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Contents
CHAPTER 1: INTRODUCTION ............................ 1-1
BACKGROUND ................................................................... 1-3
Existing Systems Designed for Old Waterfloods......... 1-3
A New System To Be Installed for a New Waterflood
or EOR Project ......................................................... 1-4
OILFIELD WATER REQUIRING TREATMENT ................... 1-4
Water Sources ................................................................. 1-4
Characteristics of Waters That Affect Their
Handling and Treatment .......................................... 1-5
Produced Waters: ........................................................ 1-5
Source Well Waters: .................................................... 1-6
Open Waters: ............................................................... 1-6
WATER TREATMENT OBJECTIVES .................................. 1-7
POSSIBLE TREATMENTS REQUIRED TO ACHIEVE
OBJECTIVES ................................................................ 1-8
Treatment Objective Injection ................................... 1-9
Filtration ....................................................................... 1-9
Removal of Free Oil from Water ............................... 1-10
Effective Corrosion, Scale, and
Biological Control ............................................... 1-11
Separate Treatment of Waters .................................. 1-11
EOR Treatment Considerations in Addition to
Those Listed Above ........................................... 1-12
Treatment Objective Surface Disposal ................... 1-12
Additional Water Treatment Objectives ...................... 1-13
Corrosion, Scale, and Biological Control ................ 1-13
Recovery of Free Oil in Water and Lost Revenue ... 1-14
Special Treatment for EOR Requirements .............. 1-14
Nonroutine Treatments of Special
Oilfield Waters ..................................................... 1-15
OILFIELD TREATMENT METHODS AND EQUIPMENT .. 1-15
GLOSSARY ....................................................................... 1-19
ii
iii
iv
vi
APPENDIX A
INDEX TO CHEVRON
CORROSION PROTECTION MANUAL ..................... 6-29
APPENDIX B
INDEX TO CHEVRON COATINGS MANUAL............. 6-31
APPENDIX C
INDEX TO CHEVRON PIPELINE MANUAL ............... 6-33
vii
viii
CHAPTER 9: WATER/FORMATION
ROCK INTERACTIONS ................................... 9-1
INTRODUCTION ................................................................. 9-3
Mechanisms of Formation Permeability Damage ........ 9-3
Formation Clay Deflocculation and Migration .......... 9-3
Formation Clay Structural Expansion ....................... 9-4
Mica Alteration ................................................................ 9-5
Differential Dissolution .................................................. 9-6
Dissolution and Reprecipitation .................................... 9-7
Precipitation .................................................................... 9-8
Identifying Potential Formation Permeability
Damage ..................................................................... 9-8
Water and Rock Analyses .............................................. 9-9
Proper Salts and Concentrations ................................ 9-10
PREVENTING FORMATION DAMAGE IN THE FIELD .... 9-13
REFERENCES................................................................... 9-15
GLOSSARY ....................................................................... 9-17
APPENDIX ......................................................................... 9-19
ix
C H A P T E R
1
Introduction
Chapter 1: Introduction
1-1
1-2
BACKGROUND
Handling and treating of water in an oil field are important factors for successful, economical operation of the
field. These factors become especially important as fields
mature and the produced water cuts increase to levels
where the volume of water treated, reinjected, or disposed of can be 10 to 50 times the volume of oil produced. Even in new, low-water-cut fields, at least as
much water as oil produced may have to be treated and
injected to maintain reservoir pressure and to control
voidage. Enhanced oil recovery (EOR) projects require
good-quality water for injection for three reasons:
1. To raise and maintain reservoir pressure.
2. To act as the carrier for the chemicals designed to free
oil from pore spaces and/or improve the sweep
efficiency.
3. To be converted to steam and transfer heat needed to
lower viscosity and mobilize heavy crudes.
Water treating systems present some special challenges.
The greatest challenge relates to the fact that oilfield
waters change continually in terms of volume and chemical and physical properties. Also, because of its reactivity
(corrosivity, scaling tendency, microbiological activity,
etc.), water causes the treating system itself to change
with time.
The following discussion illustrates some problems
involving water treating systems.
Chapter 1: Introduction
1-3
1-4
Produced Waters:
1. Generally are corrosive as a result of elevated temperature and high salinity.
2. Usually contain dissolved gases (oxygen, carbon
dioxide, and/or hydrogen sulfide), which increase
corrosiveness.
3. Will vary in terms of physical and chemical properties
with time, location, and field operations (wells shut
in, brought on line, being worked over, stimulated,
etc.).
Chapter 1: Introduction
1-5
Open Waters:
1. Are very corrosive because of high levels of dissolved
oxygen.
2. Can contain anywhere from low to very high
concentrations of suspended solids that may be organic or inorganic and can vary seasonally and/or
with the oilfield operation that is the water source.
3. May have variable chemistry, depending on the water
source.
4. Often are microbiologically active and potential
sources of bacterial contamination in surface facilities,
wellbores, and waterflooded formations.
5. May contain significant nutrients and reducible oxygen to facilitate bacterial growth.
1-6
Chapter 1: Introduction
1-7
1-8
Filtration
1. Economical water injection requires that lives of the
injection wells to be maximized. Economical justification of filtration must consider more than the capital
and costs of the filters. Filtration costs must be compared with costs for drilling new wells, working over
or redrilling plugged wells, or stimulating partially
plugged wells. An effective stimulation treatment
does more than just increase injectivity one time only.
The number of times an injector can be stimulated
successfully must also be considered. This includes
the detrimental effects of acids on well equipment and
the effect of the treatment on injection profile. There
is also the question of whether permits may be secured from regulatory agencies to drill new wells.
Regulations are becoming more restrictive for disposal wells. A proper decision to install filters must
have input from reservoir, production, gas and chemical, and design and construction engineers, as well as
from environmental coordinators.
Economical justification
for filtration must
consider its costs versus
the benefits of increased
injector life and improved
waterflood sweep
efficiency.
Chapter 1: Introduction
1-9
1-10
Waters of different
qualities should be
treated separately as a
point source.
1-11
1-12
3. A list of effluent components with maximum allowable concentrations (absolute or relative to ambient).
Effluent components include (in addition to oil
and grease content and toxicity) suspended solids,
oxygen demand, sulfides, chlorine, pH, ammonia,
radioactivity, metals, and organics.
4. Temperature.
5. Volume of water discharged.
Meeting these standards may require additional oil
removal and other equipment besides that needed for
injection. In some cases, special processes, such as activated carbon adsorption, have been required to remove
organics (e.g., phenols). Drinking water standards,
groundwater protection, and air pollution controls are
becoming more important in state and federal surface
discharge permitting processes.
Chapter 1: Introduction
It is important to control
corrosion, scale, and
bacteria growth both to
protect equipment and
maintain good water
quality.
1-13
2. The chemicals added to the water to control corrosion, scale, or biological activity may not be compatible. Included are surfactants of all types, polymers,
reducing agents, and oxidizing agents. The combination of chemicals used and the points where they are
added must be evaluated carefully.
