Engineering Encyclopedia

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Oil Field Water Treatment

Note: The source of the technical material in this volume is the Professional
Engineering Development Program (PEDP) of Engineering Services.
Warning: The material contained in this document was developed for Saudi
Aramco and is intended for the exclusive use of Saudi Aramco’s
employees. Any material contained in this document which is not
already in the public domain may not be copied, reproduced, sold, given,
or disclosed to third parties, or otherwise used in whole, or in part,
without the written permission of the Vice President, Engineering
Services, Saudi Aramco.

Chapter : Process For additional information on this subject, contact

File Reference: LAB20704 R. A. Al-Husseini on 874-2792
Engineering Encyclopedia Process
Oil Field Water Treatment

CONTENTS PAGES
OIL FIELD WATERS, ASSOCIATED PROBLEMS, AND DISPOSAL
METHODS ............................................................................................................. 1
Produced Water ........................................................................................... 1
Injection Water ............................................................................................ 3
Reasons for Treating Oil Field Waters ........................................................ 3
Disposal of Produced Water and Desalter Wash Water .............................. 3
FACTORS AFFECTING FORMATION, PREVENTION, AND REMOVAL
OF MINERAL SCALES IN OIL FIELD WATERS............................................... 4
Common Scales........................................................................................... 4
Factors Influencing Scale Formation........................................................... 4
Concentration of the Scale Forming Ions ........................................ 4
pH .................................................................................................... 6
Temperature ..................................................................................... 9
Pressure.......................................................................................... 10
Total Dissolved Solids ................................................................... 12
Scale Prevention ........................................................................................ 14
Avoiding Incompatible Waters ...................................................... 14
Dilution .......................................................................................... 14
pH Control ..................................................................................... 14
Removal of Scale-Forming Ions .................................................... 16
Scale Control Chemicals................................................................ 16
Nonchemical Scale Control Devices.............................................. 16
Scale Removal........................................................................................... 16
Identification of the Scale .............................................................. 16
Chemical Cleaners ......................................................................... 18

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FACTORS INFLUENCING PREVENTION OF MICROBIOLOGICAL

FOULING AND CORROSION............................................................................ 19
Bacteria...................................................................................................... 19
Sulfate-Reducing Bacteria ............................................................. 19
Iron Bacteria .................................................................................. 20
Sulfate-Reducing BacteriaSlime Formers...................................... 20
Identifying and Counting Bacteria ............................................................ 20
Microscopic Techniques ................................................................ 20
Culturing and Serial Dilution......................................................... 20
ATP Analysis................................................................................. 22
Robbins Device.............................................................................. 22
Rapid Check II ............................................................................... 22
Mitigation and Control .............................................................................. 23
Chemical Selection ........................................................................ 23
Application of Chemicals............................................................... 25
Cleanup .......................................................................................... 25
Sterilization .................................................................................... 25
Institute Ongoing Treatment .......................................................... 25
OIL FIELD WATER CORROSION, INFLUENTIAL IMPURITIES AND
FACTORS, AND MONITORING AND CONTROL........................................... 26
Basics of Oil Field Corrosion .................................................................... 26
Corrosion Cell................................................................................ 26
Chemical Reactions ....................................................................... 28
Factors Affecting Corrosion ...................................................................... 29
pH .................................................................................................. 29
Dissolved Solids ............................................................................ 29
Temperature ................................................................................... 31

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Pressure.......................................................................................... 31
Water Velocity ............................................................................... 31
Galvanic Effects............................................................................. 31
Deposits and Concentration Cells .................................................. 31
Cavitation....................................................................................... 32
Methods for Corrosion Control ................................................................. 32
Exclusion of Oxygen ..................................................................... 32
Inhibitors........................................................................................ 33
Coatings and Linings ..................................................................... 33
Cathodic Protection........................................................................ 34
Materials Selection......................................................................... 34
Chemical Removal of Dissolved Gases ......................................... 34
Design Factors ............................................................................... 35
Corrosion Monitoring................................................................................ 35
Coupons ......................................................................................... 35
Polarization Resistance Probes ...................................................... 40
Electrical Resistance Probes .......................................................... 40
Hydrogen Probes ........................................................................... 43
Chemical Analysis ......................................................................... 45
EQUIPMENT FOR REMOVAL OF GASES, SOLIDS, AND DISPERSED
OIL........................................................................................................................ 46
Dissolved Gas Removal ............................................................................ 46
Oxygen........................................................................................... 46
Hydrogen Sulfide........................................................................... 50
Carbon Dioxide.............................................................................. 50

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Suspended Solids Removal ....................................................................... 50

Graded Bed Filters ......................................................................... 50
Multimedia Filters.......................................................................... 54
Cartridge Filters ............................................................................. 56
Monitoring Suspended Solids........................................................ 57
Dispersed Oil Removal.............................................................................. 57
Skimmers ....................................................................................... 57
Parallel Plate Separators ................................................................ 58
Flotation ......................................................................................... 58
Coalescer........................................................................................ 58
GLOSSARY ......................................................................................................... 59

REFERENCES...................................................................................................... 63

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OIL FIELD WATERS, ASSOCIATED PROBLEMS, AND DISPOSAL METHODS

Three basic types of water are encountered in oil field operations:
• Produced water
• Water used to process crude
• Injection water.
Each type of water requires treatment for use and disposal.
Produced Water
Oil and gas are seldom produced from a reservoir by themselves. Water, called produced
water, and other impurities like salt and sediment are also produced with the hydrocarbons.
Once on the surface, the produced water and impurities, called basic sediment and water
(BS&W), must be separated from the oil and gas before further processing. The produced
water is usually very high in salinity. Figure 1 shows the analysis of a typical produced water
brine compared to two aquifer waters and seawater. Due to its high salinity and minor
amounts of oil and other impurities, produced water has little or no value.
The BS&W has to be disposed of properly. Often, it is injected into disposal wells or back
into a reservoir where it can assist in improving the yield of oil.

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Oil-Bearing
Aquifer 1 Aquifer 2 Seawater
Formation

Sodium 1,600 16,360 52,600 17,600

(Na)

Calcium (Ca) 580 3,480 23,800 620

Magnesium 100 690 3,120 2,100

(Mg)

Barium -- -- 10 --
(Ba)

Carbonate -- -- -- 20
(CO3)

Bicarbonate 180 180 130 120

(HCO3 )

Chloride 2,890 32,470 132,000 31,000

(Cl)

Sulfate 1,090 1,100 320 4,280

SO4

Strontium 14 40 950 -
(Sr)

TDS 6,454 54,320 212,930 55,740

FIGURE 1. TYPICAL GEOCHEMICAL ANALYSES OF WATER FROM VARIOUS SOURCES

(Source: Reference No. 1, “Corrosion in Wet CrudeTransmission and Processing”)

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After passing through production traps where some water may be separated from crude, the
remaining BS&W is removed from the crude in a desalting train. In this process, wash water,
which is usually from shallow wells, is injected into the crude to aid in the removal of BS&W.
This water also requires proper treatment.
Injection Water
Injection water is water that is injected (pumped) into the ground in order to pressurize oil
reserves. It assists in increasing the yield of oil from the field. Water injected at the outer
edges of a reservoir will push oil towards the producing wells within the reservoir.
Seawater is the primary source of injection water in Saudi Aramco. Other sources are also
used:
• Produced water
• Well water from other subsurface zones or shallow aquifers.
Injection water must be of high quality to allow trouble free injection over a long period of
time. It must be free of matter which would cause plugging of the formation.
Reasons for Treating Oil Field Waters
Oil field water must be treated as follows to:
• Prevent scale formation.
• Mitigate microbiological fouling and corrosion.
• Prevent corrosion.
• Remove suspended solids.
Scale formation must be prevented to avoid the plugging of formations, piping, pumps, and
other equipment. Microbiological fouling and corrosion must be mitigated to avoid plugging
and damage to formations and equipment. Corrosion must be minimized to protect equipment
and to prevent the contamination of the water with corrosion products which would cause
fouling and plugging of equipment and formations. Suspended solids need to be removed
from injection waters to prevent the plugging of formations and equipment.
Disposal of Produced Water and Desalter Wash Water
Wash water, when it exits a desalting train, is referred to as oily water. This water goes to a
water/oil separator (WOSEP). The purpose of the WOSEP is to remove oil from this water to
allow it to be used in injection wells. Also, washwater is taken from water wells and is
degassed before it is used in desalters. If not handled properly this wastewater also causes
corrosion, fouling, and scale.

