. Also

it is not required by EPA standards to separately measure the quantity of each hydrocarbon,

only a combination of all is measure which is a cost effective method as well. EPA has

approved a method 1664 which influences the companies to remove the Freon in produced

water which makes produced water more environmentally friendly when it is discharge to

ocean or aquifers.

Another method enforced by EPA is method 8100 which aids in removing the carbon

gasoline hydrocarbons which ranges from 𝐶6 𝑡𝑜 𝐶9 . Overall, it is not a very hazardous

material in produced water and however it must be limited to improve the environment. The

maximum level of Total Petroleum hydrocarbon which is allowed to be directly discharged

with produced water is 5mg/L. Any value more than this much amount can be an

environment hazard and EPA can take legal action against that particular company of

drilling. However, the allowable limit for oil in produced water is 30 mg/l if it is re-injected

in the reservoir or aquifer (EPA, 2005). According to the state of Qatar the max of oil in the

reinjected produced water is 40 ppm (QP, 2014).

49
2.9.3 Standards for COD in Produced Water:

Chemical Oxygen Demand is another aspect in produced water. EPA constantly monitors

the values of these materials in produced water which is injected back to ground or

discharged in ocean. The COD which is discharged back to aquifers and oceans in produced

water has certain aquatic toxicity. It was found developed by EPA in 1987 that COD has

certain level of toxicity which can be harmful for ocean species. If high concentration of

COD is passed to oceans it can decrease the level of oxygen in the water which can be

harmful and even a life threat to ocean species. So therefore now it has been developed that

high quantity of COD can be very harmful and it can become an environment hazard. This is

the reason why both OSHA and EPA have limited the amount of COD in produced water

which is injected back to aquifers or discharged in oceans. Presently the standard is that at

least 74% of COD must be removed before the produced water is discharged to oceans.

Special treatments are used under EPA directives and regulations to reduce the level of

effluent COD in produced water. (EPA, 2014)

2.9.4 Standards for Suspended Solids:

Produced water also contains certain amount of suspended solids. These are silt, clay, sand,

precipitated Solids and organic Material (Veil J. , 2004). Normally, in United States the

drilling facilities generates 3-249mg/L of suspended solids. EPA worked upon the treatment

and required amount of suspended solids to be allowed for the effluent produced water and

finally they come to a conclusion that a restriction of 67.5mg/L of suspended solids are only

allowed for discharged produced water. However it is encouraged that only 30mg/L of

50
suspended solids in discharged produced water into the aquifers and the oceans. More than

this amount of suspended solids available in discharging produced water can be an

environmental hazard (OGP, 1994).

2.9.5 Standards for Dissolved Gases in Produced Water:

EPA and OSHA have also set standards for discharging produced water with respect to

dissolved gases. It is necessary for the oil and gas companies to remove dissolved gases

before discharging the water to a certain extent to meet offshore and onshore discharge

regulations. The main gases which are required to be removed are light hydrocarbon gases,

carbon dioxide and hydrogen Sulfide (Arthur, et al., 2005).

Access of Hydrogen sulfide or Carbon dioxide in produced water can be dangerous for

ocean species if it is discharged without proper treatment. There are many processes which

are used to treat the produced water before it is discharged into the environment (Igunnu &

Chen, 2012).

2.10 Previous studies on produced water:

Produced water characterization is the initial step to determine the treatment method for

further usage of produced water. The following characterization of produced water was

conducted from peer-reviewed literature, government or industry documents.

(Yeung, et al., 2011), did a characterization study for metals in the produced water and the

surrounding seawater. The samples were obtained from Canadian Oceans, Thebaud stations.

Thebaud platform is one of the largest gas and light oil production platform on the eastern

51
sea board of Canada. After sample collection a denaturing gradient gel electrophoresis were

performed. Results showed that the produced water discharged from the facility contain a

variety of metals at elevated concentration, including aluminum, barium, calcium, iron,

lithium, magnesium, manganese, potassium, sodium, strontium and some traces of other

metals as well.

(Utvik & Toril, 1999), analyzed produced water from four offshore oil production platforms

in the north sea. The samples were analyzed by a gas chromatography with a mass-

spectrometric detector and atomic absorption spectrometer. Results showed that the

discharged produced water had total hydrocarbon of 46 ± 13 (mg/l). metals detected barium,

iron, zinc and some traces of radioactive material 8 Bql/l of Radium.

(Alley B. , et al., 2011), conducted an analytical study for characteristics of produced water

from five sources shale gas, convectional natural gas, conventional oil, coal-bed methane

and tight gas sands. the characteristics were compared to irrigation guidelines and surface

water discharge criteria. The study indicate that constituents such as chloride, metals, and

organics may require treatment prior to management for beneficial uses.

(Veil, et al., 2005), the report describes the results of 50 samples from an oil and gas

platform located within the Gulf of Mexico. The analysis was conducted in response to a

requirement in the U.S. environmental protection agency EPA. The aim of the analysis was

to study the amount of oxygen demanding substances contained in the produced water

discharges (FakhrulRazi, et al., 2009), conducted a review of oil and gas produced water

52
treatment. Within the review a range of produced water characteristics from different

oilfields in the world were summarized.

Table 10 represent a comparison of seawater metal concentration from two sources of

literature. While table 11 and 12 compares the produced water characteristics from different

sources of literature.

Table 10: Comparison of seawater metal concentration

Table of comparison (mg/l)

Information source
Metal

(Blumer, 2007) (Yeung, et al., 2011)

Chloride 19,375 n/a

Bromide 67 n/a

Sulfate 2,712 n/a

Potassium 387 392

Sodium 10,760 10,800

Magnesium 1,294 1,290

Calcium 413 411

Strontium 8 8.1

53
 Iron n/a 0.0034

Boron n/a 4.45

Sulfur n/a 904

Barium n/a 0.021

Aluminum n/a 0.001

Lithium n/a 0.17

Manganese n/a 0.0004

54
 Table 11: Comparison of oilfield produced water metal concentration

Table of comparison (mg/l)

Information source
Metal
(Yeung, et al., 2011) (Utvik & Toril, 1999) (Alley B. , et al., 2011) (FakhrulRazi, et al., 2009)

Method used n/a n/a ICP-AES Atomic absorption

Chloride n/a n/a 36-238534 80-200,000

Sulfate n/a n/a 8-13686 2-1560

Potassium 45.8 n/a 1.6-42.6 24-4300

Sodium 2910 n/a 405-126755 132-97000

Magnesium 85.2 n/a 2-5096 8-6000

Calcium 1220 n/a 4-52920 13-25800

Strontium 102 n/a 0.05-2.2 0.02-1000

Iron 10.3 7 0.1-0.5 0.1-100

Boron 2.2 n/a n/a 5-95

Sulfur 0.33 n/a n/a n/a

Barium 58 156 0.07-7.4 1.3-650

Aluminum 0.025 n/a 0.06 310-410

Lithium 0.86 n/a n/a 3-50

Manganese 1.27 1.4-8.1 8-6000

Mercury n/a < 0.001 n/a < 0.001-0.002

Zinc n/a 0.15 6.3-17.4 0.01-35

55
 Table 12 Comparison of produced water characteristics

Information source
Factor
(Yeung, et al., 2011) (Alley B. , et al., 2011) (Veil, et al., 2005) (FakhrulRazi, et al., 2009)

PH 5 5.18-8.9 6.26 4.3-10

Temperature
13.6 n/a 38 n/a
(°C)

Salinity (ppt) 32 n/a 100 n/a

Method used for USEPA method

n/a n/a IR
TPH 1664 A

TPH (mg/l) 50 ± 18 30-90 n/a 2-565

Alkalinity n/a 300-380 n/a n/a

Conductivity
n/a 838-1469 87,452 n/a
µS/cm

Total organic

carbon TOC n/a n/a 551 0-1500

mg/l

BOD mg/l n/a n/a 595 n/a

TKN n/a n/a 111 10-300

Phosphorus n/a n/a 0.62 n/a

56
COD mg/l n/a n/a n/a 1220

TSS mg/l n/a n/a n/a 1.2-1000

Chapter 3: Research Methodology

This chapter presents a description of the research design, methodology, instrumentation and

procedure used in the conduct of the study. It also includes the sources of data, respondents

and statistical treatment applied in the data analysis and interpretation of the study.

Moreover, this section defines the technical structure supportive of the research activities

observed in the study.

3.1 Total chemical oxygen demand (COD)

Chemical oxygen demand COD is very important indicator to determine pollutants in

produced water. COD gives indication of the amount of oxygen required to oxidize the

pollutants in wastewater. The total chemical oxygen demand TCOD were determined

according to standard method ASTM-D6238 (ASTM, 2011) by using UV-Visible

spectrometer were continuous analysis of the concentration of oxygen in a combustion

process gas effluent inside the UV-Visible spectrometer is measured. The measurement of

total oxygen demand is determined by the reduction in oxygen that is caused by the

introduction of the sample into the combustion zone of the UV-Visible spectrometer. The

quick reduction in the oxygen concentration in the carrier gas is detected by an oxygen

57
sensor and indicated on a digital display and recorded PC device connected to the UV-

Visible spectrometer.

3.1.1 Determination of Dissolved chemical oxygen demand

Chemical oxygen demand COD can be divided in to two categories, dissolved chemical

oxygen demand and suspended chemical oxygen demand. Measurements of dissolved

chemical oxygen demand DCOD is measured by UV-Visible spectrometer and follows the

same principles of the total chemical oxygen demand TCOD. Before entering the sample in

the spectrometer the sample will go through filtration unit to remove all the suspended

material which define the suspended chemical oxygen demand.

3.1.2 .Materials

 Digestion Solution: Prepared by adding 10.2 g K2Cr2O7, 167 mL H2SO4, 33.3 g

HgSO4 to 500 mL of Distilled water, dilute and complete to 1 liter.

 Catalyst Solution: Prepared by adding 5.5 g Ag2SO4 to 1 Kg of Conc. H2SO4. Stir

until dissolved.

 Stock COD standard: dissolve 0.425 g of Potassium Hydrogen Phthalate in 400 mL

distilled water and dilute to 1 L to get 1000 mg/L COD.

 Preparing a series of standard solutions that cover the expected sample

concentration.

 UV-Visible spectrometer

58
3.1.3 Method

This test method covers the determination of dissolved chemical oxygen demand in the

range from 100 to 100 000 mg/L, in produced water after filtration. Larger concentrations

may be determined by suitable dilution of the sample (ASTM, 2011).

Since the analysis is based on the change in oxygen reading of the carrier gas compared to

that when a sample is introduced, the measurement range is a function of the amount of

oxygen in the carrier gas. The higher the desired concentration range, the more oxygen is

required in the carrier gas. Under recommended conditions, the carrier gas concentration

should be between two to four times the maximum desired oxygen demand. Standards were

digested by the digester and the catalyst in 150 oC, accordingly the standards were measured

by spectrophotometer at 100, 300, 500, 700, 900, 1000 mg/l COD. After preparing the

standards the samples were measured. Each measured sample required 2.5 ml of the

produced water sample, 1.5 ml of the digestion solution and 3.5 ml of the catalyst solution.

Samples, standards and blank were added to the cultured tubes. The tubes were caped tightly

and shacked to mix the layers. Then tubes were placed in Heraeus oven at 150 ℃ for 2

hours. After that, the samples were allowed to cool for about 20 minutes until reaching room

temperature. Blank and standard tubes were placed in the Varian UV- spectrophotometer to

calibrate the device before measuring samples COD values. Produced water Sample

considered to be in the upper measurements range of the UV-spectrophotometer so the

sample were diluted 1:100 and some other samples were diluted 1:200.

59
3.2 Determination of total petroleum hydrocarbons

The total amount of petroleum hydrocarbons need to be measured in order to determine the

quality of produced water. Total petroleum hydrocarbon TPH is the measure of the

concentration or mass of petroleum hydrocarbon constituents present in a given sample.

Total petroleum hydrocarbons were determined according to standard method ASTM-

D7678 (ASTM, 2011).

3.2.1 Materials

 Mid-infrared laser spectrometer with an optical power >20 mW contained by the

spectral region of 7.25-7.30 μm. Either double-beam or single-beam and capable of

making measurements in the region from 7.25-7.30 μm or single beam instrument

tunable from 7.14 – 7.30 μm5.

 Sulfuric Acid.

 Solvent : Cyclohexane

 Separation funnel

3.2.2 Method

Produced water sample is acidified by Sulfuric Acid to pH 2.500 mL of an acidified sample

of produced water with 10 mL of cyclohexane are well mixed, after that the oil layer is

extracted by the separation funnel. The extract is. The non-polar material is referred to as

total petroleum hydrocarbons TPH and is measured by mid-infrared laser spectroscopy.

60
Then by using CaF2 cell blanks, standards and samples was installed and carried out for

scanning.

3.3 Determination of heavy metals

Heavy metals in produced water were determined using inductively coupled plasma-atomic

emissions spectrometry ICP-AES. The analysis was done to determine the major, minor and

trace elements in the produced water samples. Heavy metals were measured according to

standard method EPA-200.7 (EPA, 2004).