1-14
polymers added for EOR. Also, polymers will increase the biological activity of the system, requiring
re-evaluation of biocides.
4. Finally, added surfactants and pH changes for EOR
will dislodge scales and other deposits from pipes
and vessels. Secondary filtration or filter modifications will be needed.
5. Coalescers
6. Combinations of coalescers and skimmers
Chapter 1: Introduction
1-15
7. Precipitators
8. Flotation units
a. Dissolved gas
b. Dispersed gas
9. Disposal piles (on platforms)
10. Hydrocyclones liquid/liquid
a. Static
b. Dynamic
B. Filtration (suspended solids)
1. Sand filters
a. Upflow
b. Downflow
c. Duoflow
d. High and low rate
e. Single and multimedia
f. Coalescing
g. Horizontal and vertical
2. Precoat filters (diatomaceous earth)
3. Cartridge filters
a. Disposable cartridge
b. Backwashable
4. Fluidized bed, regeneration-type filters
a. Walnut-shell media
b. Pecan-shell media
5. Hydrocyclones solid/liquid
6. Flotation units (see Item A-1-h)
7. Dry cake filters
a. Precoat and body feed on wire-wrap screen
1. Diatomaceous earth
2. Pearlite
3. Walnut and pecan shells
b. Rotary drum filters
c. Plate-and-frame filters
C. De-aeration (oxygen removal)
1-16
1. Gas stripping
a. Nitrogen
b. Fuel gas
c. Flue gas
d. With or without packing or plates
2. Vacuum
D. Gas Stripping to Remove H2S
2. Chemical Methods (Involve Changes in Water Chemistry)
A. Surfactant Addition
1. Emulsion breakers for oil/water separation
2. Filter cleaners in backwash water
3. Relative permeability modifiers to improve
water injectivity
4. De-aerator antifoamers and defoamers
5. Some biocides
6. Corrosion inhibitors
7. Scale inhibitors
8. Oil-coalescing surfactants
B. Oxygen Scavenging
1. Various sulfides ( SO 2 , HSO 32 , SO 3 2 )
C. Biocide Addition
1. Oxidizers
a. Chlorine
b. Chlorine dioxide
2. Aldehydes
3. Quaternary amines
4. Mixed aldehyde/amines
D. Corrosion-Inhibitor Addition
1. Filming amines
2. Water dispersible or soluble
Chapter 1: Introduction
1-17
E. Scale-Inhibitor Addition
1. Phosphates
2. Phosphonates
3. Mixtures
F. Changing pH
1. Decrease
a. Adding SO2 to control scale
b. CO2 flooding (EOR)
c. Reducing alkalinity
d. Decreasing solubility of dissolved organic
compounds
2. Increase
a. Neutralizing weak acid softener spent
regenerant
b. Removing of H2S or CO2 from water
c. Neutralizing water for discharge
d. Caustic flooding (EOR)
G. Controlling Cation Concentration
1. Softening
a. Exchange divalent ions for monovalent ions
b. Lime soda
2. Direct addition of salts
a. Increase potassium concentration
b. Increase salinity
3. Mixing waters of different salinities
H. Adsorption of Dissolved Organics on Activated
Charcoal
I. Addition of Polymers
1. Filteraids
2. Coagulants
3. Polymer flood (EOR)
1-18
GLOSSARY
incompatible waters waters when mixed form solid
precipitates.
total system approach considering effects in the entire
treatment system.
Chapter 1: Introduction
1-19
1-20
C H A P T E R
2
Analytical and Test Methods
2-1
2-2
WATER ANALYSIS
Reasons for Water Analysis
Chevron produces roughly 10 times as much water as
crude oil. This water causes many problems in producing operations and in treating for use or disposal. Waterrelated problems include:
Bacterial activity.
Corrosion.
Emulsions.
Formation damage.
Environmental restrictions.
Equipment fouling.
Formation plugging.
Scale and precipitate formation.
Incompatibility.
In water sampling and analysis, we determine the type
and amount of dissolved and suspended material in the
water and the physical, chemical and microbiological
properties of the water. Water analysis is a first step in a
diagnostic procedure (1) to ascertain the possibility of
problems, (2) to determine the existence of problems,
(3) to test possible physical and chemical remedial treatments, and (4) to measure the effectiveness of these
treatments.
Critical components:
dissolved solids,
suspended solids,
physical, chemical, and
microbiological
properties.
Water is a major component of all EOR projects. In caustic and steamfloods, we must know the types and
amounts of hardness and alkalinity and the total salinity
to determine the type and extent of softening required to
minimize the formation of plugging precipitates and
fouling scale deposits in steam generators. Knowledge of
hardness, alkalinity, and total salinity is necessary to
predict the effectiveness and compatibility of chemical
floods with surfactants or foams. With CO2 floods,
knowing the changing chemistry of CO2-acidified injection water (as it moves through and reacts with the
producing formation) helps us identify formation rock
2-3
2-4
Cations
Sodium, Na+
Is the principal monovalent cation in most waters.
All commonly occurring sodium compounds are
soluble, although sodium chloride may precipitate
from highly concentrated, nearly saturated brines.
Potassium, K+
Calcium, Ca2+
Usually is the principal divalent cation.
Contributes to and may be reported as water hardness.
Combines with sulfate or carbonate ions to form
suspended solids or adherent scale deposits.
2-5
2-6
Table 1
Cations
Sodium, Na
+
Potassium, K
2+
Calcium, Ca
2+
Magnesium, Mg
2+
Barium, Ba
2+
Strontium, Sr
2+
Iron, Fe
Hardness, as CaCO3
Anions
Chloride, Cl
Salinity, Chlorinity, and
Chlorosity
Carbonate, CO 2-3 and
Bicarbonate, HCO 3
Sulfate, SO 24
Organic Acids, as Acetate
Alkalinity, as CaCO3
Dissolved Gases
Oxygen, O2
Carbon Dioxide, CO2
Hydrogen Sulfide, H2S
Neutral
Components
Silica
Bacterial Content
Oil-in-Water
Total Residue
Total Dissolved Solids
Suspended Solids
Amount
Type
Particle Size Analysis
Properties
Magnesium, Mg2+
Frequently is present in smaller amounts than calcium
except in seawater or connate waters derived from
seawater.
Contributes to and may be reported as water hardness.
May form insoluble magnesium hydroxide at high
pH.
Readily forms ion pairs with sulfate ions, thereby
decreasing the activity of free sulfate ions and increasing the apparent solubility of sulfate scales and precipitates.
Barium, Ba2+
Is frequently found in produced waters but at a lower
concentration than calcium or magnesium.
Combines with sulfate ions to form extremely insoluble barium sulfate deposits that are difficult to
remove.
May indicate the presence of other radioactive alkaline earth cations (e.g., radium).
Strontium, Sr2+
Usually is associated with but at lower concentrations
than barium.
Forms insoluble strontium sulfate or mixed
strontium/barium sulfate precipitates.