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Factors Affecting Formation, Prevention, and Removal of Mineral Scales in

Oil Field Waters
Threre are several common scales which form on the walls of piping and equipment by the
precipitation of dissolved ions. They will be described below.
Common Scales
Solubility can be defined as the limiting amount of a material which can be dissolved in a
solvent (water) under a given set of conditions. Nearly all salts of sodium and potassium have
high solubility in water. Sulfate salts of calcium, barium, and strontium, and the carbonate salt
of calcium have limited solubility.
Calcium carbonate and sulfate scales are quite common and can be precipitated from many
surface and well waters including seawater and aquifer waters. Barium sulfate scale is a
serious problem in some producing wells. This scaling occurs after a breakthrough of
seawater injection water due to the mixing of sulfate bearing seawater with barium and
strontium bearing formation waters. Strontium sulfate may be found coprecipitated with
barium sulfate in some Middle Eastern fields.
Precipitation of solid salts of these compounds may form scale when these ions are present in
the water and there is a change in the water composition which lowers the solubility below the
concentrations present.
Factors Influencing Scale Formation
The following major factors influence scale formation:
• Concentration of scale forming ions
• pH
• Temperature
• Pressure
• Total dissolved solids

Concentration of the Scale Forming Ions

The equilibrium constant, expressing the solubility of a precipitate, is the solubility product
constant, Ksp. For calcium sulfate, the precipitation reaction and the expression for Ksp are:
Ca+2 + SO4-2 = CaSO4 (solid)
Ksp = [Ca+2] [SO4-2]

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Similar equations can be written for calcium carbonate, barium, and strontium sulfate. The
term on the right of the second equation is called the ion activity product, IAP. The values in
the brackets are the activities of the ions. Activities are the effective concentrations of the ions
in units of molarity (moles/liter) and have been corrected for the diluting effect of other ions
present. When the IAP exceeds the Ksp value, a precipitate forms. Ksp values for the common
scales at standard conditions, 25 °C (77 °F) and 1 atmosphere, are shown below.
Ksp

Calcium carbonate 5 x 10-9

Calcium sulfate 6 x 10-5

Barium sulfate 1 x 10-10

Strontium sulfate 3 x 10-7

A low Ksp corresponds to a low solubility. Under standard conditions, barium sulfate is the
least soluble and calcium sulfate is the most soluble of the four compounds.
Often the term IAP/Ksp is calculated from a water analysis. It has the following significance:
IAP/Ksp

>1 the water is supersaturated and a

precipitate will form
<1 the water is undersaturated and a
precipitate will not form
=1 the water is at equilibrium
IAP/Ksp is a thermodynamic term which indicates the tendency of a scale to form or not to
form. It does not address how fast a scale will form or dissolve. Precipitates may form rapidly,
but dissolve very slowly.

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pH
The pH of the water has an effect on the solubility of calcium carbonate. This effect is due to
the fact that the carbonate ion exists interchangeably with the bicarbonate ion and dissolved
carbon dioxide.
CO2 + OH- ——> HCO3- + OH- ——> CO3-2 + H2O
The ion that predominates is based on the pH of the water as shown in Figure 2. At ambient
temperature, when the pH is greater than about 7.5, the carbonate ion appears; consequently
the driving force for the formation of calcium carbonate scale increases as the pH increases.

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PORTION OF TOTAL CARBONATES, %

100

H 2CO 3
10 –
HCO 3
–
CO 3

1.0

0.1
3 5 7 9 11
pH

FIGURE 2. IONIZATION OF CARBONIC ACID AT DIFFERENT pH

(SOURCE: REFERENCE NO. 2, Operator Training Manual)

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The effect of pH on the solubility of calcium carbonate is shown in Figure 3.

FIGURE 3. pH VS. SOLUBILITY OF CALCIUM CARBONATE

The pH of the water has little affect on the formation of the sulfate scales.

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Temperature
The solubility product constant varies with temperature. The solubility of calcium carbonate
decreases as temperature increases (Figure 4).

FIGURE 4. TEMPERATURE VS. SOLUBILITY OF CALCIUM CARBONATE

Temperature has less effect on calcium sulfate (gypsum). The solubility increases slightly up
to about 38 °C (100 °F) and then decreases at higher temperatures. Barium sulfate solubility
increases up to about 100 °C (212 °F) and then decreases. The solubility of strontium sulfate
decreases with increasing temperature.

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Pressure
The solubility of all scales in water increases with increasing pressure. This occurs because
there is a decrease in volume when a scale dissolves, as shown below.
Ca+2 + SO4-2 + H2O ——> CaSO4 (solid) + H2O
volume of solution < volume of solid + water
Pressure affects solubility in proportion to the change in volume. In low TDS water where the
change in volume from solution to solid + water is relatively large this effect is significant.
There is less effect in a high TDS water.
The calcium carbonate solubility is also greatly affected by the partial pressure of carbon
dioxide in contact with the water. As the partial pressure of carbon dioxide increases, the
solubility of calcium carbonate increases. This relationship is shown in Figure 5.

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FIGURE 5. PRESSURE OF CARBON DIOXIDE VS. SOLUBILITY OF CALCIUM CARBONATE

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Total Dissolved Solids

The solubilities of the oil field scales increase as the TDS of the water increases up to about
125 to 250 g/l NaCl, depending on the scale. Above this range there is no effect or decrease in
solubility. The upper limit for each scale is shown below.
Concentration of NaCl above which there is no increased solubility:
g/l NaCl

Calcium carbonate 200

Calcium sulfate 150

Barium sulfate 250

Strontium sulfate 125

Figure 6 shows the effect of TDS on the solubility of calcium carbonate at 25 °C (77 °F) and
14.7 psig carbon dioxide.

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FIGURE 6. TOTAL DISSOLVED SOLIDS VS. SOLUBILITY OF CALCIUM CARBONATE

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Scale Prevention
Several options that are available for preventing scale formation are as follows:
• Avoiding incompatible water
• Dilution
• pH control
• Removal of scale forming ions
• Scale control chemicals
• Non chemical scale control devices

Avoiding Incompatible Waters

It may be possible to avoid mixing two waters which do not form scale alone but together will
form scale. For example, assume you have two waste streams which must be sent through a
pipeline for disposal. One stream is a water with IAP/Ksp = 0.93 for calcium carbonate, which
is just nonscaling. The other stream is dilute waste caustic with pH > 12. It would not be
advisable to mix these waters because the resulting stream would have IAP/Ksp > 1, which
would form scale. The streams should be separated or otherwise treated before they are
mixed. Serial injection of incompatible water has been used to avoid mixing incompatible
waters.
Dilution
In order to avoid scale formation, waters high in concentration of scale-forming ions can be
diluted with water which does not contain the scale forming ions.
pH Control
In the example given above, if the caustic had been neutralized with acid it would then have
been compatible with the other water.
pH control is used to prevent scale formation in seawater used for injection. For example, at
Qurayyah the pH is strictly controlled by the addition of sulfur dioxide, which forms sulfurous
and sulfuric acids in water. Figure 7 shows how much scale could form in the injection water
produced at Qurayyah should the pH increase above the recommended range.

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FIGURE 7. AMOUNT OF CACO 3 SCALE THAT COULD FORM

FROM QURAYYAH SEAWATER AT 5,500,000 BBL/DAY
(SOURCE: REFERENCE NO. 3, Operator Training Manual)

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Removal of Scale-Forming Ions

In order to prevent scale formation the scale-forming ions can be removed from the water by
precipitation softening and/or ion exchange softening. Produced waters are softened by these
techniques in California before they are heated in steam generators and reinjected into heavy
oil producing formations.
Scale Control Chemicals
Several types of treatment chemicals can be used to prevent the formation of calcium sulfate
and carbonate scales. Some phosphonates, polyphosphates, and water soluble polymers and
copolymers act as crystal distorters and slow the growth of scale-forming crystals. Other
polymers can be used to disperse small crystals in the water so that they do not form scale on
the surfaces of equipment and piping.
Nonchemical Scale Control Devices
At some time you may be approached by someone who is selling a device which is claimed to
prevent scale formation by operating on some vague magnetic, catalytic, or electrostatic
phenomena. There are always theories to support the claimed mechanism by which these
devices work. On close examination these theories are not substantiated by any valid
scientific principle. Laboratory or field trials, should they exist, are poorly controlled and
rarely well documented. Based on available information, the use of devices which operate on
these phenomena to control scale formation is not recommended.
Scale Removal
The following steps and measures are employed to remove scale:
• Identification of the scale
• Use of chemical cleaners

Identification of the Scale

When a scale has formed on equipment the first step in deciding on a procedure for removing
it is to identify the scale. If possible, a complete laboratory analysis is recommended.
The proposed cleaning procedure can be tested on the sample before the field work begins if a
scale sample is available. This type of testing greatly improves the chances of a successful
cleaning.
Field testing of scale deposits can be used to identify certain scales if time constraints do not
allow for full laboratory testing. Watching the response of a small sample of deposit to 10 %
HCl, water, or hydrocarbon solvent can be helpful. Figure 8 contains guidelines that are
useful for interpreting field testing.