3.3.1 Materials

 inductively coupled plasma-atomic emissions spectrometry ICP

 Analytical balance, with capability to measure to 0.1 mg

 Distilled water

3.3.2 Method

Heavy metals determination was done by taking 1 ml of sample in 100 ml flask and fills it

with distilled water 100 ml. I Cap 6000 series Thermo Scientific device was used .The

plasma was ignited and an appropraite incident power with minimum reflected power was

selected. The instrument was allowed to become thermally stable before beginning which

took around 30-60 min. The samples were inserted in the auto sampler rack and the work

sheet for samples were filled.

61
3.4 Determination of ions

Inorganic anions such as bromide (Br), nitrite (NO2), nitrate (NO3) , fluoride (F-), sulfate

(SO4), chloride (Cl-), ortho-phosphate (H3PO4) were determined according to the standard

method ASTM D-4327 (ASTM, 2008). The organic anions were determined by using ion

chromatography.

3.4.1 Materials

 Ion Chromatograph

 Effluent and Regenerator Containers.

 Effluent Pump

 distilled water

3.4.2 Method

Sample was diluted by taking 1 ml of sample in 500 ml flask and filling it with 499 ml of

distilled water. Then a small volume of sample was inserted in the special tubes designed for

the ion chromatograph device. Then the sample was injected into a Metrohm 850

professional ion chromatograph after calibration. The sample was analyzed and results were

collected from computer.

3.5 Total Suspended Solids and Total Dissolved Solids

Total dissolved solids (TDS), and total suspended solids (TSS) were determined according

to standard method (ASTM D5907)

62
3.5.1 Materials

 Analytical Balance, capable of measuring to the nearest 0.1 mg

 Drying Oven, capable of maintaining a temperature between 103 and 105°C and

between 178 and 182°C. To prevent dust and sample from being blown around

 Evaporating Dishes

 Glass Fiber Filters

3.5.2 Method

To measure the total solids a weighted beaker was filled with 100 ml of well mixed

produced water sample. The sample was placed inside an oven and evaporated to dryness

and left until the sample was completely dry. To measure the total solids the weight of dried

sample was measured, subtracting the empty weight of the beaker.

To measure the total dissolved solids a well-mixed sample is filtered through a weighed

standard glass fiber filter. The filtered sample is evaporated to dryness and heated to 180°C.

Using the analytical balance the weight of the total dissolved solids is measured.

The total suspended is calculated by subtracting the total dissolved solids from the total

solids.

3.6 Determination of total sulfides dissolved in produced water

Sulfide ion is found in produced water, causing odor and corrosion problems. If acidified,

these waters can release hydrogen sulfide, which is extremely toxic even at low levels

(ASTM, 2009). The measured total sulfide consist of S −2, H2S and HS − . Total sulfides were

63
determined by titration according to standard method according to the standard methods of

the American Public Health Association (APHA, 1980). The titration method is applicable

to the measurement of total and dissolved sulfides for water in concentrations above 1 mg/l

(APHA, 1980).

3.6.1 Materials

 Titrator

 Hydrochloric acid

 Iodine

 Distilled water

 Sodium Thiosulfate

 Starch

3.6.2 Method

Approximately 0.5 ml of a sample was taken into 100 ml conical flask and diluted with 99.5

ml of distilled water. Then adding and mixing 10 ml of 0.010N iodine .Immediately 10 ml

of concentrated hydrochloric acid HCl was added and the sample was shacked vigorously.

Without delay sample was titrated with 0.010N Sodium Thiosulfate 𝑁2 𝑆2 𝑂3, till faint yellow

appeared .Then starch was added as an indicator and titration was continued until the blue

color disappeared and became like light straw color. 100 ml of distilled water was prepared

and followed the same procedure as the sample. Then total sulfide was calculated using the

following equation

𝑆 −2 (mg/l) = (1000/ml of sample) × 0.1603 × (ml blank – ml sample)

64
Sulfide reacted with the iodine in acid solution, and the remaining iodine is then determined

by titration with sodium thiosulfate.

3.7 Determination of Total carbon dioxide dissolved in produced

water

Carbon dioxide is a major respiration product of plants and animals and a decomposition

product of organic matter and certain minerals. Surface waters generally contain less than 10

mg/L, except at local points of abnormal organic or mineral decomposition; however,

underground water, particularly deep waters, may contain several hundred mg/L. When

dissolved in water, CO2 contributes significantly to corrosion of water-handling systems.

This is particularly troublesome in steam condensate systems. Loss of CO2 from an aqueous

system can disturb the carbonate equilibrium and result in calcite encrustation of confining

surfaces. Because of the delicate balance between corrosion and encrustation tendencies,

much care must be given to control of CO2. The measured total carbon dioxide represent

CO2, carbonic acid, bicarbonate ion, and carbonate ion in water. The total carbon dioxide

dissolved in produced water were determined according to standard method ASTM D-513

(ASTM, 2011).

3.7.1 Materials

 pH Meter

 Automated titrator

 CO2 Gas-Sensing Electrode.

 Mixer with magnetic stirring bar .

65
  Buffer Solution: Dissolve 294 g of sodium citrate in approximately 700 mL of water

in a 1-L volumetric flask.

 Standard Solution: 10 ml of 0.1 M sodium bicarbonate solution

3.7.2 Method

First the sample was brought to the same temperature as the electrode and standards. The pH

meter was connected to the automated titrator then, the buffer solution was placed in the

titrator. Known volume of the sample used in a flask and connected to the pH and the

automated titrator. The sample mixed continuously using the magnetic stirrer. The volume

of the sample was entered in the titrator. Then the titrator will use the buffer solution to

titrate. The result of the total carbon dioxide will appear in the titrator screen.

3.8 Sampling and Sample preparation:

Samples of produced water were taken once a day for five days from each sampling point as

shown in figure 12 and figure 13. The volume of sample is 4 L each day from each sample

point as per standard sampling method ASTM D-4057 (ASTM, 2011). The samples were

kept dark and cool (2 oC) during transport. Representative samples of produced water are

required for the determination of chemical and physical properties. To achieve the sample

representation, a manual sampling method is applied while sampling which follows ASTM

D-4057. Manual sampling is used to obtain a small portion (spot sample) of material from a

selected area within a container that is representative of the material in the area, a sample

composition is representative of the total material in the container. A series of spot samples

may be combined to create a representative sample. A sample obtained by submerging a

66
bottle to a point as near as possible to the draw-off level, then opening the sampler and

raising it at a rate such that it is approximately three-fourths full as it emerges from the

liquid.

Prior to obtaining a representative sample, sampling points shall be adequately flushed to

remove any hold ups. When flushing into a metal container, an earthing bond must be

attached between the sample line and the container to avoid static ignition. Liquid sampling

shall be carried out using metal containers. These containers will be earthed to avoid any

static ignition and are specified for hydrocarbon sampling.

Figure 12: Field A sample points

67
 Figure 13: Field B sample points

3.9 Analysis:

The samples were placed on a shaking table for one minute for homogenization. Each

sample was divided in to 3 subsamples to determine the chemical and physical

characteristics of the produced water. The table 13 includes some of the experiments that

were done during the study of produced water characterization and there corresponding

technology used.

68
 Table 13: Analytical techniques

Experiment Technology used

Total petroleum hydrocarbon (TPH) Mid-IR laser spectroscopy

Inductive coupled plasma atom emission

Heavy metals characterization
spectroscopy

Ions characterization Ions-chromatography

Chemical oxygen demand (COD) UV-Visible spectrometer

The analysis with respect to the total petroleum hydrocarbon was done by Mid-IR laser

spectroscopy as described by ASTM D-7678. One of the most common spectroscopic

techniques is infrared (IR) spectroscopy. It is mainly used to determine the chemical

functional groups in the sample. The absorption Characteristic of IR radiation frequencies is

different for each chemical functional group. That makes the IR spectroscopy a very

important tool for structural analysis. For the total petroleum experiment the interest rely

upon the total amount of petroleum groups detected by the IR.

Mercury (Hg), lead (pb), arsenic (As) and iron (Fe) and other heavy metals presented in

produced water were analyzed by inductively coupled plasma atom emission spectrometry

(ICP) as described by EPA 200.7. One of the most powerful and popular analytical tools for

the determination of traces elements in a myriad of sample types is ICP. Plasma is any form

of mater that is characterized to be able to conduct electricity and could be affected by

magnetic field. light of a wavelength characteristic of the element of interest is shone

69
through this atomic vapor. Some of this light is then absorbed by the atoms of that element.

The amount of light that is absorbed by these atoms is then measured and used to determine

the concentration of that element in the sample.

Fluoride, Chloride, Bromide, Nitrate and Sulfate were analyzed by Ions-chromatography as

described by EPA 300.1.

Chemical oxygen demand (COD) were analyzed by UV-Visible spectrometer as described

by ASTM D-6238.

70
Chapter 4: Results and discussion:
This chapter discusses the result achieved to evaluate the treatment system used to remove

the oil content from produced water. There are also evaluations of other treatment

parameters. The equipments in the treatment systems are being evaluated based on the

characterization result achieved.

This chapter also discusses wither a biological treatment is sufficient for produced water

generated from Qatar oil fields, by studying the fraction of Chemical oxygen demand (COD)

The result of an average value of some chemical and physical characteristics of produced

water sample from Field A and Field B are given in table 14. A comparison of daily samples

taken during five discrete days is shown in Appendix A for each stage of treatment.

Uncertainty in sampling and analysis, expressed as relative standard deviation (%) is also

shown in Appendix A for each stage of treatment. Samples were collected from the

discharge of the major units. The result achieved considered that Field B hydrocyclones

operate in parallel. Location of observed samples are shown in section 3.8 figure 12 for field

A and figure 13 for field B.

71
 Table 14: Characterization of produced water from Field A and Field B

Field A Field B

gravity gravity
1st stage 2nd stage 1st stage Surge
separation separation Hydrocyclon Hydrocyclon Hydrocyclon
separation separation separation Drum
tank tank A discharge B discharge C discharge
discharge discharge discharge discharge
upstream discharge

pH 6.25 6.22 6.25 6.15 5.78 5.65 5.78 5.86 6

Conductivity
107.28 107.9 105 106 109 107.5 108.5 108.3 109.6
(ms/cm)

COD ( ppm ) 8594 8823 7440 3764 16822 10280 8850 12000 7250

Readily

Biodegradable 2820 2776 2357 1331 4800 3100 3160 3240 3000
COD ( ppm )

Dissolved
5146 5669 3638 2258 11500 6420 3321 8931 4300
COD (ppm)

THC ( ppm ) 3492 1536 1592 53 1164 99 86.5 126 40

BTEX (ppm) N/A N/A N/A 4.5 N/A N/A N/A N/A 6.74

Phenol (ppm) N/A N/A N/a 1.25 N/A N/A N/A N/A 1

TSS (g/l) 18 15 14 4 15 14 38 28 2

TDS (g/l) 146 139 147 170 275 290 290 290 290

TS (g/l) 164 154 161 174 290 304 328 318 292

72
Dissolved CO2 15211 15351 13200 14945 10560 9720 9893 9724 11000
(ppm)

Sulfide (ppm ) 199 156 40 30 150 134 101 140 115

TKN (ppm) N/A N/A 85.8 86.6 N/A 116.15 116.15 116.15 116.17

Phosphate
N/A N/A N/A 0.3 N/A N/A N/A N/A 0.5
(ppm)

Ammonical

Nitrogen N/A N/A N/A 3 N/A N/A N/A N/A 3

(ppm)

4.1 Total Petroleum hydrocarbon

The main constrain of produced water is the total petroleum hydrocarbon. TPH is the only

regulated factor in produced water at the state of Qatar in case of reinjection. Across the

treatment stages for both fields the hydrocarbon content in produced water is decreasing.

According to historical data of both fields the produced water starts with THC of 5400 ppm

where at that stage it would be completely mixed with oil and didn’t go through the 1 st

separation stage.

Table 15 shows how well the unit processes remove suspended oil and particles. Each unit

process uses an individual technology. Most technologies used represent primary treatment

method. The function of most water treating equipment is to cause the oil droplets which are

73
dispersed in the water continuous phase, to separate and float to the surface of the water so

they can then be removed (Stewart & Arnold, 2011).

4.1.1 Equipment efficiency in TPH removal

Table 15 shows the percentage of oil removal for different equipment used in Field A and

Field B it also contain the capacity by volume for each equipment. The operating time for

equipments are different. According to the measured hydrocarbons before and after each

unit the most efficient equipment is the gravity separation tank but it is considered as

onshore equipment. The gravity separation tank occupies a large volume space about 25,000

m3 with long residence time it is not convenient to operate it onshore with total capacity by

volume of 0.14 h-1. The hydrocyclone has the highest capacity to remove oil content in an

offshore unit and the highest capacity by volume with percentage removal of 89.2% -

92.6% and capacity of 312 h-1.

Capacity by volume is a term of space occupancy and it is given by the following equation:

Capacity by volume = flow/volume eq.1

Where the flow is the mean flow rate, the volume is represented by equipment volume or the

space that the equipment occupies. The capacity by volume takes units of inverse time

(Judd, et al., 2014).