Iron, Fe
NORM (naturally
occurring radioactive
material) is usually
radioactive divalent
cations included in
sulfate scales.
2-7
Hardness
Originally named for and determined by reaction
with soap solution to form scum or bathtub ring.
Reported as parts per million (ppm) or milligrams per
liter (mg/L) as calcium carbonate.
Calcium and magnesium
are the principal hardness
ions and form an
insoluble scum with
soaps.
Anions
Chloride, Cl Major anion in many waters.
Anions are negatively
charged ions that move
towards the anode in an
electrolysis cell.
2-8
Salinity
Chlorinity
Now defined in parts per thousand (ppt, ) as the
number of grams of silver necessary to precipitate
the Cl- and Br- in 328.5233 g of seawater.3
Usually determined by titration with silver nitrate.
Can be calculated from ionic concentrations by
2-9
Chlorisity
Obtained by multiplying chlorinity by the density of
water at 20C.
Similar to chlorinity except chlorisity is a weight-pervolume concentration term.
Sulfate, SO 42
Forms insoluble deposits with calcium, barium,
strontium, and other alkaline earth cations.
Electron acceptor (oxidizing agent) in the biogenic or
thermal production of hydrogen sulfide.
Barium sulfate (barite) is a common component of
drilling muds and may appear as a contaminant in
produced water.
Organic Acids
Organic acids can be a
carbon and energy source
for bacterial activity.
2-10
Major component (along with carbonates and bicarbonates) of alkalinity in some produced waters.
Generally are low-molecular-weight (C2 to C4) aliphatic acids or naphthenic acids (saturated acids with
five- and six-membered rings of carbon atoms).
Alkalinity
Measure of ability to combine with or consume hydrogen ions from an acid.
Made up primarily of carbonate, bicarbonate,
and organic acid anions, with minor contributions
from other acid anions (e.g., bisulfide, borate, phosphate) and weak bases (e.g., ammonia).
Is a major factor in fixing the pH and buffer capacity
of the water.
Is usually determined by titration with standard acid
and then broken down into component parts by other
analytical and calculation methods.
Dissolved Gases
Oxygen, O2
Can cause severe corrosion if present in even low
levels.
Recommended levels 20 parts per billion (ppb) to
minimize corrosion.
Oxidizes soluble iron to precipitate iron oxides.
Dissolved oxygen is a
major contributor to the
corrosivity of oilfield
waters.
2-11
Neutral Components
Silica
Is usually present in low amounts (<100 ppm) except
when water is hot and/or has a high pH.
Is a source of scale in boilers and steam generators.
Is used as a geochemical thermometer.
Bacterial Content
Bacteria must not only be
present, they must also be
active within the system
to cause problems.
2-12
Oil-in-Water Content
Must be low and meet environmental criteria for
discharge to surface waters.
May decrease injectivity by forming emulsion
blocks in the pores of the formation or by increasing
the oil saturation and thereby reducing the relative
permeability to water.
Acts as a cementing material for other suspended
solids.
Can be used to estimate efficiency of separators and
oily water treatment equipment.
Total Residue
Is the amount of solid material left after evaporating a
water sample and drying the residue at a specified
temperature.
Composed of nonfilterable residue (suspended solids)
plus filterable residue (dissolved solids).
Suspended Solids
Particulates that may plug injection wells, foul surface
equipment, or induce turbidity in receiving waters.
2-13
2-14
Properties
pH
Defined as the negative logarithm of the hydrogen ion
activity (concentration).
Affects solubility of carbonate, hydroxide, and sulfide
precipitates or scales.
Corrosion rate increases as pH decreases.
Low pH may indicate presence of corrosive acid
gases, CO2 and H2S.
Temperature
Must be measured in the field.
Strongly affects corrosion rates, precipitate solubilities, and efficiencies of oil/water separations.
Turbidity
Is a measure of water cloudiness or opacity.
Is caused by scattering and absorption of light by
particulates (suspended solids and dispersed oil).
Can be related to suspended solids and/or oil content
only if the system is well characterized and unchanging.
Is an indirect measure of water quality (high turbidity
indicates low water quality).
2-15
Color
Is produced by dissolved, colloidal, or suspended
colored material in water.
Is an indirect measure of water purity (low color may
mean high purity or at least the absence of colored
impurities).
Perception of color strongly influenced by strength
and color of incident light.
Density
Is defined as weight per unit volume.
Density and specific
gravity are numerically
equal only when the
reference water has a
density of exactly
1.0000 g/mL.
Conductivity
Measure of the dissolved ionic components.
Resistivity (reciprocal of conductivity) used for well
logging.
Can be a quality-control parameter because conductivity is related to ionic concentration.
Sampling
Steps in chemical
analysis:
1. sample preparation
2. sample preservation
3. chemical analysis
4. reporting
2-16
Sampling Procedures
The sample must be representative of the operating
system. The system sampled should be operating as
close as possible to normal conditions of flow rate, pressure, temperature, etc. Any departures should be noted
on the sample identification form. The sample should be
taken from a flowing, well-mixed stream, unless the
purpose of the sampling is to look at subnormal operating conditions.
Some system components or properties change rapidly
with time and cannot be adequately preserved or stabilized for later laboratory determinations. These components or properties must be measured or determined in
the field as close in time and location to the sample point
as possible. Other components may change with time
but can be preserved for later analysis. Still other components are reasonably stable and do not need special
preservation techniques. A complete analysis involves
field analysis for some components and laboratory analyses with an unpreserved sample and with several specially treated samples for the remainder.
All liquid samples for analysis or preservation should be
field-filtered as soon after sampling as possible. The
purpose is to remove dispersed oil and suspended solids
(scale deposits, corrosion products, formation fines, etc.)
present in the original sample. Chevron personnel developed an automatic pressure filtration apparatus4 suitable
for field filtration. Carpenter and Campbell5 gave specific details for field sampling and filtration. Multiple
filtrations may be necessary if dispersed oil concentra-
2-17
Table 2
Sample Location
Field, lease, well, section, state, country,
gathering station, tank battery, pipeline,
pit, etc.
Date and Time of Sample
Sampled By
Sample Description
Source, zone, or formation
Color, presence of oil and/or solids, odor, any
unusual features
Sample Conditioning
Filtration, refrigeration, special preservatives
(type and amount)
System Operation
Normal, abnormal, shut in
Flow rate and pressure at sample point
Treatment chemicals (type and amount)
present
Any unusual or abnormal factors
Field Analyses Performed
Types of analyses, location of results
tions are high. Dispersed oil, even when present in
moderate quantities, quickly saturates and bleeds
through most membrane filters.
The only exceptions to field filtration are measurements
for turbidity and color. These measurements must be
made in the field with unfiltered samples. Turbidity and
frequently color result from suspended or colloidal
material that could be removed by filtration.