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Deposit Test Response

CaCO3 , FeCO3 Evolve gas (CO2) in 10 % HCl, iron

scale turns the solution yellow

Iron Oxides Slowly react and turns solution yellow

(corrosion products) in 10 % HCl

Iron Sulfides Evolves H2S in 10 % HCl giving a

strong odor

NaCl Dissolves in water

Hydrocarbons Dissolves in hydrocarbon solvent only

CaSO4 , BaSO4 No reaction to acid, water or solvent

SrSO4, sand, clay

FIGURE 8. FIELD TESTING FOR IDENTIFYING SCALES

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Chemical Cleaners
Inhibited acids, converters, chelants, caustic, and hydrocarbon solvents are available for
removing scales and deposits of corrosion products. The temperature and contact time greatly
affect the speed and effectiveness of cleanings.
Inhibited acids are commonly used to remove calcium carbonate deposits. Hydrochloric acid
effectively dissolves the scale and converts carbonate to carbon dioxide gas. Due to the
corrosive nature of hydrochloric acid, and the fact that it will generate deadly hydrogen
sulfide gas if sulfides are present, cleaning should only be performed by experienced
personnel. Chelants are compounds which dissolve hardness ions by preferentially binding to
them. They are less corrosive than acid, but are less efficient and expensive; consequently,
they are used less frequently.
Acids are ineffective on calcium sulfate scales. Inorganic converters, e.g., ammonium
carbonate, can be used to convert calcium sulfate to calcium carbonate, which can then be
removed with acid. Organic converters, such as sodium citrate, cause calcium sulfate to
become soft and swell so it can then be flushed with water. 10 % caustic (NaOH) will dissolve
up to 12.5 % gypsum scale, and 55 g/l NaCl will dissolve three times as much gypsum as will
fresh water at 40 °C (104 °F).
Proprietary scale dissolvers are required to remove barium and strontium sulfates. These are
special chelants which are often slow acting and quite costly.
Both fill-and-soak and recirculating methods can be used depending on the equipment to be
cleaned. The presence of hydrocarbon films on a scale may greatly slow its removal with the
cleaner. Two-step procedures, solvent to remove hydrocarbon, followed by cleaner to
dissolve the scale, may be required.

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Factors Influencing Prevention of Microbiological Fouling and Corrosion

In this section, the types of bacteria, how they are identified and counted, and finally
controlled will be discussed.
Bacteria
Oil field waters are environments which are very conducive to the growth and reproduction of
bacteria. Bacteria are microscopic organisms which can rapidly grow and multiply in many
waters. They are extremely small (about 0.5 microns) and thousands of species exist. They
can exist in water having a wide range of temperature (-10 to 99 °C), pH (about 1 to 10.5),
and oxygen concentration (0 % to saturation).
Bacteria live in colonies, either attached to a surface (called sessile organisms), or freely
floating in water (called planktonic organisms). The sessile organisms produce a gelatinous
substance called a polysaccharide which forms a biofilm or biomass surrounding the bacteria.
This film can reach a thickness of several millimeters and can trap suspended matter in water.
It can slough off a surface and result in plugging and fouling. For every colony detected that
is free floating, there may be 1,000 to 10,000 sessile colonies attached to surfaces in a system.
Sulfate-Reducing Bacteria
Sulfate-reducing bacteria (SRB) are particularly troublesome. Along with producing a
biofilm, they excrete corrosive acids. These bacteria convert sulfate ions to sulfide with
hydrogen sulfide as a by-product. They cause three types of problems:
• SRB generate organic acids and hydrogen sulfide which cause pitting beneath a
bacterial colony.
• In a sweet system the generation of hydrogen sulfide by the SRB will generally
increase the corrosivity of the water. H S creates the possibility of sulfide cracking
2

and blistering of steel.

• Bacteria form slimy deposits which plug equipment. In addition, ferrous sulfide
(FeS) is generated as a corrosion product by SRB. This serves as additional
suspended matter which can also result in plugging.
Bacterial fouling and corrosion can be minimized by the addition of bactericides. Stagnant
areas are highly prone to bacterial growth. Since it is impossible to sterilize (destroy all the
bacteria) any equipment, regularly scheduled treatments are required.

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Iron Bacteria
Iron bacteria convert soluble iron ions into insoluble iron hydroxide. The insolubility is a
function of the precipitated oxide which forms in a sheath around the bacteria. Iron bacteria
are aerobic, but can exist with as low as 0.5 mg/l oxygen in the water. They occur in open
ponds, supply wells, filters, lines, equipment, and injection wells. The coating and slime
masses associated with the iron bacteria set up corrosion cells, cause fouling and plugging,
and may set up an aerobic environment for SRBs.
Sulfate-Reducing BacteriaSlime Formers
The term slime-forming bacteria does not refer to a single group of organisms. There are
many bacteria which can produce a slimy capsule that can cause plugging in injection wells
and other equipment. It is difficult to specifically count slime-forming bacteria. It is assumed
that when a high total count is measured it is indicative of slime forming. Slime formers can
exist in fresh and saline waters, although they are more common in waters of low salinity.
They may exist in either aerobic or anaerobic environments. Slime formers create mucous-
like mats in open ponds, masses in shallow supply wells, viscous matter in filters, lines,
equipment, and injection wells.
Identifying and Counting Bacteria

Microscopic Techniques
A trained microbiologist can quickly identify iron and slime-forming bacteria with a phase-
contrast microscope. Epifluorescence microscopy allows rapid direct counting of the bacteria
population in a sample. Specific stains are used to make the living organisms emit light
(fluoresce) when irradiated with a special lamp. It is easy to distinguish the living bacteria
from nonliving particles of similar shape and size; therefore, it is a powerful tool for quickly
estimating the number of living organisms in a sample.
Culturing and Serial Dilution
Culturing bacteria is a technique for growing species of bacteria in a controlled laboratory
environment so that the types of bacteria in a sample of water can be counted. In this
technique a measured volume of water sample is placed in a culture medium which is a
solution containing water, food, and an indicator which turns turbid or a color when bacteria
are present. The culture is incubated for a period of time and then the presence or absence of
bacteria is determined. Different types of bacteria require different media; media can be
formulated so that only specific types of bacteria can grow in it. The number of each type of
bacteria can be estimated by running tests in different media at several dilutions.

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Extinction dilution, or serial dilution, is a field technique which can be used to enumerate
bacteria. The American Petroleum Institute has published a recommended practice, API RP
38, for examining injection water used by many laboratories. Other media can also be used to
match the water of interest. The test uses several serum bottles filled with 9 ml of sterile
growth media. One ml of water sample is injected into the first bottle and mixed; one ml of
the solution in the first bottle is injected into the second bottle; one ml of solution in the
second bottle is injected into the third bottle with a new sterile syringe. This procedure is
continued until six or seven bottles are filled. Each is diluted by a factor of ten as shown
below. After filling, the bottles must be set aside for one month before they are read.
Bottle Dilution Number of Bacteria

No. Factor in 1 ml Water Sample

1 1/10 1-10
2 1/100 10-100
3 1/1000 100-1000
4 1/10,000 1000-10,000
5 1/100,000 10,000-100,000
6 1/1 million 100,000-1 million
7 1/10 million 1 million-10 million

For example, if bacteria are indicated in bottles 1 through 5, but not bottles 6 or 7, then
10,000 to 100,000 bacteria were present in the initial 1 ml of water.
General bacteria counts of less than 10,000 per ml are usually not significant. If 100,000 per
ml or greater are found, the system should be investigated further for signs of bacterial fouling
and plugging. The presence of any SRB is considered to be a problem. Remember that these
tests detect free floating bacteria. The presence of a few floaters indicates that a great many
bacteria may be attached to piping and equipment.
Dip slide test kits for total aerobic bacteria, fungi and yeasts, and sulfide generators are
commercially available from companies like MTC under the name Easicult® test. In these kits
the media is fixed to a dip slide, dipped in the water, placed back in a holder, incubated, and
the results are read by comparing the slide to a color chart. These kits are inexpensive, easy to
use, and useful for routine monitoring of a system. When sampling water for culturing or
other microbiological testing, precautions must be taken to avoid exposing the water to any
tubing, container, or other equipment which has not been sterilized. Sterile containers must be
used to ship samples to the lab, and samples must be refrigerated and delivered to the lab
within eight hours. For field analysis it is best if the water sample is taken from a flowing
sample port directly with a sterile syringe.