74
 Table 15: Percentage removal of oil by unit process

Operating Capacity
Flow Equipment Oil Inlet Oil outlet
Equipment residence by % St.
Technology rate volume concentration concentration
type time volume removal deviation
(m3/h) (m3) (ppm) (ppm)
( min ) (h-1)

3-phase

Separation horizontal 3 1312 197 6.7 5400 1164 78% 0.026038

separator

2-phase

Separation horizontal 1 3141 191 16 5400 3492 35% 0.132954

separator

2-phase

horizontal
Separation 2 1281 135 9 3492 1536 56% 0.143481
low pressure

separator

Separation Surge drum 5 894 72 12 126 40 68.3% 0.013861

Gravity

Separation separation 360 3500 25,000 0.14 1592 53 96.7% 0.006522

tank

De-oiling
92.6%-
Hydocyclon N/A 937 3 312 1164 86.5-126 0.01637
hydrocyclone 89.2%

75
Since the hydrocyclone is the most efficient technology it is studied by many scientist and

engineers. Simon Judd had studied the performance of various offshore produced water oil

removal technologies (Judd, et al., 2014). One of the studied technologies is hydrocyclone

figure 14 represent a comparison of the observed date with the literature data. The data are

very comparable. The capacity by volume of hydrocyclone studied by Simon Judd is 450 h-
1
, while the observed hydrocyclone had a capacity of 312 h-1. It can be noticed that the

literature data of the hydrocyclone have higher efficiency than the observed hydrocyclone,

that is because of the oil droplet size. As the oil droplet size gets smaller it will be more

difficult to remove. The studied oil droplet size had a mean oil droplet diameter of 11

microns, while the literature data observed result for oil droplet size ranging 12-20 microns.

120

100

80 Observed
hydrocyclone

60

Hydrocyclone
40 literature date
(Judd, et al., 2014)
20

0
% oil removal average Oil droplet size % residual oil
(microns)

Figure 14: Hydrocyclone performance compression

76
The gravity separation tank is a powerful tool to separate oil and water. Figure 15 compares

the observed gravity separation tank with API separator from literature data (Judd, et al.,

2014). Although gravity separation tank is not structured the same as the API separator but,

the operation of both equipments are derived by the force of gravity. As shown in figure 15

gravity separation tank have much higher efficiency to remove oil than the API separator

although the observed oil droplet size that entered the gravity separation tank was much

lower than the given data of the API separator. The studied oil droplet that entered the

gravity separation tank had an oil droplet size of 24 microns while the literature date for yhe

oil droplet size that entered the API separator are 150 microns The only constrain for the

gravity separation tank is the size, as shown in figure 15 the gravity separation tank capacity

by volume is much lower than the API separator.

180

160

140

120 Observed gravity

separation tank
100

80
API separator
60
literature date
40 (Judd, et al., 2014)

20

0
% oil removal average Oil droplet size Capacity by volume
(microns) (0.01 h-1)

Figure 15: Gravity separation tank compression

77
4.1.2 Field efficiency in TPH removal

Field A starts with 1st stage discharge of 3492 ppm and ends up at the last stage discharge

with 53 ppm. The final result of Field A would be slightly above the regulation limit in the

state of Qatar if it was a monthly average, however the result of Field A doesn’t represent a

monthly average. It only represents 5 samples collected in five different days. However, an

improvement in the treatment stages might be recommended for Field A. Field B starts the

first stage discharge with THC of 1164 ppm and ends up at the last stage discharge with 40

ppm. The final result of Field B is within the environmental regulation in the state of Qatar

for produced water reinjection (QP, 2014). The reason that Field B has a lower content of

hydrocarbon in the disposed produced water might be due to the hydrocyclones. Although

there is a magnificent change in the last stage of treatment at Field A, the gravity separation

tank which reduces the petroleum hydrocarbon to about 96.75 there might be still small oil

droplet that needs to be removed. BTEX and phenols are part of the total hydrocarbon

content in produced water. The following table shows the total hydrocarbons , BTEX and

phenols for both fields A and B last stage discharge compared with produced water

characteristics studies that was done earlier in the North sea oil fields (FakhrulRazi, et al.,

2009) and Turkey oil fields (Ozgun, et al., 2013). As shown in table 16 Field A and Field B

are within the range of earlier studies results.

78
 Table 16: Total Petroleum hydrocarbon comparison with earlier studies

North sea oil fields Qatar standards

Turkey oil fields
Field A Field B (FakhrulRazi, et al., for Produced
(Ozgun, et al., 2013)
2009) water reinjection

THC (ppm) 53 40 2-565 28-195 40

BTEX (ppm) 4.5 6.74 0.39-35 6.31-38 NA

Phenols
1.25 1 0.009-23 0.53-1.90 NA
(ppm)

4.2 Oil droplet size distribution

Oil size distribution was done for 4 produced water sample. The locations were chosen for

future treatability enhancement. The oil droplet size is one of the key parameters that

determine the type of treatment. Usually small oil droplets are very difficult to remove.

There is another factor that plays a role in the treatment method and that is the shear strength

between the oil layer and the water layer.

Figure 16 and figure 17 show the sample point locations. All samples follow ASTM

regulation for sampling (ASTM, 2011). Field A Samples were selected in order to study the

changes of the particle size in the produced water at the last stage of treatment, before the

gravity separation tank and after. Field B samples were selected in order to measure the

efficiency of the hydrocyclone unit coupled with the surge drum. The distribution analysis

parameters for the oil droplet size are listed in table 17.

79
Figure 16: Field A sample point for oil size distribution

Figure 17: Field B sample point for oil size distribution

Table 17: Oil droplet size analysis

80
 Field A Field B

Parameter
Gravity Gravity
Hydrocyclon C Surge drum
separation tank separation tank
inlet discharge
upstream discharge

Mean Diameter (microns) 24.2149 2.96 11.2537 2.342

Stnd. Deviation (microns) 22.398787 2.428 13.459483 1.557466

Norm. Stnd. Dev. 0.925 0.818 1.196 0.665

Variance 0.856 0.669 1.43 0.442

Z-Avg. Diff. Coeff. (cm2/s ) 1.92E-10 1.57E-09 4.13E-10 1.98E-09

4.2.1 Field A gravity separation tank upstream:

The results showed that produced water of gravity separation tank upstream had a mean oil

droplet diameter of 24.21 microns and a standard deviation of 22.4 microns. Figure 18

shows the graphical analysis of 1st stage separation of field A produced water samples. As

shown in the figure the data represent binomial distribution 50% of oil droplet size

distribution is < 17 microns.

81
 Figure 18: Oil droplet size distribution for Field A 1st stage separation

4.2.2 Field A gravity separation tank discharge :

The second sample of field A was taken from the last stage of treatment, gravity separation

tank discharge. Produced water sample had a mean oil droplet diameter of 2.96 microns and

a standard deviation of 2.428 microns. This indicates a major reduction in the oil droplet

size. Figure 19 shows the graphical analysis of last stage of treatment at field A, gravity

separation tank produced water sample. As shown in the figure the data represent normal

distribution. The cumulative analysis is listed below:

25% of oil droplet size distribution is < 1.25 microns

50% of oil droplet size distribution is < 2.15 microns

75% of oil droplet size distribution is < 3.71 microns

82
80% of oil droplet size distribution is < 4.25 microns

90% of oil droplet size distribution is < 6.08 microns

99% of oil droplet size distribution is < 14.02 microns

Figure 19: Oil droplet size distribution for Field A last stage of treatment

The result of field A produced water oil droplet size distribution is showing a reduction. The

reduction by gravity separation tank is about 87.8%. Referring to table 14 the average

discharged concentration of oil in produced water is 53 ppm which is considered to be

slightly higher than the regulation limit according to Qatar petroleum. The produced water

from field A starts the first stage discharge with oil concentration of 3491.6 ppm as per table

14 of produced water characteristics. This indicates 98.5% reduction in the total

concentration of oil in produced water..

83
4.2.3 Field B hydrocyclon upstream:

Field B hydrocyclon inlet of produced water had a mean oil droplet size of 11.25 microns

and a standard deviation of 14.46 microns. Figure 20 shows the graphical analysis of Field B

oil size distribution on produced water that is entering the haydrocyclons. As shown in the

figure the data represent binomial distribution 50% of oil droplet size distribution is < 5.3

microns.

Figure 20: Oil droplet size distribution for Field B hydrocyclone inlet unit

84
4.2.4 Field B surge drum discharge :

The second sample of field B was taken from last stage of treatment, surge drum discharge.

Produced water had a mean oil droplet size of 2.34 microns and a standard deviation of 1.56

microns. Figure 21 shows the oil droplet size distribution of the last stage in field B the

distribution result is showing as normal distribution. As field A, filed B is also showing a

reduction in the oil droplet size.

Figure 21: Oil droplet size distribution for Field B last stage of treatment

The reduction in the hydrocyclone unit coupled with the surge drum is about 79%. Referring

to table 14 the average concentration of oil in the discharged stream of produced water is 40

ppm. Although the concentrations of the total petroleum hydrocarbon are within the limits of

85
regulation and no further treatment is required by the regulator but, the process could be

enhanced for future regulation or production capacity enhancement. The inlet stream to the

hydrocyclone unit starts with about 1164 ppm. The total reduction of oil concentration in

produced water by the hydrocyclone unit coupled with the surge drum is 96.5%.

The main reduction of the oil concentrations and oil droplet size relay on the hydrocyclone

unit coupled with the surge drum for field B. While for field A, the main reduction of the oil

concentrations and oil droplet size relay on the gravity separation tank.

4.3 Solids in produced water

It is important to observe the amount of solids in produced water due to environmental

regulation and operational philosophy. If the water is re-injected into aquifer or production

reservoirs then the impact of suspended solids will not be environmental constrain only but

it will also impact the process of oil extraction. In other words the process operation will be

upset due to the presence of suspended solids. Suspended solids may precipitate on the

pipeline which forms deppres on the pipeline that could causes a blockage of the pipeline. It

also affects the performance of other equipments as well like pumps and vessels.

However, the suspended portion of the total solids detected is not high. Table 18 shows the

total solids across the treatment stages. The treatment stages are not very sufficient in

removing the suspended solids except in the final stage where sufficient time provided. Field

B hydrocyclon stage operate in parallel, although the three hydrocyclone operates in parallel

the removal of solids is unstable. It is also noticed that the hydrocyclones are only able to

remove the suspended solids. At the last stage of field A the average measured total solids

86
 was 174 g/l with only 2% of suspended solids, while for field B it was 292 g/l with only 1%

of suspended solids.

An American study showed that the suspended solids could be ranging from 1.2-1000 ppm

(FakhrulRazi, et al., 2009). Another study that was done in turkey to characterize produced

water indicates that the suspended solids were ranging from 29-87 g/l (Ozgun, et al., 2013).

The result observed from field A and field B are closer to the result found from

characterizing produced water generated in turkey that could be due to the similarity in the

characteristics of the generated produced water.

Table 18: Total solids across treatment stages

Field A Field B

2-phase

2-phase horizontal gravity gravity 3-phase

Surge
horizontal low separation separation horizontal Hydrocyclone Hydrocyclone Hydrocyclone
Drum
separator pressure tank tank separator A discharge B discharge C discharge
discharge
discharge separator upstream discharge discharge

discharge

TSS (g/l) 18 15 14 4 15 14 38 28 2

TDS (g/l) 146 139 147 170 275 290 290 290 290

TS (g/l) 164 154 161 174 290 304 328 318 292

% TSS 11% 10% 9% 2% 5% 5% 12% 9% 1%

87
4.3.1 Solids composition:

Table 19 shows the constituents of solids present in produced water. Composition of field A

and Field B is almost similar. About 50% of the solids are chloride which is normal due to

the nature of saline water. It was noticed that O and Na were changing before and after the

treatment while the rest of the components were almost constant.

Table 19: Element of solid content by wt%

Component Field A Field B

O 13.61 17.63

Na 13.79 8.9

Mg 4.91 3.52

Al 0.48 0.53

Cl 51.69 48.67

K 2.89 1.84

Ca 12.64 18.9

Total 100 100

88
4.4 Dissolved oxygen and oxygen demand:

4.4.1 Biochemical oxygen demand:

Most aquatic habitats are occupied by fish or other animals requiring certain minimum

dissolved oxygen concentrations to survive. Dissolved oxygen concentrations may be

measured directly in produced water, but the amount of oxygen potentially required by other

chemicals in the wastewater is called oxygen demand. Dissolved or suspended oxidizable

organic material in the produced water will be used as a food source. Microorganism will

consume any organic and inorganic matter added to it and will produce biomass using

oxygen present in the produced water. The oxygen required for the degradation of the

organic matter biologically is called the Biochemical Oxygen Demand. Divided material is

readily available to microorganisms whose populations increases to digest the amount of

food available. Digestion of this food requires oxygen, so that oxygen content of the water

will ultimately be decreased by the amount required to digest the dissolved or suspended

food. Oxygen concentrations may fall below the minimum requirement of the aquatic life, if

the rate of oxygen utilization exceeds the replacement by atmospheric oxygen, and that is

the main issue and concern. The reduction of O2 means prosperities in the algae growth

which means blockage for the visible light and also decreasing the amount of dissolved

oxygen (Goldman & Horne, 1994).