For laboratory analysis, we prefer using a glass bottle
that was washed with acid, rinsed with deionized water,
and dried. Place samples in individual glass bottles for
2-18
Shipment of samples by
commercial carriers
requires special
precautions.
Field Measurements
The following components must be measured in the field
immediately after sampling and filtration:
pH.
Temperature.
Turbidity (must be done with an unfiltered sample).
Color (must be done with an unfiltered sample).
Total alkalinity.
Dissolved O2.
CO2.
Bisulfide, HS- (see Ref. 6 for a field analysis procedure
for low sulfide concentrations. As an alternative,
stabilize a separate sample with basic zinc solution).
Soluble iron(II).
Total suspended solids (primary filtration and washing with water performed in the field; subsequent
washings and weighings may be performed in the
laboratory).
Bacteria filtered or cultured from the sample in the
field with subsequent incubation and enumeration in
the laboratory.
2-19
Preserved Samples
Before sampling begins, consult the laboratory performing the analysis to determine acceptable preservation
techniques compatible with the laboratorys analytical
methods.
Cation Analysis A field-filtered sample preserved
with either hydrochloric acid or citric acid 5 is taken for
laboratory analysis of the following cations:
Sodium, Na+.
Potassium, K+.
Calcium, Ca2+.
Magnesium, Mg2+ .
Barium, Ba2+ .
Strontium, Sr2+ .
Iron(II), Fe2+ .
Many produced waters
contain components in
addition to bicarbonate
and carbonate that
contribute to the
alkalinity of a water.
2-20
Unpreserved Sample
A filtered sample with no preservatives or conditioners is
used for silica analysis. If the silica is expected to be
supersaturated at lower temperatures after sampling, the
sample should be diluted with a known volume of silicafree deionized water. The filtered sample also is used for
the common and stable anions (chloride and sulfate) and
cations (sodium and potassium). An unpreserved sample
is used to measure specific resistivity (or conductivity)
and specific gravity (or density). Additional portions of
this sample are used to measure laboratory pH, laboratory alkalinity, carbonate and bicarbonate alkalinity, and
nonvolatile acid content. These measurements are made
to check field analyses and to indicate possible gas exchange reactions, bacterial activity, or precipitation and
hydrolysis reactions that might have occurred between
sampling and laboratory analysis.
Dilution is commonly
used to preserve a
supersaturated solution of
silica.
Oil-in-Water Content
Separate samples, in individual glass bottles, are needed
for each oil-content determination (oil-in-water analysis).
If total oil content (free or dispersed oil plus dissolved
oil) is desired, the sample is not filtered. Prefiltration will
remove dispersed oil and allow estimation of dissolved
oil. Water samples containing large amounts of dispersed oil may need to be filtered several times to remove all the free oil. The filter may become saturated
with oil and permit excess oil to bleed through. If the
Currently, there is no
analytical procedure that
is specific for oil. Oil, by
definition, is whatever is
detected by a specified
analytical method.
2-21
Analytical Methods
Analytical methods for cations, anions, and dissolved
gases are summarized in Table 3; Table 4 lists the methods for neutral components and properties. The following section gives brief descriptions of the methods.
Chemical and physical properties of the sample can be
used to determine the concentrations of components or
measurement of properties.
Chemical Properties
Various procedures involving the chemical properties of
the constituents are used in water analysis.
Gravimetric analysis is
usually very accurate. It is
used to prepare and
determine analytical
standards. It is a
laboratory method.
Ba + SO 4 BaSO 4
2
2-22
Table 3
2-23
Table 4
2-24
Volumetric analysis is
convenient, inexpensive,
and widely used for a
large number of chemical
components. It is
frequently done in the
laboratory but many kits
are available for field
analysis.
Ag + Cl AgCl
W = V C E
where
W = weight of chloride ion present, mg;
V = volume of silver standard added, mL;
C = concentration of silver standard, meq/mL; and
2-25
2-26
Many electrochemical
analysis procedures have
been adopted for field
usage.
2-27
concentrations. Rugged electrodes and portable, batterypowered voltmeters are available for field measurements.
Concentration can be determined by single-point measurements and comparison with standards, or by multiple additions or subtractions of standards. The potentiometric electrodes can also be used as indicator
electrodes in volumetric titrations.
In amperometric or voltammetric analyses, the current
caused by the oxidation or reduction of an electroactive
species is measured and related to concentration. Selectivity for individual components is achieved by measuring the current at a specific applied voltage at which the
desired species is electroactive. Concentrations are
usually determined by comparison with currents obtained with standards under similar conditions. Examples of these types of measurements are electrodes for
dissolved oxygen determination and various forms of
voltammetry and polarography. Amperometric methods
can also be used as indicator electrodes in titration or
electrochemical procedures. Instruments are available
for field measurement of dissolved oxygen and various
forms of chlorine. Most other determinations are done in
the laboratory. A variant method is electrogravimetric
(plating) analysis in which the amount of electrodeposited material is determined by weighing.
The dispersed and
dissolved water in crude
oil can be quickly and
accurately determined by
an automatic coulometric
titrator (Karl Fisher
titration).
2-28
Currently used
chromatographic methods
have little or no
connection with color.
Physical Properties
Measures of some physical properties of a water sample
are frequently needed. Most of these measurements are
relatively simple and self-explanatory. They include
density or specific gravity measured with a hydrometer,
a pycnometer, or a Westphal balance and temperature
measured with a thermometer or thermistor. Many
portable pH meters can also provide temperature readouts.
A number of
organizations publish
standard analytical
methods. These methods
should be used whenever
possible to assure
accuracy and precision.
2-29
Analytical Report
The analytical report is
the final step in the
sampling and analysis
procedure. The reliability
of the data in the report
depends upon all of the
preceding steps in the
procedure.
2-30
Information from sampling and analysis is usually presented in a Water Analysis Report. The amount of information presented and the report format vary among
laboratories. In general, a report should contain sufficient information to identify the sample point and system
conditions at the time of sampling. It should list the
components or properties determined and the units of
concentration or measurement for each component or
property, respectively. Additional sections may present
solubility calculations, graphical display of water
composition, and water type or classification.
Sample Identification
The report should include sufficient information to identify where, when, how, and by whom the sample was
taken. This information should be available from a Water
Sample Description form completed for each sample
taken and submitted for analysis. This information,
discussed in the previous section, is summarized in
Table 2. Table 5 shows a Sample Data Sheet.5
Components as presented
in an analytical report are
not necessarily in that
form in the sample.
2-31
Table 5
Date:
Operator:
Sample designation:
Local contact:
Address:
Phone:
API Number:
Lease/Well:
Field:
State:
Country:
Rge:
Location:
Producing
Intervals:
Producing
Formation:
Method of Production:
Hydraulic Lift
Rod Pump
Other:
Production Rates:
Oil
Sample Point:
Other:
Wellhead
Sec:
Twp:
Centrifugal Pump
Gas
Gas Lift
Water
Flowline
(Day, Month)
Separator
Tank
2-32
EW2
EW1
where
W1 = weight in original form,
W2 = weight in converted form,
EW1 = equivalent weight of original form, and
EW2 = equivalent weight of converted form.