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ATP Analysis
ATP (adenosine triphosphate) is present in the cells of all living organisms and is destroyed
shortly after cell death. ATP Analysis is therefore useful in detecting the presence of viable
bacteria in water. It is particularly useful in determining if a bactericide is effective in killing
organisms in a system. The test method is based on the reaction of ATP with luciferin in the
presence of the luciferase enzyme, which emits light. The amount of light emitted by the
luciferase enzyme in the bacteria is measured by a photometer and corresponds to the number
present. This test provides a very rapid count of the bacteria and other organisms in a water. It
is not able to discern types of bacteria, e.g., slime formers and SRB.
Robbins Device
The Robbins Device allows an estimate of the number of sessile bacteria in a water system. It
was developed by Robbins and Costerton at the University of Calgary. It consists of a device
with small sterile steel studs inserted into a slipstream of the stream of interest. The studs are
mounted flush with the pipe wall and provide a surface on which sessile bacteria can grow.
After a given exposure time the studs can be removed and the number of bacteria on each
stud can be determined by a number of methods. Such probes are commercially available
from treatment companies.
Rapid Check II
Conoco has developed a test for SRB. The latest version is called RapidCheck II. It is not
based on culture growth, but instead involves immunoassay technology which uses purified
antibodies to detect the APS reductase enzyme present in all SRB. In the test, bacteria are
trapped in a filtration medium, impurities are washed away, cells are disrupted (lysed)
chemically which releases the APS reductase enzyme, the immunoreagent is added, and the
sample is passed through a membrane. In ten minutes a color develops if SRB are present,
and a chart is used to estimate the number. The speed of the test is its greatest advantage,
hence the name RapidCheckII. A disadvantage of the test is its poor sensitivity. Remember
that if any SRB are present a problem exists, and the test only detects about 1,000 SRB per
ml. By testing 100 ml of water the detection limit is lowered to 100 SRB/ml. This is an
improvement on earlier tests, but when 100 SRB/ml are present the problem may be serious.

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Mitigation and Control

When investigating a microbiological problem in an injection system, samples should be
taken at the source, in vessels, tanks, filters, and at several injection well heads to find where
the problem originates and determine where treatment is needed.
If water entering a system is sweet (not contaminated with hydrogen sulfide) and the
hydrogen sulfide odor is noticeable in the system, it is likely that SRB are generating the
hydrogen sulfide. The presence of black water in a sweet system is another indication, but not
positive proof, of SRB. The corrosion product of SRB is FeS, which is black and generates
hydrogen sulfide when it is acidified.
Chemical Selection
Several factors must be considered in the selection of treatment chemicals. A decision must be
made whether a bactericide or biocide is needed. Bactericides kill bacteria and biocides kill
other organisms as well. The terms toxicant or microbiocide encompass both bactericides and
biocides. If organisms, such as algae (common in surface waters) and plankton (tiny plant or
animal life from seawater) are present, then a biocide is needed. Oxidizing biocides such as
chlorine are very effective in seawater and many well water systems. However, when more
than a few ppm of oil, sulfide, or ammonia are present it is very difficult to control bacteria
with an oxidizing biocide because these materials consume the oxidizer; consequently,
nonoxidizing biocides are frequently used in oil field waters.
The nonoxidizing biocide should be selected based on toxicity studies, compatibility with the
water and other chemicals present, and economics. Toxicants do not kill organisms
instantaneously; consideration must be given to the contact time available. A lethal
concentration must be applied with any biocide. If less than the lethal dosage and contact time
is used, the kill will be incomplete and high bacteria counts will reappear quickly. All
nonoxidizing biocides have limited pH ranges in which they are effective and many are
incompatible with certain chemicals. For example, glutaraldehyde which is an effective
bactericide is incompatible with ammonia and amines; therefore, it cannot be used with many
amine based corrosion inhibitors. Figure 9 lists some of the toxicants used in oil field waters.

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Oxidizers Organics Metals

Chlorine Triazine Copper salts

Sodium Hypochlorite Methylene-bis-thiocyanate Arsenic salts

Glutaraldehyde

Calcium Hypochlorite Formaldehyde Silver salts

Hydrogen Peroxide Isothiazolinones Mercury compounds

Bromochlorohydantoins Quarternary Amines Organo-tin compounds

Phenols

Acrolein

Ethylene oxide

DBNPA

Carbamates

Trichlorophenols

Pentachlorophenols

FIGURE 9. TOXICANTS USED IN OIL FIELD WATERS

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Application of Chemicals
The method of application, batch vs. continuous injection, must also be considered. Since
chlorine is inexpensive it is often dosed continuously. Nonoxidizers are usually dosed
batchwise, which also minimizes the development of resistant organisms. Even so, it may be
necessary to switch nonoxidizers occasionally because organisms develop resistance to them.
Cleanup
A combination of chemical or mechanical cleaning prior to the application of a toxicant is
much more effective than the application of a toxicant alone. When a problem is detected in
an injection system, lines should be cleaned as required by scraping, chemicals, or acid.
Vessels and tanks should be opened and cleaned and injection wells should be backflowed.
Often, chlorine followed by acid is used in the cleanup.
Sterilization
Once the system is cleaned the bacteria can be killed with a high dose of toxicant. Proper
attention must be paid to dosage, contact time, and chemical compatibility. When possible,
the entire system, from source to injection well, should be treated.
Institute Ongoing Treatment
Complete sterilization of any system is never possible; some bacterial colonies always
survive. The survivors may have been protected by deposits which were not penetrated by the
cleaning or biocide, or they may have been located in a deadleg where the biocide could not
circulate effectively. To prevent recurrence of fouling, ongoing treatment is required.
When the system is relatively clean, surfactants (detergents) are often effective and aid in the
penetration of the biomass by the toxicants. Regularly scheduled cleaning of pipelines by
scraping is good practice. Biocide application is most effective when coordinated with such
mechanical cleaning.

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Oil Field Water Corrosion, Influential Impurities and Factors, and Monitoring
and Control
In oil field water, corrosion is an electrochemical reaction between a metal and a chemical in
the water. The chemical in the water is usually dissolved oxygen, carbon dioxide, or hydrogen
sulfide. These chemicals, which react with the metal, are called oxidants or corrodants.
Basics of Oil Field Corrosion

Corrosion Cell
A simple corrosion cell is shown in Figure 10. Every electrochemical cell consists of a metal,
an anode, a cathode, and water. Oxidation, i.e., dissolution of a metal or formation of a metal
oxide, occurs at the anode. The oxidation reaction must be balanced by a reduction reaction in
which an oxidant or corrodant accepts the electrons at the cathode.

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Oxidizers Organics Metals

Chlorine Triazine Copper salts

Sodium Hypochlorite Methylene-bis-thiocyanate Arsenic salts

Glutaraldehyde

Calcium Hypochlorite Formaldehyde Silver salts

Hydrogen Peroxide Isothiazolinones Mercury compounds

Bromochlorohydantoins Quarternary Amines Organo-tin compounds

Phenols

Acrolein

Ethylene oxide

DBNPA

Carbamates

Trichlorophenols

Pentachlorophenols

FIGURE 10. CORROSION CELL

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Chemical Reactions
For steel, the anodic reaction involves the production of ferrous ions (Fe+2) and electrons (e-)
from iron metal (Fe).
Fe ——> Fe+2 + 2e-
Similar reactions can be written for other metals. In oxygen corrosion the cathodic reaction is:
1/2 O2 + H2O + 2e- ——> 2OH-
when dissolved oxygen is present, and where oxygen (O2), water (H2O), and electrons
combine to form hydroxide ions (OH-). Further reactions often occur in water, forming
ferrous (Fe+2) and ferric (Fe+3) oxides and hydroxides. Oxygen corrosion is characterized by
severe pitting.
When carbon dioxide is present, sweet corrosion can occur. The corrodant is the hydrogen ion
(H+) formed when carbon dioxide dissolves in water.
CO2 + H2O ——> HCO3- + H+
The hydrogen ion forms hydrogen gas in its cathodic reaction.
2H+ + 2e- ——> H2 (gas)
The corrosion product of steel with carbon dioxide is ferrous carbonate (FeCO3). Carbon
dioxide corrosion is characterized by mesa-type formations, which are localized areas of deep,
sharp-sided pits adjacent to areas of little corrosion.
Sour corrosion can occur when hydrogen sulfide is present. Hydrogen sulfide is also a weak
acid that forms a hydrogen ion which reacts at the cathode. Ferrous sulfide (FeS) is the
corrosion product. Black iron sulfide scales and black water result from hydrogen sulfide
attack.
The function of a corrosion inhibitor is to slow the rate of one or more of these reactions.
Anodic inhibitors slow an anodic reaction, i.e., the rate at which the metal is dissolved.
Cathodic inhibitors function by precipitating films of salts at locally high pH generated at the
cathodic site. These films are less protective than those generated by anodic inhibitors.
Inhibitors which affect both cathodic and anodic reactions are termed mixed inhibitors.