The reaction for biochemical oxidation:

89
Oxidizable material + bacteria + nutrient + O2 → CO2 + H2O + oxidized inorganics such as

NO3 or SO4 eq.2

Oxygen consumption by reducing chemicals such as sulfides and nitrites is illustrated as

follows:

S- + 2 O2 → SO4- eq.3

NO2- + ½ O2 → NO3- eq.4

Eq.2 shows another reason for the presence of high concentration of CO2. Since the amount

of CO2 is very high it could be also an indication that the oxidizable material are consuming

lots of O2. Those biochemical reactions create what is measured in the laboratory as

Biochemical oxygen demand. According to the laboratory work done for the produced water

samples from both Field A and Field B the average BOD for the water samples is very small

compared to chemical oxygen demand which is very high. The average chemical oxygen

demand is 9314ppm. The reason of the low BOD is the chemical injected to improve

filtration process. Due to that chemicals injection most of the bacteria will be killed.

4.4.2 Chemical oxygen demand:

Oxidizable chemicals such as reducing chemicals within the sample initiate chemical

reactions, those chemical reactions are responsible for the chemical oxygen demand. Figure

22 and figure 23 shows total COD concentration changes across the treatment stages for

Field A and Field B. Field A starts with COD concentration of 9213 to 7249 ppm at the

discharge of the first stage and end up by COD concentration of 4986 to 2589 ppm at the

90
discharge of the last stage of treatment. That would lead to COD reduction nearly about

57%. While Field B starts the discharge of the first stage of treatment with COD

concentration of 20754 to 13578 ppm and end up by COD concentration of 8022 to 6439

ppm. So Field B treatment method is reducing the COD concentration is about 79%. Table

20 indicates the recovery of the chemical oxygen demand after each stage, also the total

recovery of all the units.

12000

10000

8000
Sample 1
Sample 2
6000
Sample 3
Sample 4
4000 Sample 5
Average

2000

0
2-phase horizontal 2-phase horizontal gravity separation gravity separation
separator discharge low pressure tank upstream tank discharge
separator discharge

Figure 22: COD changes across treatment stages in Field A

91
 25000

20000

15000 Sample 1
Sample 2

10000 Sample 3
Sample 4

5000 Sample 5
Average

0
3-phase HydrocyclonA Hydrocyclon B Hydrocyclon C Surge Drum
horizontal discharge discharge discharge discharge
separator
discharge

Figure 23: COD changes across separation and treatment stages in Field B

Although Field B starts the treatment with higher COD concentration than Field A, the

treatment method used in Field B is more efficient in reducing the COD concentration than

Field A. That would be due to the usage of Hydrocyclones in Field B Field. Hydrocyclones

are showing high COD reduction even though hydrocyclone C indicates less COD

concentration reduction than hydrocyclon A and hydrocyclone B , which might be due to the

operational philosophy used by the operators on Field B field it still shows that

hydrocyclone treatment stage records the highest COD concentration reduction of about

38%. According to earlier studies done to characterize produced water generated in turkey

the COD in ppm of produced water could be ranging from 545-2773 (Ozgun, et al., 2013).

Felid A and Field B high concentration of COD could be explained by the treatment method

used, there is no special treatment used to reduce the COD concentration.

92
 Table 20: average COD concentration and % recovery across treatment stages

2- phase low
2-phase Gravity Gravity
pressure
horizontal separation separation
Field A horizontal NA
separator tank tank
separator
discharge upstream discharge
discharge

Field A average COD

8723.8 8823 7440 3764 NA
concentration (ppm)

Field A % recovery NA 0% 16% 49% NA

Field A total % recovery 57%

3-phase

horizontal Hydrocyclon Hydrocyclon Hydrocyclon Surge drum

Field B
separator A discharge B discharge C discharge discharge

discharge

Field B average COD

16822 10280 8850 12000 7250
concentration (ppm)

Field B % recovery NA 39% 47% 29% 30%

Field B total % recovery 57%

93
4.4.2.1 COD Fractions

COD fractions are classified as biodegradable COD (bCOD) and non-biodegradable COD

(nbCOD) as discussed in literature review chapter figure 9. Biodegradable COD can be in

the form of particulate or can be soluble in water. The soluble COD is referred to as readily

biodegradable COD (rbCOD) while particulate COD is refered to as slowly biodegradable

COD (sbCOD). The other class of COD which is non-biodegradable can also be in the

soluble (nbsCOD) or particulate (nbpCOD) form. The following equations were used to find

the fractions of COD (Vollertsen & Jacobsen, 2002).

COD = bCOD + nbCOD eq.8

nbCOD = sCODe + nbpCOD eq.9

bCOD = rbCOD + sbCOD eq.10

COD can be sorted as total of soluble particles and total non-soluble particles. This can be

achieved by adding soluble biodegradable COD and soluble non-biodegradable COD, as

well as adding biodegradable particulate and non-biodegradable particulate.

COD = sCOD + pCOD eq.11

sCOD = rbCOD + nbsCOD eq.12

4.4.2.1.1 Readily biodegradable COD

A material is described or classified as ‘readily biodegradable’ if there is evidence from

standard tests that it will be broken down by living organisms and thus removed from the

94
environment. To pass the most stringent tests defined by the Organization for Economic Co-

operation and Development, at least 60- 70% of the material must be broken down within

ten days (OECD, 2005).

A detailed characterization of the produced water organic matter can be achieved, dividing

the total COD into fractions with different microbiological properties. One of the COD

fractions is the active agent in the microbial transformations: the heterotrophic microbial

biomass. Other fractions are substrate for this biomass. Some of the substrate is readily

biodegradable and some is more slowly biodegradable. Slowly biodegradable COD must be

hydrolyzed before it can be utilized by the heterotrophic biomass. The other part of the

organic matter is inert which is not biodegradable at all (Vollertsen & Jacobsen, 2002).

It can be observed from the definition of biodegradable COD that there is a relation between

BOD and the biodegradable COD. bCOD can be converted to BOD by dividing bCOD by a

factor ranging between (1.6 to 1.7) (Vollertsen & Jacobsen, 2002).

bCOD  (1.6 to 1.7) BOD eq.13

Table 21 includes the fractions of COD and the rate of biodegradable COD as well as the

other fraction rate. The results had a small changing margin for all treatment stages in both

fields. This indicates that the fraction of COD is not changing with treatment stage. The

average readily biodegradable rate for all samples from both fields is 63.3% while the

average biodegradable COD rate is 51.5%. it can be pointed out that COD fraction in the

produced water samples analyzed indicates that more than half of the produced water is

95
 biodegradable and more than half of the biodegradable COD is readily biodegradable.

Knowing that, it can be concluded that biological treatment is helpful for both fields.

Table 21: COD fractions and biodegradability rates

Non Readily Slowly

Field Sample Location nbCOD bCOD sbCOD nbpCOD
Biodegr
Biodegra Biodegr Biodegr
adable
(ppm) (ppm) (ppm) (ppm) dable adable adable
COD %
COD % COD % COD %
2-phase

separator
4174 4421 1601 1848 51.4 48.6 63.8 36.2
discharge

2-phase low

pressure

separator 4441 4382 1606 1548 49.7 50.3 63.3 36.7

Field
discharge

A
gravity

separation tank
3451 3989 1632 2170 53.6 46.4 59.1 40.9
upstream

gravity

separation tank
1781 1983 652 854 52.7 47.3 67.1 32.9
discharge

3-phase
Field
separator
8886 7936 3136 2186 47.2 52.8 60.5 39.5
B discharge

96
 Hydrocyclone A

discharge 5195 5085 1985 1875 49.5 50.5 61.0 39.0

Hydrocyclone B

discharge 3675 5175 2015 3514 58.5 41.5 61.1 38.9

Hydrocyclone C

discharge 6613 5387 2147 922 44.9 55.1 60.1 39.9

Surge Drum

discharge 3200 4050 1050 1900 55.9 44.1 74.1 25.9

4.4.2.1.2 Readily biodegradable COD / COD ratio

COD is the amount of oxygen required to completely oxidize waste chemical material

present in the produced water. RBCOD is the readily biodegradable substrate. The following

table shows the ratio of the readily biodegradable COD and the total COD presented in the

samples of produced water. The ratio of RBCOD/COD is very comparable for both Field B

and Field A. This ratio is an indication of the toxicity of the produced water. The ratio range

for all samples is between (0.27-0.41) which is low ratio. This low ratio could be an

indication of toxicity or bad biodegradability or could be both. Field A shows an

improvement of (3.2% to 9.4%) from one separation stage to other. The total change of the

ratio from the first stage of separation to the last stage of separation is calculated as the

following equation:

(𝐼𝑛𝑓𝑙𝑢𝑛𝑒𝑡 𝑅𝑎𝑡𝑖𝑜−𝐸𝑓𝑓𝑙𝑢𝑒𝑛𝑡 𝑅𝑎𝑡𝑖𝑜)

Percentage of ratio improvement = ∗ 100% eq.14
𝐸𝑓𝑓𝑙𝑢𝑒𝑛𝑡 𝑅𝑎𝑡𝑖𝑜

97
 ( 0.35−0.33)
Field A percentage of RBCOD/COD ratio total improvement = ∗ 100% = 6%
0.33

RBCOD/COD ratio changes is quite low, however there is a slight improvement of the ratio

from stage to stage. These changes are due to the type of physical and chemical treatment,

were in physical treatment some of the biodegradable suspended solids and light density

biodegradable component is removed by density difference. Low density component is

removed in the early stages when the two phase separation takes place, the gas phase

separate from the liquid phase by the effect of momentum change. Some of the gas molecule

might carry on part of the low density biodegradable material. While the biodegradable

suspended solids is removed in the last stage filtration. Results shows that the last stage of

treatment have greater influence on the produced water sample than the earlier stage of

treatment. Chemical injection also helps in separating the low density biodegradable

material.

Field B shows an improvement of (3.4% to 20%) from one separation stage to other. The

total change of the ratio from the first stage of separation to the last stage of separation is

calculated using eq.14. Field B percentage of RBCOD/COD ratio total improvement is

41.4%. The total recover of Field B is higher than Field A in term of RBCOD/COD ratio.

Using hydrocyclons added great benefits for Field B separation process over Field A. Ratio

improvement in hydrocyclon fluctuate from (3.4% to 20%) that’s because the performance

of the hyrocylone is not steady state but, dynamic depending on the turbulently of the flow

and the flow rate were the pressure difference is the main driver for the hydrocyclons.

98
Overall RBCOD/COD Ratio for both Field B and Field A implement a slow biodegradation

of the contaminants.

Table 22: RBCOD/COD ration for Field A and Field B

percentage of
Sample COD RBCOD RBCOD/COD
ratio
Location (ppm) (ppm) Ratio
improvement %

2-phase separator
8594 2820 0.33 NA
discharge

2-phase low pressure

8823 2776 0.31 0%
Field separator discharge

A gravity separation tank

7440 2357 0.32 3.2%
upstream

gravity separation tank

3764 1331 0.35 9.4%
discharge

3-phase separator
16822 4800 0.29 NA
discharge

Hydrocyclon A
10280 3100 0.30 3.4%
Field discharge

B Hydrocyclon B
8850 3160 0.36 20%
discharge

Hydrocyclon C
12000 3240 0.27 N/A
discharge

99
 Surge Drum discharge 7250 3000 0.41 14%

Biodegradable organics plays an important role in oxygen depletion which has a great

impact on the aquatic life. The lack of oxygen may put the aquatic life in great danger were

the amount of the dissolved oxygen is not sufficient for the survival of aquatic organisms.

The biodegradable organics acts as substrate for the microorganisms, the microorganisms in

turn needs nutrients and oxygen in order to have the energy to biodegrade the organics.

The mechanism that affects organic matter, pathogens and nutrients are chemical reactions

such as hydrolysis, photolysis, oxidation, reduction or microbial activity.

4.5 Extraneous and intrinsic conductivity

Electrical conductivity (EC) is a measurement of the dissolved ions in an aqueous solution,

which relates to the ability of the material to conduct electrical current through it.

Conductivity measurement is very extensive and functional method for quality control

purposes. Conductivity measured by estimation of the total number of ions in a solution or

direct measurement of components in process solutions.

The conductivity of water is directly linked to the concentration of the ions and their

mobility. The conductivity depends on the value of the pH, on the temperature of

measurement and on the amount of CO2 which has been dissolved in the water to form ions.

The conductivity due to these factors is intrinsic conductivity. The conductivity is also

100
affected by the concentration of ions already present in the water such as chloride, sodium

and other ions. This conductivity is extraneous conductivity.

Table 23 shows the total detected ions in produced water. Chloride represent the major ions

in produced water, followed by sodium and calcium. There were traces of nitrate detected

on the early stages of Field A. the chloride ions is the dominate ions because of the

chemicals injection during the oil extraction process.

Figure 24 represents the total ions concentration existing in produced water of Field A and

Field B with respect to conductivity. The data of total ions represent 4 sample points for

field A and five sample points for Field B. Conductivity and concentration from each sample

point represent an average of 5 measurements.