2-33
Units of Measurement
The units of measurement must be included for each
component or property listed in the analytical report.
Some form of concentration units will be listed for most
components. Properties typically have their own measurement units.
Concentration Units Concentration units express the
ratio of the amount of the specified substance or component in a given amount of the total system. A large
number of concentration terms are possible, depending
on how the units of substance and system are selected.
Fortunately, only a few are used for oilfield water analyses. Calculational conversion between units by mathematical factors is discussed later in Concentration Conversion Factors.
Before discussing specific concentration units in detail,
we should define a few basic chemical terms.
Atomic weight weight
of a single atom relative
to a carbon-12 atom.
Molecular weight
weight of a molecule
compared to the weight of
a carbon-12 atom.
2-34
Element
Hydrogen
Sodium
Magnesium
Calcium
Carbon
Oxygen
Sulfur
Chlorine
Symbol
H
Na
Mg
Ca
C
O
S
Cl
Atomic Weight
1
23
24
40
12
16
32
35.5
Molecular weight relative weight of a single molecule compared with the mass of the carbon-12 atom.
Molecular weight is equal to the sum of the atomic
weights of the atoms making up the molecule multiWater Treatment Handbook
Multiplier
Symbol
Multiplier
Atomic Weight
2 Na =
1 S =
4 O =
Sum =
223 =
132 =
416 =
Molecular
Weight of Na2SO4
Product
46
32
64
= 142
Equivalent weight is
relative to reacting
weight.
Substance
H+
Na+
Ca2+
Cl
HCO 3
2
CO 3
CaCO3
Atomic or
Molecular
Weight
1
23
40
35.5
61
60
100
Valence
+1
+1
+2
-1
-1
-2
2
Equivalent
Weight,
mg/meq.
1
23
20
35.5
61
30
50
2-35
There are four basic types of concentration terms, depending on how the amounts of the substance and system are specified. The amount of substance present can
be expressed in terms of its physical properties (mass or
weight and, in a few cases, volume) or its chemical properties (chemical reacting equivalents or stoichiometry).
The unit amount for the system can be expressed in terms
of its mass or its volume. (For water analyses, the sample
solution is the system.)
Weight-based and
volume-based
concentration units are
numerically equal only
when the solution density
is exactly 1.0000 g/mL.
2-36
(mg / L)
.
(density, kg / L)
2-37
(mg / L)
.
(density, kg / L)
= 10 (wt.)= 0.001(ppm).
Grains per Gallon (gpg) The weight in grains
(1 grain = 64.8 mg) of stated substance in one gallon
(1 gal = 3.785 L) of solution. This concentration unit is
sometimes encountered in water softening applications.
Conversion between mg/L and gpg is:
gpg = 17.12 (mg / L).
2-38
(mg / L)
.
(milliequiv. wt.)
(ppm)
(eq. wt.)
2-39
and
mg / L as CaCO 3 =
Normality is the
concentration term most
widely used by analytical
chemists.
Molarity is independent
of chemical reactions.
(mg / L)
(eq. wt.)
Molarity (M) The number of moles (weight of substance in grams divided by molecular weight in grams)
per liter of solution. This unit is used for analytical
reagents or systems containing a single compound. It is
related to normality as molecular weight is to equivalent
weight. It is not as confusing as normality, because a
reacting equivalence is not involved. Conversion to
molarity from weight concentration or normality is
M = 0.001
(mg / L)
(mol. wt.)
or
2-40
M=
N
(# of equiv./mole)
Molarity is not
temperature dependent;
especially important in
thermodynamic
calculations.
2-41
Table 9
To convert from
To convert from
mg/l
meq/L
multiply by
meq/l
mg/L
multiply by
Cation
mg/L
CaCO3
multiply by
CaCO3mg/L
multiply by
0.1112
0.2775
0.01456
0.04990
0.03148
0.03581
0.05372
0.9921
0.1441
0.08226
0.03640
0.07281
0.04350
0.5544
8.994
3.604
68.67
20.04
31.77
27.92
18.62
1.008
6.939
12.16
27.47
13.73
22.99
18.04
A13+
B3+
Ba2+
Ca2+
2+
Cu
2+
Fe
3+
Fe
+
H
+
Li
2+
Mg
2+
Mn
4+
Mn
+
Na
NH +4
+
Pb
2+
Sr
2+
Zn
5.564
13.89
0.7286
2.497
1.575
1.792
2.688
49.64
7.211
4.116
1.822
3.645
2.177
2.774
0.1797
0.07201
1.373
0.4005
0.6348
0.5580
0.3720
0.02014
0.1387
0.2430
0.5490
0.2744
0.4594
0.3605
0.4830
1.142
1.531
2.070
0.8755
0.6533
0.009653
0.02283
0.03060
103.6
43.81
32.69
2-42
To convert from
meQ/L
mg/l
multiply by
mg/L
meq/l
multiply by
Anion
0.02336
0.01251
0.02821
0.03333
42.81
79.97
35.45
30.00
BO
Br
Cl
2
CO 3
0.01724
58.00
0.05264
0.01639
19.00
61.02
CrO 4
F
HCO 3
0.02084
47.99
0.01031
96.99
0.03024
0.01233
33.07
81.07
0.01030
97.07
0.007880
0.02174
126.9
46.01
0.01613
62.00
0.05880
0.03159
17.01
31.66
0.06238
0.02629
16.03
38.04
NO 3
OH
3
PO 4
2S
2
SiO 3
0.02498
40.03
SO 3
0.02083
48.03
SO 4
CaCO3
mg/L
multiply by
CaCO3mg/L
multiply by
2-
1.169
1.597
1.412
1.669
0.8555
0.6262
0.7084
0.5995
0.8628
1.159
2.634
0.8201
0.3797
1.219
HPO 4
1.043
0.9590
H 2 PO 4
HS
HSO 3
0.5159
1.938
1.513
0.6172
0.6609
1.620
HSO 4
I
NO 2
0.5155
1.940
0.3943
1.089
2.536
0.9195
0.8071
1.239
2.942
1.581
0.3399
0.6327
3.122
1.315
0.3203
0.7602
1.250
0.8000
1.042
0.9589
2-43
2-44
Table 11 Con centration Con version Factors
CO NV ERSIO NS W ITH IN PH YSICA L CON CEN TR ATIO N U NITS
SOU GHT
C ONCEN TRATI ON
m g/L
A
wt %
B
m g/L, A
wt %, B
ppt, C
ppm , D
gpg , E
1E-4*A /R
1E-3*A /R
A/R
17.1*A
1E4*R*B
10*B
1E4*B
1.71E5*R*B
2E-3*C
1.71E4*R*C
ppm
D
gp g
E
R*D
1E-4*D
1E-3*D
17.1*R*d
5.84E-2*E
5.84E-6*E/R
5.84E-5*E/R
5.84-2*E/R
m eq/L
F
epm
G
m eq /L, F
epm , G
m g/L as C aCO 3 , H
Nor mality, N
M olar ity, M
M olar ity, m
F/ R
50*F
1E-3*F
1E-3*F /#
1E-3*F /(#*S)
R*G
50*R*G
1E-3*R*G
1E-3*R*G/ #
1E-3R*G/(#*S)
2E-5*H/#
2E5*H/(#* S)
1E3*N
1E3*N/R
5E4*N
N/#
N/(#* S)
Mo larity
M
Mo lality
m
1E3*#*M
1E3*#*M/R
5E4*#*M
#*M
M /S
1E3*#*S*m
1E3*#S*m/ R
5E4*#*S*m
S*#*m
S*m
SOU GHT
C ONCEN TRATI ON
m g/L
A
m eq/L
F
m g/L, A
m eq /L, F
Nor mality, N
A/J
1E-3*A /J
J* F
1E-3*F /#
A dditional definitions:
J
R
=
=
S
=
TDS =
milliequivalent weight, mg
solution density, kg/L
(R TDS1E 6) , weight of solv ent in 1-liter of solution, kg
num ber of equiv alent/m ole
1E3*J*N
1E3*N
N/#
Mo larity
M
1E3*#*J*M
1E3*#*M
2-45
sumed and purely hypothetical combinations. The combinations used could vary from one analysis to another,
depending on the purpose or use of the analysis. Presenting analytical results in this format is not recommended because the combinations are arbitrary and
falsely portray the dissolved species as existing in solution as specific, nonionized compounds.