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Factors Affecting Corrosion

The rate of corrosion is affected by many environmental factors. Often there are competing
corrosion and passivating reactions. In the corrosion reaction the protective oxide, sulfide or
carbonate scale is broken down. In the passivating reaction, a protective scale is formed. The
problem is to form a protective scale much faster than it is broken down by the environmental
factors.
pH
Decreasing the pH by the addition of an acid, such as carbon dioxide or hydrogen sulfide, will
cause the corrosion rate to increase.
Dissolved Solids
Increasing the dissolved solids increases the electrical conductivity of the water which
accelerates the corrosion. When there is a high chloride concentration, ferric and ferrous
chlorides which readily dissolve in water cause the protective film to breakdown, working
against the formation of protective iron oxide, sulfide, or carbonate films. Figure 11 shows the
general relation between dissolved solids and corrosion rate.

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FIGURE 11. EFFECT OF DISSOLVED SOLIDS ON CORROSION RATE

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Temperature
The rates of chemical reactions generally increase as the temperature increases. This is true
for corrosion reactions also. In water systems that are open to the air the corrosion rate may
decrease slightly at temperatures above about 80 °C (176 °F) where the dissolved gases
escape due to their lower solubility in the hot water.
Pressure
When oxygen, hydrogen sulfide, or carbon dioxide are present as a gas above the water,
increased pressure causes more of the corrosive gases to dissolve in the water. This increased
concentration of dissolved gases will cause an increased corrosion rate.
Water Velocity
The velocity of water can affect corrosion in two ways. If the water is stagnant or the velocity
is too low, deposits can form on the surfaces of piping and equipment resulting in differential
corrosion cells. If the velocity of water is too high, corrosion increases due to the effects of
erosion or erosion-corrosion. To minimize these effects upper and lower limits on water
velocities are required.
In small diameter piping, 5-20 cm (2-8 in), typical velocities are 0.9-1.5 m/s (3-5 ft/s).
Velocities up to 2.1 m/s (7 ft/s) may be used. These velocity limits become prohibitive
economically in large seawater injection systems lines. In these systems the lines are sized for
velocities up to about 3.0 m/s (10 ft/s). Above this velocity, corrosion and pressure drop due
to friction increases at unacceptable levels.
Galvanic Effects
Coupling different metals together should be avoided in water systems. When these couples
cannot be avoided the metals must be carefully selected to avoid galvanic corrosion. Galvanic
corrosion accelerates the attack of the metal, which is inherently less corrosion resistant.
Deposits and Concentration Cells
Scales and sludges in equipment form concentration cells which cause underdeposit
corrosion. SRB thrive under deposits and cause pitting at these locations. Scheduled cleaning
of pipelines and designing equipment to avoid dead legs are used to deter underdeposit
corrosion.

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Cavitation
Cavitation is caused by the repeated formation and collapse of bubbles (cavities) in a liquid. It
occurs when there is a pressure drop which forms the bubble (a small quantity of vapor with
the liquid) followed by an increase in pressure which causes the bubbles to collapse. The
forces present in these rapidly collapsing bubbles damage metal. Cavitation occurs in
centrifugal pumps when the pressure on the pump suction is too low. It can also occur
downstream of a control valve in an injection system when a portion of the flow from a high
pressure pump is sent back to a water tank at atmospheric pressure.
Methods for Corrosion Control
Methods for controlling corrosion involve changing the material, changing the composition of
the water, putting a barrier between the water and the metal, using corrosion inhibitors, or
installing cathodic protection. The role of a corrosion engineer is to determine the cause of the
corrosion and select the most cost-effective solution.
Exclusion of Oxygen
Whenever possible, oil field water systems should be designed to eliminate contact of the
water with air. Injection water systems, desalting operations, and water disposal systems can
be designed to be closed from the atmosphere from the beginning of a process to the end. This
involves covered tanks, maintaining inert gas blankets in tanks, deaerating source water
chemically and mechanically, repairing leaking pumps, etc. To control oxygen corrosion at
Qurayyah, where seawater for injection is treated, the oxygen content is maintained at less
than 0.01 ppm. Depending on the temperature and salt content, water in contact with air will
dissolve about 8 mg/l oxygen; therefore, the plant at Qurayyah is capable of removing 99.9 %
of the dissolved oxygen.
The majority of the oxygen is removed mechanically in a deaerator which will be discussed in
a following section. The remaining oxygen must be removed by a chemical oxygen
scavenger. At Qurayyah, sulfur dioxide (SO2) is used. The sulfur dioxide is produced at
Qurayyah by burning elemental sulfur. The sulfur dioxide forms sulfurous acid (H2SO3) when
dissolved in water which reacts with dissolved oxygen to form sulfuric acid.
O2 + 2H2SO3 ———> 2H2SO4
sulfurous acid sulfuric acid
The amount of these acids present is only enough to slightly decrease the pH of the water, so
acid corrosion is not a problem. The sulfite and bisulfite oxygen scavengers previously
discussed are also useful in oil field waters.

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There are two common methods for measuring oxygen content of water in a treatment plant:
continuous in-line oxygen meters or off-line wet chemistry tests, e.g., Chemets.
The plant at Qurayyah utilizes continuous in-line oxygen meters at the outlet of the deaerator.
The instrument used has the capability of measuring from 0 to 20 mg/l. If the preset
specification value is exceeded, an alarm is generated by the meter to alert the operating
personnel to the problem.
Chemets is a tradename of Chemetrics, Inc., a supplier of various field test kits. There is a
series of field test kits for the determination of dissolved oxygen in either the ppb
concentration range or in the mg/l concentration range. These tests are based on the fact that
the reacting chemical will develop a color in the presence of dissolved oxygen.
The reagent is stored in an evacuated glass ampule. The ampule is inserted into a stream and
the tip is broken so the water is drawn up into the ampule without exposing the water to air.
The color is then compared to a standard color solution or chart to determine the
concentration of dissolved oxygen in the sample.
Inhibitors
Corrosion inhibitors can be used to minimize corrosion due to hydrogen sulfide and carbon
dioxide in water. Some special inhibitors are effective against oxygen, but it is usually better
to exclude the oxygen than to try to inhibit the corrosion.
After determining the cause of corrosion, an inhibitor should be selected based on laboratory
or field tests, or experience elsewhere. Compatibility of the inhibitor with biocides, oxygen
scavengers, and other treatment chemicals should be verified. Water soluble or dispersible
inhibitors are most often used in water.
Inhibitors are only effective when there is free access to the metal surface. Like biocides, they
are most effective in cleaned systems. A good inhibitor should be effective when dosed at
about 5 to 25 mg/l. After an inhibitor program is started, corrosion monitoring should be used
to track the effectiveness of the treatment.
Coatings and Linings
The corrosion of steel or other metals by water can be prevented by the application of a
coating or lining. To be effective, the coating must be impervious to water, salts, and other
corrosives, be free of pinholes or other discontinuities, and of sufficient thickness and strength
to prevent the water from contacting the metal.
The coating must be selected for compatibility with the environment and temperature. Proper
surface preparation and application of a coating is very important in maintaining long-term
trouble free protection. Since coatings lose some of their protective properties as they age,
cathodic protection is sometimes used in conjunction with a coating or lining.

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Cathodic Protection
Cathodic protection (CP) is a method of controlling corrosion of steel by making the metal
surface the cathode in an electrochemical cell by the application of a direct electrical current.
In water this is most frequently achieved by attaching a sacrificial or less noble metal, such as
magnesium, aluminum, or zinc to the steel. The corrosion is not eliminated but transferred to
the sacrificial anode which corrodes at an accelerated rate. In conjunction with coatings and
linings, CP reduces corrosion at holidays or damaged locations in the coating.
CP has been successfully used for many years to protect ship bottoms, wharfs, and offshore
structures from corrosion.
Sacrificial anodes are relatively easy to install in tanks, vessels, heat exchangers, and other
equipment. Once installed there are minimal maintenance costs. The disadvantages of
sacrificial anodes are: the electrical driving force is limited so a limited area is protected, and
anode life may be short when protecting large bare surfaces.
Materials Selection
In some severe environments it is economically justifiable to select corrosion resistant
materials to solve a corrosion problem. Copper alloys, stainless steels, nickel-based alloys,
and nonmetallics are all possible choices. Each alternative to steel has its advantages and
disadvantages. All properties, such as corrosion resistance, mechanical properties, strength,
weight, availability, ease of construction and repair, and also costs, must be considered in
selecting the materials of construction.
Chemical Removal of Dissolved Gases
Since carbon dioxide, hydrogen sulfide, and oxygen are the common corrodants in oil field
water, corrosion can be reduced by removing these gases by chemical and mechanical means.
Chemical removal of oxygen was discussed previously, and mechanical removal will be
discussed in a following section.
Hydrogen sulfide can be converted to sulfate, which is less corrosive by oxidants, such as
chlorine, hydrogen peroxide, ozone, and chlorine dioxide. H2S also reacts with aldehydes
such as formaldehyde and acrolein. Figure 12 shows how much of the different reagents are
required to scavenge H2S.