101
 Table 23: Total ions present in produced water

Field A Field B

2-phase
2-phase gravity gravity 3-phase
horizontal
horizontal separation separation horizontal Hydrocyclon Hydrocyclon Hydrocyclon Surge Drum
low pressure
separator tank tank separator A discharge B discharge C discharge discharge
separator
discharge upstream discharge discharge
discharge

Fluoride (ppm)
0.04 5.1 4.112 0.034 3.3 2.5 2.8 2.7 2.9

Chloride (ppm)
111860 124900 73330 101300 211160 163980 200100 195480 229360

Bromide (ppm)
29 15.9 12.4 31.9 36 40 52 49 44

Nitrate (ppm)
2.1 7.6 N/D N/D N/D N/D N/D N/D N/D

Sulfate (ppm)
17.8 49.3 39.6 15.6 15 30 41 41 48

Sodium (ppm) 702 817.4 479.1 611.2 1488 1122 1156 1124 1860

Calcium (ppm)
129.4 165 88.38 100.5 283 294.4 368.7 296.9 360.1

Magnesium
30.2 23.82 40.08 34.15 46.28 47.49 56.79 46.48 56.82
(ppm)

Potassium
19.96 16.07 24.49 21.25 47.78 50.97 62.03 50.4 60.82
(ppm)

Total Ions
112790.50 126000.19 74018.16 102114.63 213079.36 165567.36 201839.32 197090.48 231792.64
(ppm)

102
Figure 24 shows the correlation of the extraneous conductivity, it indicates that the

conductivity is directly proportional to the total number of ions existing in produced water.

The coefficient of determination is very high for field A it is 0.9441 and for field B it is

0.9852 . Figure 24 proves the fact that the conductivity is proportional to the concentration

of ions by following the equation of state, the slop and the intercept of both relations are

very close. But not only the concentration that affect the conductivity there are also other

factors affect the conductivity like the mobility of the ions, valence of ions and temperature.

The ions that are detected by the ion-chromatography device are Fluoride, Chloride,

Bromide, Nitrate and Sulfate. Sodium, calcium magnesium and potassium were measure by

Inductive coupled plasma atom emission spectroscopy Other ions were below detection

point or didn’t exist.

111

110

109 y = 3E-05x + 102.1

Conductivity ms/cm

R² = 0.9852
108 Field A

107 Field B
Linear (Field A)
106
Linear (Field B)
105 y = 6E-05x + 100.62
R² = 0.9441
104
0 50000 100000 150000 200000 250000 300000
Total existing ions ppm

Figure 24: The relation of conductivity and total existing ions for Field A and Field B

103
Table 24 compares the result of last stage of treatment for both Field A and Field B ions

concentration and conductivity, with some produced water analysis that was done earlier in

the North sea oil fields (FakhrulRazi, et al., 2009) and Turkey oil fields (Ozgun, et al.,

2013). The comparison shows similar results for most of the ions. the diverted result of ion

concentration such as chloride ions could be explained by referring to some facts such as the

differences in the geographical area, the amount of oil produced to the water ratio and the

treatment method used to treat the produced water. Not only that the diversion of Field A

and Field B from Turkey oil fields result could be due to the nature of oil field. It is not

stated in the article that the oil fields are offshore oil fields. The diversion of the

conductivity data could be due to the differences in total ions concentration and the

temperature difference. It also could be due to the facts stated above.

Table 24: comparison of Field A and Field B ions concentration and conductivity with other oil fields

Field A Field B North sea oil fields Turkey oil fields

discharge discharge (FakhrulRazi, et al., 2009) (Ozgun, et al., 2013)

Conductivity
106 109.6 136-586 9.5-39
(ms/cm)

Fluoride (ppm) 0.034 2.9 N/A 0.33-2.68

Chloride (ppm) 101300 229360 77-3990 236-17270

Bromide (ppm) 31.9 44 N/A 10.68-60.6

Nitrate (ppm) < 0.001 < 0.001 N/A 0-2.03

Sulfate (ppm) 15.6 48 10-300 45.2-252

104
Sodium (ppm) 611.2 1860 132-97000 2025-7740

Calcium (ppm) 100.5 360.1 13-25800 26-1595

Magnesium
34.15 56.82 8-6000 23.1-148
(ppm)

Potassium
21.25 60.82 24-4300 116.7-330
(ppm)

4.6 The relation between ions and dissolved CO2

Another factor that affects the total number of ions existing in the produced water are the

dissolved CO2. The reason of CO2 existence in the produced water sample is due to the

presence of insoluble inorganic carbon in the produced fluid and in the pipe line in the form

of precipitation the predominant inorganic carbon are CaCO3 and MgCO3. These inorganic

carbons formed due to the chemical precipitation and incorporation of mineral carbon into

microbial shells that are existing in the extracted fluid. The cycle of CO2 starts from the

dissolved atmospheric CO2 in to the sea water, and with present of energy from the sun light

photosynthesis takes place. The product of this chemical process are CH2O biomass and O2.

This photosynthesis is some time referred to as algal photosynthesis. Algal photosynthesis

fixes inorganic carbon from HCO3- ion in the form of biomass represented as CHO3- in a

process that also produces carbonate ion CO32-. Carbonate undergoes an acid-base reaction

to produce OH- ion and raise the pH. That explains the reason of high pH in the samples.

The carbonat ions also react with Ca2+ ions to precipitate solid CaCO3. With the presence of

dissolve oxygen the biomass degraded to CO2 and water. Within the hydrocarbon reservoir

105
there are additional reactions that occurs and are responsible for the presence of CO2. The

following chain of reactions are the reactions responsible for the presence of CO2:

𝑃ℎ𝑜𝑡𝑜𝑠𝑦𝑛𝑡ℎ𝑒𝑠𝑖𝑠
2𝐻𝐶𝑂3− + ℎ𝑣 → {𝐶𝐻2 𝑂} + 𝑂2 (𝑔) + 𝐶𝑂32− eq.1

𝑃𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑖𝑜𝑛
𝐶𝑎2+ + 𝐶𝑂32− → 𝐶𝑎𝐶𝑂3 (𝑆) eq.2

𝑑𝑒𝑔𝑟𝑎𝑑𝑎𝑡𝑖𝑜𝑛
𝐶𝐻2 𝑂 + 𝑂2 → 𝐶𝑂2 + 𝐻2 𝑂 eq.3

𝑀𝑖𝑐𝑟𝑜𝑏𝑎𝑖𝑙 𝑎𝑐𝑡𝑖𝑜𝑛
2𝐶𝐻2 𝑂 + 𝑆𝑂42− + 2𝐻 + → 𝐻2 𝑆 + 2𝐶𝑂2 + 2𝐻2 𝑂 eq.4

18000

16000

14000
y = 0.0433x + 10190
Dissolved CO2 ppm

12000
R² = 0.9149
10000 Field A
8000 Field B

6000 Linear (Field A)

Linear (Field B)
4000 y = 0.0202x + 6103.6
2000 R² = 0.7301

0
0 50,000 100,000 150,000 200,000 250,000 300,000
Total ions ppm

Figure 25: The relation between CO2 and dissolved ions in produced water

Figure 25 represent the total ions concentration and the concentration of CO2 existing in

produced water of Field A and Field B. The data of total ions represent 4 sample points for

106
Field A and 4 sample points of Field B. Total ions concentration and concentration of CO2

from each sample point represent an average of at least 3 measurements.

According to figure 25 as the concentration of CO2 increases the concentration of total ions

presented in the produced water also increase. The source of the fluid in Field B differ from

Field A. Field A have higher concentration of dissolved CO2 than Field B that gives an

indication about the presence of carbonate. Both reservoirs considered as a carbonate

reservoir but the amount of carbonate in the reservoir that are located in Field A have higher

concentration of carbonate. The presence of carbonate causes real problems for the oil

extraction process. The presence of carbonates causes scale formation inside the pipelines.

The more scale forming inside the pipeline the more it will upset the process of extraction, it

could start by increasing the pressure of the fluid and extend to complete blockage in the

pipe line. To avoid the scale issues acidic chemicals are injected in the pipeline and the

reservoir. Beside the production process issues carbonate and dissolved CO2 can causes real

environmental threat to the aquatic life. The average concentration of dissolved CO2 at the

last stage of treatment is 14945 ppm for Field A and 11000 ppm for Field B. according to

earlier studies done to characterize produced water the amount of dissolved CO2 changes

with the age of reservoir.

4.7 Heavy metals concentration

High concentration of heavy metals contributes in toxicity of produced water. Heavy metals

concentration varies in different geographical locations, however the concentrations of both

fields are showing similar result since the distance barrier of the two fields is less than 100

107
km. The results of heavy metals characterization shows high concentration of sodium,

magnesium, potassium, calcium, strontium, boron and iron. Table 25 includes the

concentration of heavy metals for field A and field B. Excessive amount of some of the

above substance can cause changes to an ecological system. However, some constituents of

produced water are more easily to deal with by the environment than the others (Stephenson,

1992).

Table 25: Heavy metals concentration for Field A and Field B discharge

Concentration for field A Concentration for field B Literature data of

Metal
discharge (ppb) discharge (ppb) metal concentration

Sr 3623.75 6535.20 20-100000

B 379.68 1023.66 500-9500
Fe 205.20 519.94 100-10000
Li 108.55 281.46 300-5000
Al 49.44 58.82 25-60
Ba 21.27 34.15 70-100000
Cu 13.23 24.46 N/A
Pb 9.10 4.26 N/A
Zn 3.98 9.06 10-35000
Mn 3.84 3.77 1.27-6000
Cr 3.57 7.64 N/A
As 1.86 4.19 A/S
Hg 1.50 1.40 < 1- 2
Sb 0.11 0.01 N/A
Ag 0.07 0.01 N/A
Cd 0.03 0.04 N/A

108
 Be 0.00 0.01 N/A

Table 25 compares the concentration of metal in produced water at the discharge stage. With

values from literature of 4 sources (Yeung, et al., 2011), (Utvik & Toril, 1999), (Alley B. , et

al., 2011) and (FakhrulRazi, et al., 2009). The comparison indicates that most of the metal

concentrations are within the range of literature value except Lithium, zinc and Barium

which is slightly lower than the range.

4.8 Sulfides in produced water

Dissolved sulfide can be in the form of H2S, HS- or S-. Sulfides are the main responsible

components for corrosions in the pipeline and equipment it is also environmentally very

harmful. Result of the measured sulfide is shown in table 14. Hydrogen sulfide can be

calculated by two methods The first method is determined from the total measured sulfide.

The second method is stated by OSHA and this method integrates the sulfide ions measured

by the ions chromatography in to hydrogen sulfate (OSHA, 2003). Hydrogen sulfide is one

of the most dangers components in produced water. All oil and gas producers are challenged

by the presence of hydrogen sulfide as it is harmful to the personal, environment and

equipments. Equipments are usually designed to handle 2% of hydrogen content in the

produced stream. While the atmospheric regulation of hydrogen sulfide most not exceeds 10

ppm (OSHA, 2011).

109
Chapter 5: Suggested method for produced water
treatment

5.1 Typical methods of produced water treatment

The process of the produced water in Qatar starts with fluids extraction from the reservoirs.

After the fluid extraction there will be more than one technique to separate the oil from the

water. Each production station will have its individual separation technique. Some stations

separate the oil and the water through a three phase separator in the offshore station others

send the fluid after degasification through pipelines to Halul where the storage tanks are

located. In the storage tank a water-oil separation occurs with respect to the density

difference. The difference in specific gravity causes the oil to float to the surface of the

water. After the separation of oil and water, there are two options for the produced water

either to dispose in the water into disposal jackets or to re-injected it in the reservoirs.

Before doing so, the water must be treated as it will contain some droplets of oil, dissolved

and dispersed. According to the amount of the oil presence in the produced water the

treatment procedure can be planed. The oil droplets vary from 0.5 to 200 microns in

diameter. The size of oil droplet is one of the most important parameters that control the

produced water treating performance.

According to Stokes’ Law, The increasing velocity of an oil droplet is proportional to the

square of the droplet diameter. In support of equipment that operates on the principle of

Stokes’ law, the diameter of the oil droplet has the main effect on the separation and

extraction of the oil droplet from the water. The ability of a particular de-oiling device or

110
system to remove and recover dispersed oil decreases as the droplet size decreases. Oil

droplet size distribution is a fundamental characteristic of produced water and must be

considered in designing and sizing of treatment system to meet regulatory standards for

effluent water compliance. Table 26 illustrates the method of separation with the

corresponding oil droplet size removal capacities (Stewart & Arnold, Produced Water

Treating Systems, 2011).

Table 26 shows different methods used to separate the water from oil. By using gravity

separation method the produced water will contain from 100 microns to 150 microns of the

oil drop size. Storage tanks, Skimmer tanks, vessels are example of equipment used for

gravity separation tanks. Cross flow separation, mixed flow separation, interceptor and

corrugated plate are example of equipment used for plate coalescence. Hydro-cyclones and

centrifuges are example of equipment used for enhanced gravity separation. Dissolved gas,

hydraulic dispersed gas and mechanical dispersed gas are examples for equipment used for

gas flotation. Precipitators, coalescers are examples of equipment used for enhanced

coalescence. Multimedia membrane is an example of equipment used for filtration. So, the

three basic phenomena that are used in the design of common produced water treating

equipment are Gravity separation, dispersion, Coalescence and Flotation (Stewart &

Arnold, 2011) .