Solubility Calculations
Solubility calculations
will tell if a precipitate
will form they cannot
tell how fast a precipitate
will form.
Reliable solubility
calculations at any point
in a system requires
accurate chemical analysis
at the same point.
2-46
reasonable estimates for extremes in salinity, temperature, or pressure. They frequently neglect the effect
of ion pairing upon ion activities in concentrated solutions. Simple calculations based on analytically measured ion concentrations rather than thermodynamically
calculated ion activities underestimate the solubility of
CaSO4 in seawater because they neglect the reduced
activity owing to MgSO4 ion pair formation. Unless
these program, database, and analysis limitations are
understood and accounted for, solubility calculations and
scaling tendencies reported on water analysis forms can
be misleading.
Caution!!
Simple calculation
procedures may not be
adequate for complex and
concentrated oilfield
waters.
Composition Diagrams
A number of ways to express water analysis data graphically have been proposed. A graphical presentation
usually permits more rapid comparison of a number of
water analyses and highlights differences and similarities
that might be missed by someone scanning tabular data.
With the availability of PCs and database programs for
data comparison, use of diagrams for comparison is
declining. Patton10 and Ostroff12 described a number of
these diagrams.
Quality Control
In the broadest sense, quality control or quality assurance
is the sum total of all methods, procedures, and practices
used to determine and maintain the quality of the analytical data produced by a laboratory. An excellent discussion of this aspect of quality assurance is given in Sec.
1020 of Ref. 2 (17th edition). In this chapter, quality
control is used in a more limited sense to indicate correctness or reliability of analysis. A complete geochemical
analysis including the major anions and cations, measured total dissolved solids, conductivity, density, and
pH is required to check for correctness of analysis.
Anion/Cation Balance
Determining the anion/cation balance is the primary
method of checking an analysis. This procedure is based
on the fact that aqueous solutions are electrically neutral
and therefore the sum of the concentrations of anions
2-47
[(cations) (anions)]
[ (cations) + (anions)]
Acceptable
Difference
0.2 meq./L
2%
(2 - 5)%
2-48
Calc. TDS, mg / L = Na + + K + + Ca + + Mg + +K
2
2
+ CO 3 + HCO 3 + Cl + SO 4 + C 2 H 3 O 2 +K , mg / L
2
CO 2
3 , HCO 3 , C 2 H 3 O 2 , HS , and any other ion in the
measured TDS
< 1.2
calculated TDS
Measured TDS is more likely to be greater than calculated TDS (1) because a significant component may have
been omitted in the analysis and hence in the calculated
TDS or (2) because of contamination or incomplete dehydration. If the ratio of measured/calculated TDS ratio is
<1, the larger of the anion or cation sums and the measured TDS may be wrong and should be checked or
reanalyzed. If the ratio >1.2, components in the smaller
of the ion sums should be reanalyzed.
Specific gravity is a
reliable measure of TDS
only for high TDS
solutions.
2-49
Table 12
Reference
Abbreviations:
Sp. Gr. = Specific Gravity
2-50
Ion
Sodium
Potassium
Calcium
Magnesium
Carbonate
Bicarbonate
Chloride
Sulfate
Conductivity (25C)
mhos/cm
Per meq/L
Per mg/L
48.9
2.13
72.0
1.84
52.0
2.60
46.6
3.82
84.6
2.82
43.6
0.715
75.9
2.14
73.9
1.54
2-51
where
G = conductivity of solution,
C = concentration of solution,
= equivalent conductivity at infinite dilution,
and
k1,k2 = constants for relaxation of ion cloud electrophoretic effects relative to ion mobility.
Calculation procedures13 for solutions of mixed anions
and cations are best performed on a PC. The theoretical
equations are valid up to a TDS concentration of about
5,000 mg/L. The complex calculations and dilutions
required for most samples make this method a second
choice. The first choice is the method using extensive
dilution and calculation with simple conductivity factors.
Measured Conductivity vs. Ion Sums The anion and
cation sums, in meq/L, should be numerically equal to
approximately 1% of the conductivity, in mhos/cm.
100 Anion( meq L)
= 0.9 1.1
and
100 Cation( meq L )
Conductivity(mhos cm)
= 0.9 1.1
2-52
Measured TDS( mg L)
= 0.55 0.7
and
Calculated TDS( mg L )
= 0.55 0.7
Conductivity(mhos cm)
For solutions with pH <5 or pH >9, the ratio will be <0.55
because of the high conductivity of the hydrogen and
hydroxyl ions, respectively. For high-TDS waters or
waters containing appreciable amounts of ions with
pronounced tendencies to form ion pairs (e.g., Ca 2+, Mg2+,
and ), the ratio will be >0.7 because of the presence of
fewer current-carrying ions.
OH , CO 2
3 , or HCO 3 is possibly present, and
The pH should be measured when the sample is analyzed. This method depends heavily on the accuracy of
the pH calibration and analytical procedures used to
determine the types of alkalinity present. It is not reliable
for waters containing large amounts of organic acids that
act as buffering agents and thereby fix the pH. It applies
only to the species present at the time of analysis and pH
measurement.
2-53
Solubility Calculations
Solubility or saturation
calculations are not
reliable indicators of the
accuracy of an analysis.