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FIGURE 12. CHEMICALS FOR REMOVAL OF HYDROGEN SULFIDE

Carbon dioxide cannot be removed by oxidizers or other chemicals. It can be neutralized by

alkalis or removed by mechanical means.
Design Factors
Several design factors can be used to minimize corrosion in water systems:
• Avoid crevices at welds, fasteners, etc.
• Avoid low flow regions - dead legs.
• Avoid high velocities and impingement.

Corrosion Monitoring
A number of techniques are available for monitoring corrosion both on-stream,
off-stream, and in the laboratory. Techniques that are applicable while the equipment is
in-service include: corrosion coupons, electrical resistance probes, linear polarization probes,
hydrogen probes, and chemical analysis of streams.
Coupons
A corrosion coupon is a small piece of material of interest which is exposed to the water
stream for a period of time and then removed and evaluated for corrosion or other damage.
Corrosion coupons are widely used to monitor corrosion in water systems. Some advantages
include the following:
• Inexpensive; a large number can be exposed economically.
• Various sizes, shapes, and forms (welded, stressed, with crevices) are available.
• Long exposure times are possible.

Disadvantages include the following:

• Coupon response time is slow and rapid changes in corrosivity are not detected.
Coupons reflect the average corrosion rate over the exposure period.
• Localized corrosion may not be initiated on the coupon during its exposure time.

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• Certain forms of corrosion cannot be detected by coupons.

• Velocity effects, erosion-corrosion, and heat transfer effects are often not indicated
by coupons.

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Proper selection of the coupon shape, surface finish, metallurgical condition, and geometry
allow evaluation of specific forms of corrosion. Rectangular or circular shaped coupons are
commonly used to evaluate uniform corrosion (see Figure 13). Proper preparation and
handling of coupons are required for meaningful monitoring. After the surface is finished, the
coupon must be stored in a dry container, in paper bags treated with vapor-phase inhibitors, or
in plastic bags with a sheet of paper treated with an inhibitor. Clean gloves should be worn
when handling coupons to avoid corrosion by contact with the skin. When removing coupons
from equipment, care should be taken to blot the coupon dry without removing any scales or
deposits. The appearance should be noted. When sending coupons for evaluation, the
following information should be included: the location, system or unit, location of the coupon
in system or unit, coupon identification number, metal, date installed, date removed, initial
weight, and other information.

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FIGURE 13. CORROSION COUPONS

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The coupon should be cleaned and reweighed as soon as possible after removal from the test.
The procedures for cleaning depend on the test material and the extent of corrosion. After
cleaning, the forms of corrosion to be expected in the equipment are revealed. Visual and
microscopic observations may be helpful in evaluating the coupon and metallographic
examination may also be useful. Special localized effects may be present which invalidate the
calculation of a uniform corrosion rate and signal other corrosion mechanisms. For example, a
coupon might undergo edge attack, crevice corrosion, stress corrosion near the stenciled
identification numbers, pitting, selective corrosion (e.g., dealloying), blistering, intergranular
corrosion, embrittlement, or erosion-corrosion. In addition, there may be inadvertent
mechanical damage or galvanic corrosion.
If the attack is uniform the corrosion rate of a coupon can be calculated using the following
equation (note that the numbers in the formulas are conversion factors that are used to
calculate the corrosion rate in conventional units):
534 x 1000 x W = mils per year (mpy)
DAT

where:
W = weight loss, grams
D = density of the metal, gram/cc
A = Coupon area, sq. in.
T = Exposure time, hours

If the coupon area is measured in sq. cm, the equation becomes:

3450 x 1000 x W = mils (0.001 inch) per year (mpy)

DAT

or,

876 x 100 x W = mm per year (mm/y)

DAT

40 mpy = 1 mm/y, approximately.

The numbers in the preceding equations are simply conversion factors which are required to
calculate the corrosion rate in the desired units.

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Polarization Resistance Probes

Another popular system for on-line corrosion monitoring is the linear polarization technique,
instrumented in the widely used CORRATER® systems from Rohrback Corporation. It is
based on the principle that a linear relationship exists between a small electrical potential
applied to a metal in a conductive liquid environment and the resulting current. The measured
current bears a direct relationship to the corrosion rate.
With linear polarization the corrosive medium must be a conductive liquid, such as water. It is
not useful in gases or hydrocarbon streams. Advantages include:
• Instantaneous and sensitive measurements of corrosion rates are possible.
• The probe test specimen does not have to be seen or removed.
• Process changes can be followed and corrosion control can be very rapidly
adjusted.
• Corrosion rates from less than 1 mpy to greater than 1000 mpy can be measured.
• Direct reading and recording of corrosion rates are possible with commercially
available instruments, minimizing any calculation error.

The major disadvantage is that linear polarization cannot distinguish solution oxidation-
reduction processes from corrosion (metallic oxidation); consequently, it is not applicable to
alkaline sour water with cyanide, polysulfide, or thiocyanate present.
Electrical Resistance Probes
Electrical resistance monitoring equipment, such as Rohrback Corporation’s
CORROSOMETER® systems, can be used to monitor process streams or other environments
through special sensing probes. The probe consists of a wire or element exposed to the
stream, and an electrical resistance sensing circuit with temperature compensation (see Figure
14). As the wire corrodes, its cross-sectional area decreases. This causes the electrical
resistance of the element to increase. Corrosion rates are obtained by converting the increase
in resistance to metal loss. Advantages include the following:
• Measurement can be made frequently without removing the probe from service to
obtain a history of corrosion.
• Measurements are rapid or continuous allowing adjustment of the corrosion control
program, if required.
• The technique is highly sensitive. Changes of less than a microinch can be detected.

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Disadvantages include the following:

• Localized corrosion (pitting, crevice, galvanic, stress corrosion cracking, fatigue,
etc.) will not be progressively identified.
• If the corrosion product adheres to the metal and has a resistivity near that of the
metal, little or no corrosion would be indicated. The formation of conducting
deposits would have the same adverse effect.

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FIGURE 14. ELECTRICAL RESISTANCE PROBE CIRCUIT

(SOURCE: REFERENCE NO. 4, Corrosion Monitoring, Primer)

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Hydrogen Probes
In oil field waters hydrogen sulfide reacts with steel to form iron sulfide and atomic hydrogen
(Ho). In some environments the recombination of atomic hydrogen to molecular hydrogen is
poisoned on the surface by the sulfide.
Fe + 2HS- ——> FeS + 2Ho + S-2
The atomic hydrogen diffuses into the steel where it recombines to form molecular hydrogen,
which causes hydrogen embrittlement and blistering. Hydrogen probes can be used to
quantify this type of damage.
The probe consists of a pressure gauge connected to a hollow cavity in a steel probe (Figure
15). An inert fluid is used to fill the cavity to ensure sensitivity. The probe is inserted into a
stream. As the external surface of the probe corrodes, atomic hydrogen passes through the
probe wall into the cavity. The rate of increase in pressure is related to the corrosion rate.

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FIGURE 15. HYDROGEN PROBE

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Chemical Analysis
Chemical analysis of water can be used to track corrosion by detecting the presence of
corrodants, corrosion products, the concentration of inhibitors, pH, acidity, oxygen, chloride
content, conductivity, and other chemical characteristics of water.
The concentration of steel corrosion products (called iron counts) in a water stream is often a
useful relative measure of corrosion. Changes in concentration are directional guides that
relate to corrosion rates. Iron counts are not reliable in all systems because the solubility of
the corrosion products is low. If areas of low flow are present, the iron may be deposited in
these areas; therefore, the iron count in the water gives a misleadingly low indication of the
corrosion.