Table 26: Methods used to separate oil from water (Stewart & Arnold, 2011)

Method of oil/water separation Oil Drop size (Microns)

Gravity Separation 100-150

111
 Plate Coalescence 30-50

Enhanced gravity separation 10-30

Gas flotation 10-20

Enhanced Coalescence 10-15

Filtration 1+

Gravity Separation is the most usually used water treating equipment relays on the forces of

gravity to separate the oil droplets from the water. For the oil droplets being lighter than the

volume of water they displace and have a buoyant force applied upon them. Dispersion

means that the process of a discontinuous phase (oil) being split into small droplets and

scattered throughout a continuous phase (water). When a large amount of energy is input to

the system in a short period of time this dispersion process occurs. The energy input

overcomes the natural tendency of two immiscible fluids to reduce the contacting surface

area between the two fluids. The dispersion process is completely opposed of coalescence,

which is the process in which small droplets collide and join into larger droplets. The water

treating process based on coalescence systems is more time dependent than the process of

dispersion. In a dispersion of two immiscible liquids immediate coalescence hardly ever

occurs when two droplets collide. The flotation process is characterized by connecting the

injection of fine gas bubbles into the water in the water stick to the oil droplets buoyant

force and the oil droplet is greatly increased by the presence of the gas bubble. The oil

droplets are then removed when they rise to the water surface (Stewart & Arnold, 2011).

112
 Figure 26: Typical produced water treatment process

Generally various equipment is used to treat produced water. Figure 26 shows a typical

water treatment system. Water from the separators and coalescers first goes to a sand

cyclone which removes most of the sand. The sand is further washed before it is discharged.

The water then goes to a hydrocyclone, a centrifugal separator that will remove oil drops.

The hydrocyclone creates a standing vortex where oil collects in the middle and water is

forced to the side. Finally the water is collected in the water de-gassing drum. Dispersed gas

will slowly rise to the surface and pull remaining oil droplets to the surface by flotation. The

surface oil film is drained and the produced water can be discharged to sea. Recovered oil in

the water treatment system is typically recycled to the third stage separator (Devold, 2006).

If the water cut is high, there will be a huge amount of produced water. Often this water

contains sand particles bound to the oil/water emulsion. The environmental regulations in

most countries are quite strict. Table 27 shows the regulation followed in some countries.

The produced water must follow the standards before disposal. These standards are

developed by the government regulatory agencies. The presence of oil in the produced water

113
might affect the aquatic life if it was in high concentration. The regulatory agencies in most

cases specify the analytical method for determining the oil content. Table 27 summarizes the

sea disposal standards in offshore for several countries. In the case of onshore operation the

disposal of produced water is prohibited into freshwater streams and rivers as it might kill

freshwater fish and vegetation due to the high salinity (Stewart & Arnold, 2011). In Qatar it

is acceptable if the concentration of the oil in the disposed produced water ranges from 30

mg/l to 40 mg/l (QP, 2014).

Table 27: Produced water disposal standards (Stewart & Arnold, 2011)

Country Oil Concentration limitations (mg/l)

USA 29

Nigeria, Angola, Cameroon 50

Malaysia, Middle east 30

Thailand, Brunei 30

Ecuador, Columbia, Brazil 30

5.2 Modifying Field A treatment method

5.2.1 Designed produced water process

5.2.1.1 General treatment process:

Generally, various equipments are used. Water from the separators routed to the sand filters

to remove the suspended solids. Then it goes to coalescers which have a membrane filter to

114
enhance the oil-water separation. After that, it will be routed to the hydro-cyclin, which is a

centrifugal separator that removes the remaining oil droplets. These stages qualify the water

to meet the environmental standards and regulations.

5.2.1.2 Objective and degree of treatment:

The aim of this project is to design a water treatment unit (primary and tertiary treatment) to

treat the produced water and reduce the oil contents from (5.4 x 104 mg/l to 39 mg/l) and less

to satisfy the environmental regulation and standard and to follow the environmental law

corresponding to the state of Qatar. The water is then re-injected in the reservoir to maintain

the pressure in the reservoir to enhance the oil production.

By suggesting this method of treatment the effluent produced water will have less than 40

mg/l the effluent range of produced water is (39 mg/l – 20 mg/l), according to the material

balance that was done by considering the inlet and outlet flow rate from each unit.

5.2.1.3 Design period and capacity:

The production facility is designed to process fluid capacity of 420 BFPD and up to 520

BFPD. The fluid comes from 9 different reservoir formations and layers. The percentages of

formation of these different reservoirs are as follow:

Shuaiba (Includes Shuaiba Infill, Shuaiba Transition, Shuaiba D Laterals) : 51.5%

Arab D (Includes Arab D Infill, Arab D Subgas) : 33.9%

Uwainat : 3.5%

Nahr Umr : 6.4%

115
Kharaib : 2.8%

Arab C : 1.9%

The water cut of the fluid will be varying from 40% to 75%. The average quantity of normal

operation condition for produced water that is being separated in the facility is 300 BWPD.

The proposed design of water treatment unit have the capacity to treat up to 400 BWPD (

1.2 m3/hr ). The future increase of the produced water was considered in the design capacity.

Figure 27 shows the fluid forecast which was considered during designing the produced

water treatment unit.

Figure 27: Field A fluid production forecast

116
5.2.1.4 Location of treatment plant:

The treatment unit is located within the offshore production facilities, in approximately 100

feet of water. The location was chosen to be offshore to have a cost effective treatment that

is next to the wells which reduces the pipe line usage.

5.2.1.5 Layout of treatment plant:

The treatment of produced water is divided into five stages. First stage consists of 2-phase

separation unit (3 separators in parallel) to remove the associated and generated gas that

associate the fluid which is been extracted from the reservoir. The second stage consist 3-

phase separation units (4 separators in parallel). Third stage of treatment is filtration unit

were the produced water passes through a multi-media filter. The media of the filter is

consist of Anthracite, Fine Garnet, Course Garnet and Pea Gravel. The fourth stage is also a

separation but in this stage the produced water passes through a coalescer. The last step is

de-oiling step, the produced water in this stage is being cleared from the oil droplet to have

normal characteristics of sea water. The first two steps are classified as primary treatment.

The remaining steps are tertiary treatment. The efficiency of each unit is assumed based on

experience of previous operation, equipment vendors data and literature data (Stewart &

Arnold, 2011). Both the two phase separator and the three phase separator have the tendency

to remove 90% to 95% of gas in the fluid. The three phase separator have the tendency to

remove 97.5% of the oil in fluid. Sand filtters are able to remove 30% of oil. Coalescers are

able to remove 90% of oil content in produced water. Hydrocyclones are able to remove

95% of oil in produced water. Finally the discharged stream will end up with 39.6 ppm.

117
5.2.1.6 Consideration aspects in the design:

 First point to be considered in the design is the site limitation, as the treatment unit is

located on offshore facilities most of the area will be used for production

equipments, pipeline, emergency exits and evacuation passage so the type of

treatment must be well designed with minimum area capacity. In most cases of

offshore treatment unit the movement of equipment due to waves is also considered.

But, in the existing case the structure is fixed and there will be no effect of

movement.

 The treatment unit needs to achieve produced water with maximum of 40 ppm on

daily basis.

 At this stage of design, the equipments controlling system, safety system, relieving

system and drainage system are not being considered.

 Procedure of start-up, shutdown and emergency operation are not being considered

on this stage.

 This design shall to go through process risk managements, HAZOP study, DSA

study, What-if analysis study and JSA site survey.

5.2.1.7 Selection of separation units:

The selection of a suitable separator for a given application depends on several factors,

such as:

 feed composition, i.e. the phase ratio of the liquid phases.

 required separation efficiency.

118
  required gas and liquid handling capacity.

 whether Liquid/Liquid separation or Gas/Liquid separation is the controlling factor

(in Gas/Liquid/Liquid separators)

 required fouling tolerance.

These requirements may be conflicting, such as high fouling tolerance and high separation

efficiency. Figure 28 indicates the most common separators used for different applications.

The figure indicates which equipment is recommended and which shall not be used. This

figure serves as a first selection guide, after which a final choice can be made after

consulting.

According to the operation characteristics and condition, horizontal open two-phase settler

will be used in the first stage of treatment because in this stage separation primary dispersion

would be expected. The separation efficiency depends on the droplet size distribution of the

dispersed phase. It is normal to distinguish between primary and secondary dispersions. A

primary dispersion is one in which the majority of the dispersed droplets are larger than 30

μm. These are droplets large enough to separate from the dispersion by gravity settling. A

secondary dispersion is one in which the majority of the dispersed droplets are smaller than

30 μm. In this stage the oil droplet size is expected to be the maximum. Horizontal open

two-phase settler separator could handle the bulk and fouling condition. The term bulk

separation is used for separation in open settlers designed for a cut-off diameter of 150 μm.

This is equivalent to an entrainment rate of ≤1.5 %v. The second stage of separator is a

horizontal open three phase settler with weir arrangement, because it will provide oil and

water interface barrier and it could be used for handling and controlling the gas to make

119
sure, at this stage, no gases will be contained in the fluid. After the second stage of

separation a secondary dispersion will be expected to occur. So, best separation equipment

to handle the secondary dispersion is coalescer with compressed coalescer bed.

120
 Figure 28: bases of separator selection (Shell Group, 2008)

Figure 29 shows a simplified process flow diagram with the material balance. This process

modification is suggested for Field A to reduce the oil and solid contents.

Figure 29: suggested process flow diagram for Field A

121
Chapter 6: Conclusions and Recommendations
Produced water is the largest waste in the oil and gas industries. As the world energy

demand increase the production of the produced water waste will increase rapidly. That’s

why it is very important to pay attention for this byproduct and water waste. In 2022 the

expected increase of produced water production in Field A is about 12% according to Field

A future production expectation. According to Qatar Petroleum the production of Produced

water in 2008 was more than 177 million barrels.

The difference between Field A and Field B is that Field A uses a gravity separation

technology as the main treatment unit while Field B uses the hydrocyclones for the main

treatment unit for produced water. The characteristics of the produced water prior the

treatment was almost the same for Field A and Field B a comparison study was done in

order to evaluate the efficiency treatment stages for both fields. Result indicates that

hydrocyclones are the most efficient equipment in oil removal with removal percentage that

reached 92.6% for 11 micron oil droplet average size with a total capacity by volume is 312

h-1

Physical and chemical characteristics of produced water were measured such as

conductivity, pH, traces of heavy metal concentration, total solids content in produced

water, dissolved gases, fractions of COD and total petroleum hydrocarbon content.

The major components present in produced water are chloride, Sodium and calcium.

Sulfides were also present; sulfides could be in three forms (H2S, HS- or S-).

122
The conductivity of produced water is directly proportional to the amount of total exciting

ions, that’s why the conductivity is very high due to the high ion concentration presence in

produced water. Both oil fields A and B have similar conductivity ranging from 104 ms/cm

to 108 ms/cm.

It was observed that the total solids content in produced water were higher in Field B. It was

also observed that the total amount of solids in both fields were almost constant across the

treatment stages with a percentage difference less than 15%. However, the concentration of

total suspended solids and the amount of total dissolved solids were not constant. The

concentration of total suspended solids were decreasing across the treatment stages while,

the concentration of total dissolved solids were increasing across the treatment stages.

COD fractions indicate that biological treatment is helpful to reduce the COD concentration

for produced water from both fields, since the percentage of the readily biodegradable COD

is higher than 59% for all treatment stages. The concentration of COD decreases across the

treatment stages. The total recovery percentage across all the treatment stages was 57% for

both fields.

Produced water starts with total petroleum hydrocarbon content that may reach up to 54000

ppm and must be reduced to meet the environmental regulation for either disposal into the

sea or reinjection in the reservoir. According to the state of Qatar the environmental

regulation for the reinjection is 40 ppm, while according to EPA for direct dispose into the

sea the regulation is 5 ppm of total hydrocarbon content.

123
There is high risk when dealing with produced water due to the hazards material content in

produced water. The hazards material can lead to personal, environmental and company

asset damages. This hazards material can be in the form of hydrocarbon, salinity, toxic

metals and toxic production chemicals.

A treatment method was suggested for field A in order to meet the future environmental

regulation. In order to suggest an appropriate treatment method oil droplet size distribution

analysis was carried. The oil droplet size is an initial characteristic to determine the

treatment method.