OIL-IN-WATER ANALYSIS
The objectives of this analysis are (1) to determine the
amount of oil in water (oil content) before discharge to
the ocean or other surface waters for regulatory purposes, (2) to determine the amount of dispersed or free
oil in injection water for water-quality studies, or (3) to
2-54
Dissolved Oil
The individual components of crude oil vary widely in
their solubilities in water. Table 14 lists water solubilities15 of some typical hydrocarbons. General trends in
solubility behavior are evident. For any given class of
hydrocarbon compounds (a homologous series), the
logarithm of the solubility decreases linearly with the
molar volume of the hydrocarbon molecule; aqueous
solubility decreases as the number of carbon atoms in the
molecule increases. Ringed compounds (cycloalkanes)
are more soluble than paraffins (alkanes) with the same
number of carbon atoms. Double and triple bonds within
the carbon chain increase solubility with
2-55
Table 14
Class
Alkane
Alkene
Alkyne
Cyclic
Aromatic
Compound
Propane
n-Hexane
n-Octane
Propene
1-Hexene
1-Octene
1, 5-Hexadiene
Propyne
1-Hexyne
1-Octyne
Cyclohexane
Cyclohexene
Cyclooctane
Benzene
Toluene
Naphthalene
Formula
C3H8
C6H14
C8H18
C3H6
C6H12
C8H16
C6H14
C3H4
C6H10
C8H14
C6H12
C6H10
C8H16
C6H6
C7H8
C10H 8
Solubility, ppm
62.4 2.1
9.5 1.3
0.66 0.06
200 27
50 1.2
2.7 0.2
169
3640 125
94 3
24 0.8
156 9
213 10
7.9 1.8
1780 45
515 17
34
Cyclohexene
Hexadiene
Cyclohexane
Hexyne
Hexene
Hexane
94 ppm >
50 ppm >
9.5 ppm
Aromatics, unsaturates,
and oxygen-containing
organic molecules have
high water solubilities.
2-56
acid is dissociated into its base form (R-COO-), the solubility increases by approximately three orders of magnitude over the undissociated acid form. Thus, for the C12
dodecane series, the variation in water solubilities is:
Dodecanoate
(Laurate),
C11H 23COO -
Dodecanoic
(Lauric) Acid,
C11H 23COOH
Dodecane C 12H26
55 ppm >
0.01 ppm*
Free Oil
Crude oil may also exist as a discrete, immiscible phase
in produced water. Oil droplet diameters range from
submicrometers to 100 micrometers or larger. The
larger droplets tend to be unstable and coalesce into still
larger droplets that rapidly separate and rise to the top of
the system. Although there are fewer large droplets than
the small droplets, the large droplets contain the bulk of
the volume or weight of the dispersed oil. Because of
2-57
their size, they usually are easily removed by conventional separation equipment gravity separators,
flotation units, liquid/liquid hydrocyclones, filters, etc.
The small oil droplets tend to form stable dispersions.
According to Stokes law, the rise velocity of lighter oil
droplets in water is proportional to the square of the
droplet radius. The low rise velocity of small droplets is
easily surmounted by convective currents within the
system from temperature gradients and fluid flow and
mixing. The small droplets become stirred within the
system and do not rise to the top. Small drops can be
stabilized and kept from coalescing to more readily
separated larger drops by a variety of solid particles and
added or naturally occurring surfactants. Small droplets
frequently have large surface charge densities that further impede coalescence. Although the number of these
droplets is high, the oil volume contained in them is
usually a small fraction of the total free oil. Small droplets are difficult to remove with conventional separation
equipment. Despite their small size, they may cause
extensive reservoir plugging by altering the nature of the
surfaces in the pores of the reservoir rock and by acting
as a glue for other particulates present (e.g., corrosion
products, scale particles, formation fines, spent acids, and
precipitated asphaltenes).
Sampling
Sampling procedures for oil-in-water analyses are very
critical for obtaining results that are truly representative
of the bulk water stream. Free oil readily adsorbs onto
and contaminates most surfaces. All glassware used for
sampling and testing should be thoroughly cleaned and
then rinsed with the extracting solvent before use.
Samples should be taken and stored directly in glass
bottles with metal-foil-lined, screw-cap closures. Plastic
containers should never be used because free oil readily
adsorbs onto plastic surfaces and is difficult to remove
even with repeated solvent washes. See the previous
section on sampling for chemical analysis for precautions
about shipping samples in glass containers.
2-58
Analytical Procedures
Several methods, differing in complexity, specificity to oil
and possible interferences, are available. The method of
choice is usually dictated by the ultimate use of the
acquired data; for example, to satisfy regulatory agencies
for NPDES permitting, U. S. Environmental Protection
Agency (EPA) Method 413.1 must be used. A measure of
free or dispersed oil (not including dissolved organics) as
given by the API colorimetric method or a modification is
more useful for evaluating oil water treating chemicals
and equipment.
Filtering the water sample before analysis is said to
distinguish between free oil and dissolved oil. The unfiltered sample is said to contain total oil (free + dissolved); the filtrate is said to contain dissolved oil.
This method of separation is not reliable or complete
because significant amounts of free oil may bleed
through the filter media and appear in the filtrate, especially when the samples contain large amounts of free oil.
Multiple filtrations may be necessary to remove all the
2-59
free oil. The additional filtration steps increase the possibility that some dissolved oil will be lost because of
adsorption on surfaces.
2-60
available, a reference oil is prepared by mixing nhexadecane, iso-octane, and chlorobenzene. Like Method
413.1, this method will detect dispersed and dissolved oil
and other organics that are extractable and have carbonhydrogen groups that absorb infrared radiation in the
region of measurement. Organic acids and other extractable materials may give high results if the calibration
curve is prepared from only oil or standard hydrocarbon
mixtures. (Organic acids form dimers in the extracting
solvent. These dimer acids have a broad absorption band
in the same region as the carbon-hydrogen bands and can
cause interference if the proper background level is not
selected.) This method usually gives higher results than
Method 413.1 because of smaller losses of volatile, light
hydrocarbons. The higher results could also be due to
spectral interferences of the type indicated for dimer
acids. Method 413.2 cannot be used for NPDES permitting.
2-61
Quality Control
Five issues are involved in quality control for an oil-inwater analysis:
1. Sampling procedure. How representative is the
analyzed sample of the system being studied?
2. Sample container material. How much of the oil in
the sample is irreversibly lost to the walls of the
sample container?
3. Extraction efficiency. The three EPA procedures discussed specify the extraction conditions and do not
permit variations. The designated fluorocarbon
solvent was chosen because of its relatively low
2-62
Accuracy closeness of
determined value to
the correct or true
value
Precision repeatability
of measurements.
2-63
SUSPENDED SOLIDS
Sampling and Analytical Procedures
A variety of analytical procedures can be used, depending on the type and sophistication of the information
desired. The sampling procedures for all analytical
methods for suspended material have one common goal:
2-64
2-65
Frequently, these procedures listed in this NACE standard are also used to measure water quality for injection
by determining the filtration rate of a water sample
through a membrane filter under specified conditions.