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Equipment for Removal of Gases, Solids, and Dispersed Oil

The removal of dissolved gas, suspended solids, and dispersed oil from water is accomplished
by a variety of techniques. The following section describes these techniques and the
equipment used for removal.
Dissolved Gas Removal
Removing dissolved gases from the water stream is the first step in the treatment process.
Oxygen, being the most undesirable gas, is removed first.
Oxygen
There are two process used to remove dissolved oxygen from water: nitrogen deaeration and
vacuum deaeration.
Deaeration towers or strippers are used for the mechanical removal of dissolved oxygen from
waters saturated with air. These towers can typically remove 95 % of the oxygen. Figure 16
shows a cut-away view of a deaeration tower used at the Qurayyah facility to deaerate
seawater for injection.

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FIGURE 16. ELEVATION AND CUTAWAY VIEWS OF THE DEAERATOR TOWER

(Source: Reference No. 5, OPERATOR TRAINING MANUAL)

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Seawater enters the deaerator at the top and falls down over fourteen trays into the storage
section. Stripping nitrogen enters the tower below the bottom tray, moves upward through the
trays, and exits out the vent at the top of the tower.
The deaerator vessel is constructed of steel and is coated with protective coatings. The trays
are constructed of type 316 stainless steel to prevent corrosion.
By reducing the partial pressure of oxygen by dilution with another gas (nitrogen, steam, or
others), it is possible to remove the oxygen from water. Since most gases are less soluble at
high temperatures, by increasing the temperature of the water the concentration of the
dissolved gases can be further reduced. In steam generating systems steam is available for the
stripping gas. In the oil field, natural gas, nitrogen, or others may be used.
For maximum stripping it is necessary to provide thorough mixing of the stripping gas and the
oxygen laden water. This is accomplished by the use of fourteen trays in the tower. The
amount of oxygen left in the seawater will decrease as the flow of nitrogen is increased.
Strippers will remove oxygen more effectively in the summer than in the winter months due
to the changes in ambient water temperature. The nitrogen gas used for stripping must have a
very low oxygen content.
If a water has a tendency to foam, the efficiency of stripping decreases. The design of the
column should provide low water velocities to prevent foaming. Chemical antifoams may also
be required.
Vacuum deaerators work on the principle that if the pressure of the gas in contact with water is
lowered, the concentration of dissolved gases in the water decreases. A single-stage cold
water vacuum deaerator can reduce the free carbon dioxide to less than 5.0 mg/l as CO2 and
the free oxygen to less than 0.1 mg/l as O2. To achieve these removal levels the units are
normally operated at a water flowrate of less than 73.5 m/hr (30 gpm/ft2). Incoming water is
sprayed on top of a packing bed at least 3.0 m (10 ft) deep. The breakup of the water into
small droplets permits the release of the gases from the water under full vacuum. The gases
and water vapor are removed by either vacuum pumps or steam operated jet eductors. Figure
17 depicts a cold water vacuum deaerator.

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FIGURE 17. COLD WATER VACUUM DEAERATOR

(SOURCE: REFERENCE NO. 6, Demineralization by Ion Exchange)

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One to three stages are common in a cold water vacuum deaerator. The water enters the upper
stage, which operates at the highest pressure, and is sealed from the stage below by a layer of
water. The water flows down to the other stages and out the bottom.
Hydrogen Sulfide
Hydrogen sulfide can be removed from water in a stripping tower by using air or flue gas as
the stripping gas. When air is used the process is called aeration. This saturates the water with
oxygen so that it is not useful for corrosion control. In some locations, the odor of hydrogen
sulfide in the exhaust air also creates a problem.
Hydrogen sulfide is stripped most efficiently when the pH of the water is low and where the
strippable H2S forms predominate over the bisulfide (HS-) or sulfide (S-2) forms. The pH
should be less than 5.0 at ambient temperatures.
Carbon Dioxide
Carbon dioxide can be removed by aeration or vacuum deaeration. Like hydrogen sulfide,
stripping is pH dependent, and the stripping efficiency is improved by lowering the pH.
Suspended Solids Removal
Filtration is a common water treatment process used to remove suspended solids such as sand,
mud, corrosion products, and oil from water. Injection water is nearly always filtered to avoid
plugging of the formation by suspended solids.
A filter system will normally include a pressure vessel, either vertical or horizontal, an
internal water distributor/collection system, a media support system, and pressure gauges on
both the inlet and outlet. It will also include external piping and valving for the raw water feed
and treated water discharge, backwash, vessel draining, air scour (in some filters), etc.
Graded Bed Filters
Granular media filters using a single filter bed of sand are applicable to aqueous streams
containing up to 20 mg/l of total suspended solids (TSS) achieving an effluent quality of 1
Nepholometric Turbidity Unit (NTU). Silica sand is the most common filtration media,
particularly for single media filters. Other common materials used include anthracite and
crushed garnet.

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Media selection is a function of the following factors:

• Raw water suspended solids characterization.
• Filtered water quality.
• Desired length of filter runs.
• Number of filters.

In addition to the filtration media, different grades of gravel and stone are normally used to
provide a bed support structure for the media. The selection and configuration of the filter
media will depend upon a number of critical operational and design parameters. Figure 18
presents the various filter materials and their physical characteristics.

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Material Effective Size Specific Gravity

Silica Sand 0.4 to 0.8 mm 2.65

Anthracite 0.7 to 1.5 mm 1.6

Crushed Garnet 0.2 to 0.4 mm 4.5

FIGURE 18. MATERIAL/EFFECTIVE SIZE/SPECIFIC GRAVITY

Single media filters utilizing silica sand will provide a limited removal of suspended solids.
They should only be applied to waters containing 1 to 20 mg/l of suspended solids.
An alternative approach to provide a limited improvement over downflow service sand filters
is to operate the filter in an upflow service mode. In this system the backwash water will also
be injected upflow. The drawback to upflow filter service is that there are limitations to the
flowrate that can be utilized. The media must not fluidize or be lifted during the service cycle.
If this occurs a sudden release and breakthrough of suspended solids in the effluent water will
result. Figure 19 provides an illustration of the two approaches.

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FIGURE 19. SINGLE MEDIA FILTERS

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The Qurayyah facility utilizes horizontal sand pressure filters equipped with an air scour. A
polyelectrolyte flocculant is injected into the water ahead of the filter to improve the removal
of suspended solids from the seawater.
Multimedia Filters
The multimedia filter is an improvement to the single media filter and has two or more media
layers. Multimedia filters are used for treatment of aqueous streams containing as high as 50
mg/l TSS with the capability to achieve a 0.1 NTU effluent quality. Depending on the type of
suspended solids in the raw water up to five different types of media have been utilized in a
single vessel. The most common configurations for multimedia filters are as follows:
• Dual Media: Consists of a layer of anthracite placed on top of a layer of silica sand.
• Tri-Media: Consists of a layer of anthracite on top of silica sand and a bottom layer
of garnet.

These configurations can increase the filter run length by 200 to 600 % over the single media
sand filters. Figure 20 illustrates a typical multimedia filter utilizing anthracite, sand, and
garnet media.

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FIGURE 20. TYPICAL MULTIMEDIA FILTER

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A typical operating sequence involves the following:

• On-line service until loaded with solids.
• Backwash and optional air scour to remove the filtered solids and reclassify the bed.
• Drain and rinse to settle the bed.
• Return to service

Where the raw water supply contains an appreciable amount of colloids or suspended solids
with a particle size less than 0.45 microns, the addition of a polyelectrolyte ahead of media
filters has been very successful in improving the filterability of these types of suspended
solids. This process is called in-line coagulation. The function of the polyelectrolyte is to
provide a nucleus where the smaller suspended solids can attach and agglomerate. This
provides a much larger particle size which is easily filtered from the water.
There are three general categories of organic polyelectrolytes: cationic, which are positively
charged; anionic, which are negatively charged; and nonionic, which are not charged. The
proper polyelectrolyte and dosage is selected using jar tests.
Cartridge Filters
Cartridge filters possess a limited capacity for suspended solids and should only be used for
their secondary, precautionary removal ahead of equipment such as reverse osmosis units,
which are very sensitive to fouling by suspended solids. Cartridges are available in pleated
paper and plastics, sintered metals, woven mesh screens, woven fibers, and other materials.
Field tests should be used to evaluate a cartridge filter before selecting one.
Cartridges often have nominal ratings, for example 5, 10, or 25 microns. These ratings must
be viewed critically, since they may have little relation to the size of particles which are
actually passed. Also, the ratings from one manufacturer cannot be compared to another since
standard tests are not used to develop these ratings. Absolute ratings are more reliable.
Disposable and backwashable cartridges are available. Backwashable types should be
considered unless it is certain that plugging will be infrequent. Maintenance and replacement
costs can be very high with disposable cartridges.