124
 APPINDIX A
Table 28: Trails for produced water characteristics from Field A 1st stage separation

Trail 1 Trail 2 Trail 3 Trail 4 Trail 5

PH 6.22 6.20 6.26 6.25 6.32

Conductivity (ms/cm) 107 107.5 107.6 107.3 107

COD (ppm) 9184 9213 8760 7249 9213

Readily

Biodegradable COD 2387 3324 3300 2578 2511

(ppm)

Dissolved COD (ppm) 2656 5347 6298 5210 6219

THC (ppm) 4220 4125 3567 2987 2559

TSS (ppm) 23.28 16 20.5 18 12.77

TDS (ppm) 160 140.5 145.5 145 139.8

TS (ppm) 183.28 156.5 166 163 152.57

Dissolved CO2 (ppm) 15014 14983 15430 14995 15635

Sulfide (ppm) 200 205 179.8 191 217.7

125
 Table 29: Uncertainty in characteristics analysis for Field A 1st stage separation samples

Standard
Median Average MAX MIN Variance
deviation

PH 0.045826 6.25 6.25 6.32 6.2 0.0021

Conductivity
0.277489 107.3 107.28 107.6 107 0.077
(ms/cm)

COD (ppm) 846.5759 9184 8723.8 9213 7249 716690.7

Readily

Biodegradable 454.409 2578 2820 3324 2387 206487.5

COD (ppm)

Dissolved COD
1476.739 5347 5146 6298 2656 2180758
(ppm)

THC (ppm) 717.9504 3567 3491.6 4220 2559 515452.8

TSS (ppm) 4.044156 18 18.11 23.28 12.77 16.3552

TDS (ppm) 8.151871 145 146.16 160 139.8 66.453

TS (ppm) 11.86643 163 164.27 183.28 152.57 140.8122

Dissolved CO2
302.15 15014.00 15211.40 15635.00 14983.00 91296.30
(ppm)

Sulfide (ppm) 14.30804 200 198.7 217.7 179.8 204.72

126
 Table 30: Trails for produced water characteristics from Field A 2nd stage separation

Trail 1 Trail 2 Trail 3 Trail 4 Trail 5

PH 6.35 6 6.4 6.25 6.1

Conductivity (ms/cm) 108 107.5 107.9 108.1 108

COD ( ppm ) 9145 10047 8175 8639 8109

Readily

Biodegradable COD 3104 2567 2987 2893 2329

(ppm)

Dissolved COD (ppm) 4987 5348 5689 5876 6445

THC (ppm) 2167 1967 1350 1100 1093.8

TSS (ppm) 14 14.2 14.5 14 17.2

TDS (ppm) 138 138.7 139.5 139.4 140

TS (ppm) 152 152.9 154 153.4 157.2

Dissolved CO2 (ppm) 14987 16119 15219 16345 14085

Sulfide (ppm) 155 160 156 154 156.5

127
 Table 31: Uncertainty in characteristics analysis for Field A 2nd stage separation samples

Standard
Median Average MAX MIN Variance
deviation

PH 0.168077 6.25 6.22 6.4 6 0.02825

Conductivity
0.234521 108 107.9 108.1 107.5 0.055
(ms/cm)

COD (ppm) 800.8458 8639 8823 10047 8109 641354

Readily

Biodegradable 319.8765 2893 2776 3104 2329 102321

COD (ppm)

Dissolved COD
550.8153 5689 5669 6445 4987 303397.5
(ppm)

THC (ppm) 501.0374 1350 1535.56 2167 1093.8 251038.5

TSS (ppm) 1.368211 14.2 14.78 17.2 14 1.872

TDS (ppm) 0.779102 139.4 139.12 140 138 0.607

TS (ppm) 1.984943 153.4 153.9 157.2 152 3.94

Dissolved CO2
396.4991 15098 15211 15670 14733 157211.5
(ppm)

Sulfide (ppm) 2.280351 156 156.3 160 154 5.2

128
 Table 32: Trails for produced water characteristics from Field A gravity separation tank upstream

Trail 1 Trail 2 Trail 3 Trail 4 Trail 5

PH 6.3 6.3 6.25 6 6.4

Conductivity (ms/cm) 106 105.5 105 104 104.7

COD (ppm) 7500 7154 8176 7435 6935

Readily

Biodegradable COD 1876 1945 2900 2187 2877

(ppm)

Dissolved COD (ppm) 4235 3598 2900 2187 5270

THC (ppm) 1657 1809 1100 2187 1205.5

TSS (ppm) 13.9 13.85 14.2 14.1 14

TDS (ppm) 147.5 147 147 146.9 147.2

TS (ppm) 161 162 161.5 161 160.9

Dissolved CO2 (ppm) 14000 14220 13500 12089 12191

Sulfide (ppm) 55 50 35 30 30

129
 Table 33: Uncertainty in characteristics analysis for Field A gravity separation tank upstream samples

Standard
Median Average MAX MIN Variance
deviation

PH 0.15 6.3 6.25 6.4 6 0.0225

Conductivity (ms/cm) 0.763544 105 105.04 106 106 0.583

COD (ppm) 469.6121 7435 7440 8176 6935 220535.5

Readily

Biodegradable COD 498.8121 2187 2357 2900 1876 248813.5

(ppm)

Dissolved COD (ppm) 1190.743 3598 3638 5270 2187 1417870

THC (ppm) 446.314 1657 1591.7 2187 1100 199196.2

TSS (ppm) 0.212955 104 14.01 104.01 103.57 0.04535

TDS (ppm) 0.750533 147 147.12 148 146 0.5633

TS (ppm) 0.603697 251 161.28 251.67 250 0.36445

Dissolved CO2 (ppm) 1002.85 13500 13200 14220 12089 1005701

Sulfide ( ppm ) 11.72604 35 40 55 30 137.5

130
 Table 34: Trails for produced water characteristics from Field A gravity separation tank discharge

Trail 1 Trail 2 Trail 3 Trail 4 Trail 5

PH 6.2 6.2 6 6.2 6.15

Conductivity (ms/cm) 107 107.2 106 105 105

COD (ppm) 4284 2589 3535 4986 3426

Readily

Biodegradable COD 984 1179 1523 1277 1692

(ppm)

Dissolved COD (ppm) 1833 1949 2805 1277 3426

THC (ppm) 48 40 56 51 68

TSS (ppm) 2 4 1 3 10

TDS (ppm) 178 173 172 176 151

TS (ppm) 180 177 173 179 161

Dissolved CO2 (ppm) 15340 13880 15897 12897 16711

Sulfide (ppm) 25 27 40 33 25

131
 Table 35: Uncertainty in characteristics analysis for Field A gravity separation tank discharge samples

Standard
Median Average MAX MIN Variance
deviation

PH 0.086603 6.2 6.15 6.2 6 0.0075

Conductivity (ms/cm) 1.052616 106 106.04 107.2 107.2 1.108

COD ( ppm ) 909.8068 3535 3764 4986 2589 827748.5

Readily

Biodegradable COD 280.0062 1277 1331 1692 984 78403.5

(ppm)

Dissolved COD (ppm) 851.7482 1949 2258 3426 1277 725475

THC (ppm) 10.38268 51 52.6 68 40 107.8

TSS (ppm) 3.535534 3 4 10 1 12.5

TDS (ppm) 10.88577 173 170 178 151 118.5

TS (ppm) 7.745967 177 174 180 161 60

Dissolved CO2 (ppm) 1541.883 15340 14945 16711 12897 2377404

Sulfide (ppm) 6.480741 27 30 40 25 42

132
 Table 36: Trails for produced water characteristics from Field B 1st stage separation

Trail 1 Trail 2 Trail 3 Trail 4 Trail 5

PH 5.6 5.8 5.8 5.8 5.8

Conductivity (ms/cm) 108 108.5 110 110 109

COD (ppm) 15786 13578 17004 16988 20754

Readily

Biodegradable COD 5278 3199 2845 6008 6670

(ppm)

Dissolved COD (ppm) 12897 12346 13897 10065 8295

THC (ppm) 1302 988 1298 1173 1059

TSS (ppm) 13 23 20 12 5

TDS (ppm) 290 255 300 244 286

TS (ppm) 303 278 320 256 291

Dissolved CO2 (ppm) 11670 8985 9550 10998 7417

Sulfide (ppm) 166 167 148 139 130

133
 Table 37: Uncertainty in characteristics analysis for Field B 1st stage separation samples

Standard
Median Average MAX MIN Variance
deviation

PH 0.089443 5.8 5.76 5.8 5.6 0.008

Conductivity
0.894427191 109 109.1 110 108 0.8
(ms/cm)

COD (ppm) 2603.754 16988 16822 20754 13578 6779534

Readily

Biodegradable 1700.726 5278 4800 6670 2845 2892469

COD ( ppm )

Dissolved COD
2277.289 12346 11500 13897 8295 5186046
(ppm)

THC (ppm) 140.6076 1173 1164 1302 988 19770.5

TSS (ppm) 7.092249 13 14.6 23 5 50.3

TDS (ppm) 24.14539 286 275 300 244 583

TS (ppm) 24.33721 291 289.6 320 256 592.3

Dissolved CO2
1472.66 10954 10560 12023 8333 2168738
(ppm)

Sulfide (ppm) 16.35543 148 150 167 130 267.5

134
 Table 38: Trails for produced water characteristics from Field B Hydrocyclone A

Trail 1 Trail 2 Trail 3 Trail 4 Trail 5

PH 5.66 5.7 5.7 5.6 5.59

Conductivity (ms/cm) 107 107 108 107.5 108

COD (ppm) 11980 10988 10032 10789 7611

Readily

Biodegradable COD 2987 3005 2967 2811 3730

(ppm)

Dissolved COD (ppm) 6127 5982 5492 6799 7700

THC (ppm) 105 113 85 90 102

TSS (ppm) 12 26 11 16 5

TDS (ppm) 288 277 289 290 306

TS (ppm) 300 303 300 306 311

Dissolved CO2 (ppm) 9680 9683 9952 10012 9273

Sulfide (ppm) 104 155 119 125 167

135
 Table 39: Uncertainty in characteristics analysis for Field B Hydrocyclone A samples

Standard
Median Average MAX MIN Variance
deviation

PH 0.052915 5.66 5.65 5.7 5.59 0.0028

Conductivity
0.5 107.5 107.5 108 107 0.25
(ms/cm)

COD (ppm) 1645.859 10789 10280 11980 7611 2708853

Readily

Biodegradable 360.5218 2987 3100 3730 2811 129976

COD (ppm)

Dissolved COD
854.5347 6127 6420 7700 5492 730229.5
(ppm)

THC (ppm) 11.37981 102 99 113 85 129.5

TSS (ppm) 7.778175 12 14 26 5 60.5

TDS (ppm) 10.36822 289 290 306 277 107.5

TS (ppm) 4.636809 303 304 311 300 21.5

Dissolved CO2
292.3465409 9683 9720 10012 9273 85466.5
(ppm)

Sulfide (ppm) 26.15339 125 134 167 104 684

136
 Table 40: Trails for produced water characteristics from Field B Hydrocyclone B

Trail 1 Trail 2 Trail 3 Trail 4 Trail 5

PH 5.7 5.7 5.7 5.6 6.2

Conductivity (ms/cm) 108 109 108.4 108.5 108.5

COD (ppm) 7533 10433 9019 7799 9466

Readily

Biodegradable COD 4012 3467 2998 3009 2314

(ppm)

Dissolved COD (ppm) 3923 2782 3134 3256 3510

THC (ppm) 80 79.7 99 85 88.8

TSS (ppm) 31 31.5 42 43.5 42

TDS (ppm) 299 298 287 285 281

TS (ppm) 330 329.5 329 328.5 323

Dissolved CO2 (ppm) 8843 10177 9994 8317 12134

Sulfide (ppm) 122 130 90 80 83

137
 Table 41: Uncertainty in characteristics analysis for Field B Hydrocyclone B samples

Standard
Median Average MAX MIN Variance
deviation

PH 0.238747 5.7 5.78 6.2 5.6 0.057

Conductivity
0.356370594 108.5 108.48 109 108 0.127
(ms/cm)

COD (ppm) 1199.27 9019 8850 10433 7533 1438249

Readily

Biodegradable 629.4668 3009 3160 4012 2314 396228.5

COD (ppm)

Dissolved COD
426.5677 3256 3321 3923 2782 181960
(ppm)

THC (ppm) 7.941662 85 86.5 99 79.7 63.07

TSS (ppm) 6.194756 42 38 43.5 31 38.375

TDS (ppm) 8.062258 287 290 299 281 65

TS (ppm) 2.850439 329 328 330 323 8.125

Dissolved CO2
1474.721 9994 9893 12134 8317 2174804
(ppm)

Sulfide (ppm) 23.28089 90 101 130 80 542

138
 Table 42: Trails for produced water characteristics from periods for Field B Hydrocyclone C

Trail 1 Trail 2 Trail 3 Trail 4 Trail 5

PH 5.8 5.7 5.7 5.7 6.4

Conductivity (ms/cm) 108 108 108.4 108.4 108.5

COD (ppm) 13099 13934 14500 9088 9379

Readily

Biodegradable COD 2299 3019 3334 2917 4631

(ppm)

Dissolved COD (ppm) 9957 10774 8722 9146 6056

THC (ppm) 130 115 138 110 135

TSS (ppm) 29 28 29 26 28

TDS (ppm) 291 291 290 289 289

TS (ppm) 320 319 319 315 317

Dissolved CO2 (ppm) 11567 9923 10954 12023 8333

Sulfide (ppm) 139 176 133 152 100

139
 Table 43: Uncertainty in characteristics analysis for Field B Hydrocyclone C samples

Standard
Median Average MAX MIN Variance
deviation

PH 0.304959 5.7 5.86 6.4 5.7 0.093

Conductivity
0.240831892 108.4 108.26 108.5 108 0.058
(ms/cm)

COD (ppm) 2576.215 13099 12000 14500 9088 6636886

Readily

Biodegradable 863.4767 3019 3240 4631 2299 745592

COD (ppm)

Dissolved COD
1789.194 9146 8931 10774 6056 3201214
(ppm)