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Monitoring Suspended Solids

There are three tests used to monitor suspended solids. Turbidity is the most common.
Suspended particles in water scatter light. Turbidity is a measure of the amount of light
scattered by a water sample. Today, nephelometric turbidimeters are most common. They
measure the amount of light scattered at 90 degrees from the source. The standard unit of
measurement is the nephelometric turbidity unit (NTU). The amount of scattering is
dependent on the amount, size and shape of the suspended solids; therefore, turbidity is only a
relative measure of the suspended solids present. However, turbidimeters are widely used
because they provide a rapid and simple test, and on-line instruments are available. Laser light
scattering can be used to measure the number of particles which fall within a given particle
size. This is useful in selecting a filter.
Suspended solids can also be measured by passing a water sample through a filter (usually 0.5
micron) and weighing the solids which are retained by the filter. This is useful when more
than about 5 mg/l suspended solids are present. Down stream of filters less than 1 mg/l is
often produced. At this location this test is not useful.
Particle counters are sometimes used to quantify suspended solids in very pure water. A
Coulter particle counter is used at the Qurayyah facility to measure the quality of the filtered
injection water.
Dispersed Oil Removal
The effluent water from a desalting train and the produced water from the production traps
must be disposed of, generally by injection into disposal wells. Oil and oily solids in these
wastewaters are referred to as carryover and result in injection well plugging. Oil and oily
solids can be separated from the water using a number of techniques.
Skimmers
Free oil is oil which separates from water because it has a lower specific gravity and forms a
separate liquid phase. Free oil can be separated from the water in a skimmer tank. A skimmer
tank provides an area of low water velocity and sufficient time for the free oil to rise to the
surface of the water where it can be skimmed off.

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The effluent water from the desalter and the produced water are often collected in a water/oil
separator. This is a large horizontal gas blanketed vessel where water and oil separate by
gravity. Recovered oil is returned to the process stream and the wastewater is sent to disposal
wells. Sufficient wastewater storage is required to hold the water during short periods when
injection capability is lost. A wastewater surge tank (WWST) is generally provided for this
purpose. This tank is normally held at a low level and may hold a low level of stagnant water
for a prolonged period.
Parallel Plate Separators
These separators also work on gravity and consist of an array of tilted (about 45 degrees)
parallel plates about 5-10 cm (2-4 in) apart. Oily water enters the top and flows down. The oil
only has to rise less than 5-10 cm (2-4 in) before it hits a plate. On the plate the tiny oil
droplets coalesce and travel upstream where they are collected at the top. The clean water
leaves from the bottom. Tilted flat plates and corrugated plates are used.
Flotation
Flotation is another separation process based on gravity. It uses fine bubbles of gas which are
injected into or formed near the bottom of a vessel. As these bubbles rise they become
attached to the oil and solids and help lift them to the surface for collection.
Coalescer
A coalescer is a vessel packed with a media which has a large surface area. The media causes
fine oil droplets to coalesce into larger drops which rise to the surface for collection. The
following types of coalescing media are used:
• Polyurethane foam pack
• Polystyrene divinyl benzene resin beads
• Granular media
• Walnut shells.

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GLOSSARY

anode The location in an electrochemical cell where oxidation

(consumption of a metal) occurs.
ATP analysis A rapid test for counting viable bacteria.
backwash In filtration, the process of passing water upward through a
bed of media to lift and separate the media and flush captured
solids out of the bed.
bacteria Microscopic organisms which can grow in many waters.
bactericide A material which destroys bacteria.
basic sediment and The impurities in crude oil which are removed in a
water (BS&W) desalting operation.
biocide A material which destroys living organisms.
biofilm The gelatinous matter produced by bacteria.
cathode The location in an electrochemical cell where reduction
(consumption of the oxidant) occurs.
cathodic protection A technique for controlling corrosion by making the metal
surface the cathode in an electrochemical cell.
cavitation Formation of bubbles by rapid pressure changes.
chelants Chemical compounds used to remove scales which form
soluble complexes with metallic ions (e.g., calcium, iron,
etc.).
Chemets Trade name of Chemetrix, Inc. for a field test kits for the
chemical analysis in water.
coalescer A device which aids in removal of oil from water by
coalescing small droplets of oil on the surface of special
media.
converter A chemical which converts a scale to another more soluble
material which can be removed by flushing or acid cleaning.

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corrosion Damaging attack of metal by its environment.

corrosion coupon A small piece of metal which is exposed to an environment
and then evaluated to measure the corrosivity of a system,
material performance, and/or effectiveness of a corrosion
control program.
culturing Growing bacteria in a controlled environment in order to
identify or count the types of bacteria present.
deaeration tower A vertical vessel used to remove gases (oxygen, hydrogen
sulfide, carbon dioxide, etc.) from water.
desalter A vessel in which salt and sediment are removed from crude
oil.
electrical resistance A device for rapidly measuring the corrosivity of a water
probe based on the change in electrical resistance of a wire or
element.
epifluorescence A technique which allows rapid counting of the population
microscopy of bacteria in a sample.
filter A device for removing suspended solids from water.
flotation Separation of oil from water using fine bubbles of gas.
galvanic corrosion Corrosion caused by coupling dissimilar metals in a
conductive environment.
gypsum A form of calcium sulfate scale.
hydrogen probe A device for measuring the damaging effect of hydrogen.
incompatible waters Waters do not form scale separately, but when mixed form a
scale.
inhibited acids Acids used for cleaning equipment which contain a corrosion
inhibitor to protect the metal during exposure.
inhibitor A chemical which slows the rate of corrosion.
injection water Water which is injected into producing reservoirs to aid
production.

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in-line coagulation The use of chemical coagulants to improve filtration.

ion activity product (IAP) A calculated term which is related to the solubility of a salt or
mineral scale.
iron bacteria Bacteria which convert soluble iron to insoluble iron
compounds which cause fouling and plugging.
microbiological fouling The adhesion of microbiological growth to process
and corrosion components, filters, piping, membranes, etc. which can
damage and reduce the efficiency of the component.
oxidant Any substance or compound that can add electrons, in a
chemical reaction.
oxidation Corrosion reaction in which a metal is dissolved as an ion
accompanied by a loss of electrons.
oxygen corrosion Corrosion of steel by dissolved oxygen in water.
oxygen scavenger A substance which chemically reacts with low concentrations
of dissolved oxygen to remove the oxygen from the water.
parallel plate separator A device consisting of an array of plates used to separate oil
from water.
polarization resistance A device for rapidly measuring the corrosivity of a water
probe based on electrochemical measurements.
produced water Water which is produced with oil and gas.
RapidCheckII The name of a test kit marketed by Conoco for rapidly
counting sulfate reducing bacteria.
Robbins device A device used to count bacteria which grow on a metal
surface.
sacrificial anode A piece of metal which corrodes and thereby protects a metal
to which it is connected.
scale Solid material formed on the walls of piping and equipment
by the precipitation of dissolved ions.

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serial dilution A technique for counting bacteria involving repeated dilution

of a sample.
skimmer A device for removing oil on the surface of water.
slime formers A general group of bacteria which form gelatinous capsules
and slimy deposits.
solubility The limiting amount of a material which can dissolve in a
solvent (water).
sour corrosion Corrosion of steel by hydrogen sulfide in water.
sterilization Completely killing organisms with the use of a biocide or a
chemical which is toxic to organisms or heat.
stripper A deaeration tower.
sulfate reducing Corrosive anaerobic bacteria found in water systems.
bacteria (SRB)
suspended solids Undissolved particulate materials present in water which can
be removed by screening or filtration devices.
sweet corrosion Corrosion of steel by carbon dioxide in water.
total dissolved solids The sum concentration of all the dissolved salts in a
(TDS) water usually calculated in mg/l or g/l.
turbidity The cloudiness of water used as a quick, convenient measure
of the relative amount of suspended solids present.

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References

1. Bansal, K. M., Holland, S., Chen, E. Y., “Corrosion in Wet Crude Transmission and
Processing”, Arabian American Oil Company, Dharan, Saudi Arabia, presented as
Paper Number 36, Corrosion 85, Boston Massachusetts, USA.

2. Petrotech Consultants, Inc., Operator Training Manual, Qurayyah Seawater Supply

System.

3. Petrotech Consultants, Inc., Operator Training Manual, Qurayyah Seawater Supply

System.

4. “Corrosion Monitoring Primer, Edition 3”, Rohrbacu Cososco Systems, 11841 East
Smith Ave., Sante Fe Springs, CA 90670.

5. Petrotech Consultants, Inc., Operator Training Manual, Qurayyah Seawater Supply

System.

6. Applebaum, Academic Press, Demineralization by Ion Exchange, Page 119, Figure

5.5

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