THC (ppm) 13.39776 130 126 140 107 179.5

TSS (ppm) 1.224745 28 28 29 26 1.5

TDS (ppm) 1 290 290 291 289 1

TS (ppm) 2 319 318 320 315 4

Dissolved CO2
1681.42 9550 9724 11670 7417 2827160
(ppm)

Sulfide (ppm) 27.79388 139 140 176 100 772.5

140
 Table 44: Trails for produced water characteristics from Field B surge drum

Trail 1 Trail 2 Trail 3 Trail 4 Trail 5

PH 6 6 5.9 6 6

Conductivity (ms/cm) 109 110 109 109.8 110

COD ( ppm ) 6965 7004 6439 8022 7820

Readily

Biodegradable COD 2591 2766 3139 2980 3524

(ppm)

Dissolved COD (ppm) 4000 3912 4500 4189 4899

THC (ppm) 38 39 41 40 42.5

TSS (ppm) 27 27 27 28 31

TDS (ppm) 285 288 293 291 293

TS (ppm) 312 315 320 319 324

Dissolved CO2 (ppm) 12223 12156 9055 8933 10433

Sulfide (ppm) 129 153 142 137 139

141
 Table 45: Uncertainty in characteristics analysis for Field B surge drum samples

Standard
Median Average MAX MIN Variance
deviation

PH 0.044721 6 5.98 6 5.9 0.002

Conductivity
0.517687164 109.8 109.56 110 109 0.268
(ms/cm)

COD (ppm) 655.8098 7004 7250 8022 6439 430086.5

Readily

Biodegradable 359.2819 2980 3000 3524 2591 129083.5

COD (ppm)

Dissolved COD
403.6292 4189 4300 4899 3912 162916.5
(ppm)

THC (ppm) 1.746425 40 40.1 42.5 38 3.05

TSS (ppm) 1.732051 27 28 31 27 3

TDS (ppm) 3.464102 291 290 293 285 12

TS (ppm) 4.636809 319 318 324 312 21.5

Dissolved CO2
2701.59 10345 11000 14230 8033 7298600
(ppm)

Sulfide (ppm) 8.717798 139 140 153 129 76

142
 References:
Alley, B., Beebe, A., Rodgers Jr, J., & Castle, J. (2011). Chemical and physical

characterization of produced waters from conventional and unconventional fossil

fuel resources. Chemosphere, 85, 74-82.

APHA. (1980). Standard methods for the examination of water and wastewater. USA:

American Public Health Association.

Arthur, J. D., Bruce, P., Langhus, G., & Patel, C. (2005). Technical summary of oil & gas

produced water treatment technologies. USA: All Consulting, LLC.

Ashagi, K., Ebrahimi, M., & Czermak. (2007). Ceramic-ultra and nanofiltrationmembranes

for oilfield produced water treatment. The Open Environmental Journal, 1, 1-8.

ASTM. (2008). Standard test method for Anions in Water by Suppressed Ion

Chromatography. USA: American Society for Testing and Materials.

ASTM. (2009). Standard test method for sulfide ion in water. USA: American Society for

Testing and Materials.

ASTM. (2011). Standard practice for manual sampling of petroleum and petroleum

products. USA: American Society for Testing and Materials.

ASTM. (2011). Standard test method for total oxygen demand. USA: American Society

forTesting and Materials.

143
ASTM. (2011). Standard test method for total petroleum hydrocarbons in water and

wastewater with solvent extraction using Mid-IR Laser Spectroscopy. USA:

American Society for Testing and Materials.

ASTM. (2011). Standard test methods for total and dissolved carbon dioxide in water. USA:

American Society for Testing and Materials.

Batley, G. E., & Kookana, R. S. (2012). Environmental issues associated with coal seam gas

recovery: managing the fracking boom. Environmental Chemistry, 9(5), 425-428.

Retrieved April 19, 2014

Blumer, D. J. (2007). PEH:Properties of Produced Water. In E. Larry W. Lake, & J. R.

Fanchi (Ed.), Petroleum Engineering Handbook (Vol. I, pp. 465-497). Society of

Petroleum Engineers.

Chakraborty, M., Bhattacharya, C., & Datta, S. (2003). Effect of drop size distribution on

mass transfer analysis of the extraction of nickel (II) by emulsion liquid membrane.

Colloids and Surfaces A: Physicochemical and Engineering Aspects, 224, 65-74.

Colborn, T., Kwiatowski, C., Scultz, K., & Bachran, M. (2011). Natural Gas Operations

fromm a Public Health Perspective. Human Ecological Risk Assessment. An

International Journal, 17(5), 1039-1056.

Davies, P. (2013). Background paper on produced water solids in relation to coal seam gas

production. Australia: Macquarie University.

144
Devold, H. (2006). Oil and gas production handbook an introduction to oil and gas

production. Switzerland: ABB ATPA Oil and Gas.

EPA. (2004). Standard operating procedure for the analysis of metals in waters and

wastewaters by ICP method 200.7 using the Perkin Elmer Optima 3300 DV and

4300 DV. USA: United States Environmental Protection Agency.

EPA. (2005). United States Environment Protection Agency. Retrieved April 18, 2014, from

remediation general permit fact sheet excerpts:

http://www.epa.gov/region1/npdes/remediation/RGP2010_FactSheet_AttachmentA.

pdf

EPA. (2011). United States Environmental Protection Agency. Retrieved January 15, 2014,

from Information Sheet Regulating Petroleum Industry Waste Water Discharges in

United States and Norway:

http://nepis.epa.gov/Exe/ZyPURL.cgi?Dockey=P100B9AW.TXT

EPA. (2014). United States Environment Protection Agency. Retrieved April 18, 2014, from

Section B. Clean Water Act Requirements:

http://www.epa.gov/dfe/pubs/pwb/tech_rep/fedregs/regsectb.htm

FakhrulRazi, A., Alireza, P., Luqman, C. A., Dayang, R. A., Sayed, S. M., & Zurina, Z. A.

(2009). Review of technologies for oil and gas produced water treatment. Journal of

Hazardous Materials, 170, 530-551.

145
Farag, A. M., & Harper, D. D. (2013). A review of environmental impacts of salts from

produced waters on aquatic resources. International Journal of Coal Geology.

Ferro, B. D., & Smith, M. (2009). Society of Petroleum Engineers. Retrieved April 12, 2014,

from Challenges in reusing produced water:

http://www.spe.org/industry/docs/reusingwater.pdf

Frankiewiwicz, T. (2001). U.S. Department of Energy. Retrieved January 15, 2014, from

Fact Sheet Physical-separation:

http://www.netl.doe.gov/research/coal/crosscutting/pwmis/tech-desc/physep

Frintrop, P., Kenneth, L., & Jerry, N. (2011). Produced Water Environmental Risks and

Advances in Mitigation Technologies. USA: Springer.

Goldman, C. R., & Horne, A. J. (1994). In Limnology (p. 111). USA: McGraw-Hill.

Hayes, T., & Aurther, D. (2004, October 12-15). Overview of Emerging Produced Water

Treatent Technologies. The 11th International Petroleum Environmental

Conference.

Healy, R., Bartos, T., Rice, C., McKinley, M., & Smith, B. (2011). Groundwater chemistry

near an impoundment for produced water, Powder River Basin, Wyoming, USA.

Journal of Hydrology, 403, 37-48.

Igunnu, E. T., & Chen, G. Z. (2012). Produced water treatment technologies. International

Journal of Law-Carbon Technologies.

146
Iowa state university. (2011). wastewater other useful expressions-aerobic II rbcod and bod.

Iowa: Iowa State University. Retrieved 2014, from Iowa state university.

Jackson, R. E., Gorody, A. W., Mayer, B., Roy, J. W., Ryan, M. C., & Van Stempvoort, D.

R. (2013). ground water protection and unconventional gas extraction:the critical

need for field based hydrological research Groundwater. National Ground Water

Association, 488-510.

Judd, S., Qiblawey, H., Al-Marri, M., Clarkin, C., Waston, S., Ahmed, A., & Bach, S.

(2014). The size and performance of offshore produced water oil-removal

technologies for reinjection. Separation and purification technology, 134, 241-246.

Leiknes, T., & Semmens, M. (2000). Membrane filtration for preferential removal of

emulsified oil from water. Water science Technology, 41(10-11), 101-108.

Liu, D. H., & Liptak, B. G. (1999). In Groundwater and Surface Water Pollution (pp. 2-10).

CRC Press.

Metcalf & Eddy, Tchobanoglous, G., David Stensel, H., & Tsuchihashi, R. (2013). In

Wastewater Engineering Treatment and Resource Recovery (Vol. FIFTH EDITION,

pp. 660-679). USA: McGraw-Hill Education.

OECD. (2005). guideline for testing of chemicals. France: The Organisation for Economic

Co-operation and Development.

OGP. (1994). Production Water Treatment Current and Emerging Technologies.

International Association of Oil and Gas Producers.

147
OSHA. (2003). United States Depatment of Labor. Retrieved September 1, 2014, from

Occupational Safety & Health Administration Hydrogen Sulfide Method no. 1008:

https://www.osha.gov/dts/sltc/methods/validated/1008/1008.pdf

OSHA. (2011). United States Depatment of Labor. Retrieved September 1, 2014, from

Occupational Safety & Health Administration Hydrogen Sulfide Exposure limits:

https://www.osha.gov/dts/chemicalsampling/data/CH_246800.html

OSHA. (2014). United States Department of Labor. Retrieved August 4, 2014, from

Training Marine Oil Spill Response Workers under OSHA's Hazardous Waste

Operations and Emergency Response Standard:

https://www.osha.gov/Publications/3172/3172.html

OSPAR. (2014). OSPAR COMMISSION . Retrieved April 12, 2014, from Quality Status

Report 2010: http://qsr2010.ospar.org/en/ch07_03.html

Ozgun, H., Ersahin, M. E., erdem, S., Atay, B., Sayili, S., Eren, E., . . . Koyuncu, I. (2013).

Comparative evaluation for characterization of produced water ganerated from oil,

gas and oil-gas production fields. Clean Soil Air Water, 41(12), 1175-1182.

QP. (2014). Qatar Petrolume. Retrieved July 8, 2014, from Oil and Gas Fields:

https://www.qp.com.qa/en/QPActivities/QPOperations/Pages/OilAndGasFields.aspx

QPD-Jaban. (2014). Qatar Petrolume Development CO., Ltd. Japan. Retrieved July 8, 2014,

from Introduction: http://www.qpd-jp.com/

148
Ray, J., & Engelhardt, F. (1993). Produced water technological environmental issues and

solution (Vol. I). USA: environmental Science Research.

Rice, C., & Nuccio, V. (2000). Water Produced with Coal-Bed Methane. USA: U.S.

Geological Survey.

Shell Group. (2008). Design and enginering practice. Netherlands: Royal Dutch Shell

Group.

Stephenson, M. T. (1992). A Survey of produced water studies. In P. R. James, & R. E. F.,

Produced Water Technological Environmental Issues and solutions (Vol. 64, pp. 1-

10). USA: Environmental Science Research.

Stewart, M., & Arnold, K. (2011). Produced water treatment field manual (Vol. I). UK:

Gulf Proffessional publication.

Tibbetts, P., & Buchanan, I. (1992). A comprehensive determination of produced water

composition. New York: Plenum Press.

Torgeir, B., Jarle, K., & Steinar, S. (2013). Environmental impact of produced water and

drilling waste discharges from the norwegian offshore petroleum industry. Marine

Environmental Research, 92, 154-169.

UK Oil and Gas. (2014). Oil & Gas UK The Voice of the Offshore Industry. Retrieved April

13, 2014, from WorldWide and UKCS Economic Report 2011:

http://www.oilandgasuk.co.uk/economic_report/production.cfm

149
Utvik, R., & Toril, I. (1999). Chemical charicterisation of produced water from four offshore

oil production platforms in the north sea. Chemosphere, 39(15), 2593-2606.

Veil, J. A., & Clark, C. E. (2009). Produced water volumes and management practices in

the united states. Argonne National Laboratory. U.S.A: U.S. Department of Energy .

Veil, J. A., Kimmell, T. A., & Rechner, A. C. (2005). Characteristics of produced water

discharged to the gulf of mexico hypoxic zone. Argonne National Laboratory. U.S.A:

U.S. Department of Energy .

Veil, J. A., Puder, M. G., Elcock, D., & Redweik, R. J. (2004). A white paper describing

produced water from production of crude oil, natural gas, and coal bed methan.

U.S.A: U.S. Department of Energy Argonne National Laboratory.

Vollertsen, J., & Jacobsen, T. (2002). Biodegradability of wastewater a method for COD

fractionation. In Water Sciennce and Technology (Vol. 45, pp. 25-34). IWA

Publishing.

Xinquan, R. (2013). In Advanced Water Injection for Low Permeability Reservoirs: Theory

and Practice (Vol. I, pp. 43-47). Gulf Professional Publishing.

Yeung, C., Law, B. A., Milligan, T. G., Lee, K., Whyte, L. G., & Greer, C. W. (2011).

Analysis of bacterial diversity and metals in produced water, seawater and sediments

from an offshore oil and gas production platform. Marine Pollution Bulletin, 62(10),

2095-2105.

150