These tests are discussed in Chapter 4. Ref. 18, included
as an Appendix in Chapter 4, gives specific details for
test performance and interpretation of results.
2-66
Other Procedures
Patton gives simple field tests suitable for qualitative
analysis of many scale deposits (Ref. 10, Pages 90-91; Ref.
11 Pages 75-76). For more detailed characterization,
specific laboratory procedures using wet chemical analysis, either alone or in combination with XRD
(PETROCHEM analysis), are available for many solid
components. ASTM19-23 has published various procedures
for sampling and analyzing many water-formed deposits
that appear in oilfield systems.
Quality Control
Specific procedures to assess the accuracy and precision
of suspended solids analyses are not available. Duplicate
samples may show considerable variations and are not
reliable as quality-control checks. Strict and reproducible
adherence to established procedures will usually improve precision.
Some suspended solids are unstable when dried or exposed to air. For example, iron sulfide may be pyrophoric and rapidly revert to sulfur dioxide and iron
oxides when exposed to air. Samples for analysis should
be fresh and/or suitably preserved so that there is reasonable assurance that we are analyzing what was originally present in the system. When identifying the composition of the solids is more important than knowing the
amount of solids present, field chemical tests may be
more suitable than laboratory analysis for samples that
might undergo changes.
2-67
2-68
REFERENCES
1. Ford, W. L. and Deevy, E. S. Jr.: The Determination
of Chlorinity by the Knudsen Method, Woods Hole
Oceanographic Inst., Woods Hole, MA (1946).
2. Standard Methods for the Examination of Water and Waste
Water, American Public Health Assn./American Water
Works Assn./Water Pollution Control Federation,
15th edition (1980) and 17th edition (1989).
3. Strumm, W. and Morgan, J. J.: Aquatic Chemistry,
second edition, John Wiley & Sons, New York City
(1981).
4. Thomas, N. L. and Campbell, W. L.: Technical
Memorandum. Assembly and Operation of the Automatic Pressure Filtration Apparatus, COFRC
TM89000551 (June 1989).
5. Carpenter, A. B. and Campbell, W. L.: Introduction
to Inorganic Geochemistry. Appendix C Procedures
for Sampling and Chemical Analysis of Formation
Waters, COFRC LN89000516 (1989).
6. Subcasky, W. J.: Final Report Evaluation of Sulfide
Ion Selective Electrode, COFRC TS88000784 (July
1988).
7. Annual Book of ASTM Standards, Section 11 Water
and Environmental Technology, American Soc. for Testing and Materials, listed annually.
8. RP 45, Recommended Practice for Analysis of Oilfield
Waters, American Petroleum Inst., Dallas (1968).
9. Methods for Chemical Analysis of Water and Waste,
U.S. Environmental Protection Agency, EPA-600/4-79020 (March 1983).
10. Patton, C. C.: Applied Water Technology, first edition,
Campbell Petroleum Services, Norman, OK (1986).
11. Patton, C. C.: Oilfield Water Systems, second edition,
Campbell Petroleum Services, Norman, OK (1981).
12. Ostroff, A. G.: Introduction to Oilfield Water Technology,
second edition, Natl. Assn. of Corrosion Engineers,
Houston (1979).
2-69
2-70
GLOSSARY
Accuracy combination of bias and precision of an
analytical procedure, which reflects the closeness of a
measured value to a true value.
Acid-insoluble suspended solids the amount of
suspended solids retained by a membrane filter after
an acid wash in NACE Standard Test Method TM
1073-84.
Acid-soluble suspended solids the amount of suspended solids removed by an acid wash in NACE
Standard Test Method TM 1073-84.
Acidity a measure of the capacity of a water to react
with the hydroxide ions of an added base.
Alkalinity a measure of the capacity of a water to
react with the hydrogen ions of an added acid.
Analyte the component or material being determine in
a chemical analysis procedure.
Anion negatively charged ions in solution that move
towards the anode (electrode at which oxidation
occurs) in an electrolysis cell.
Anion/cation balance a primary method of checking
the reliability of an analysis. This procedure is based
on the fact that aqueous solutions are electrically
neutral and therefore the sum of the concentrations of
anions must equal the sum of the concentrations of
cations (all concentration are expressed in
milliequivalents per liter).
Anode electrode at which oxidation (loss of electrons)
takes place.
Atomic weight relative weight of an atom of the
element compared with the weight of the carbon-12
atom.
Black water suspended iron sulfides, usually found in
reducing environments with measurable sulfide
levels.
Cathode electrode at which reduction (gain of electrons) takes place.
2-71
2-72
2-73
2-74
2-75
2-76
2-77
2-78
C H A P T E R
3
Oil/Water Separation
3-1
3-2
PREFACE
This chapter discusses the removal of dispersed oil from
water for reinjection, discharge, downhole disposal, or
reuse in EOR projects. Much of the chapter focuses on
the processes used to remove oil from water. However,
like the rest of this handbook, this chapter does not give
detailed design information on specific processes. The oil
removal processes and technologies are explained in
detail. The information presented is sufficient for selecting a specific process technology but not for designing a
process in detail.
An important part of this chapter is dedicated to integrated treatment systems and equipment selection. If
you are designing, optimizing, or troubleshooting a
water treatment facility, this philosophy will help you
meet your goal of cost-effective water treatment.
This chapter also forms the basis for the Chevron Oil/
Water Separation Seminar. The seminar notes, available
from your colleagues who have attended, are another
source of information.
Injection Requirements
The effect of residual oil in injection water on the permeability of subsurface formations is currently not well
understood. In certain reservoirs, the effects of emulsion
formation in the wellbore are known and injectivity loss
can be predicted. However, these emulsions are not
usually formed by the oil droplets in the injection fluid,
but by residual oil/injection water interactions. Our
3-3
3-4
Disposal Requirements
When defining disposal of oily waters, we generally talk
about subsurface disposal into a specific zone or reservoir. Surface disposal of oily waters is considered discharge.
Subsurface-disposal water-quality requirements are
similar to those for injection. The water must meet the
quality constraints set by the disposal zone. Again,
injectivity loss must be minimized and filtration equipment protected. Disposal wells can be drilled into zones
identified as suitable for disposal. Or existing wells
within an existing reservoir can be recompleted to disposal standards. In both cases, the water will probably
be treated to a low level of oil, <10 ppm, before reinjection. However, many disposal zones are selected because
of their high permeabilities and hence may be more
tolerant of oil than injection zones in the same field. We
cannot yet define the ideal level of oil concentration for
subsurface disposal zones. The optimum level is usually
defined as the maximum oil concentration that the disposal zone can tolerate with no injectivity loss or contamination outside the disposal zone.
3-5
Discharge Requirements
EOR Requirements
The steamflood is a common form of EOR in Chevron
operations. Produced water is treated and turned into
steam before reinjection into the oil reservoir. Several
treatment stages are required to meet the stringent inlet
3-6
specifications of the steam-generating boilers. Oil removal is one. Most once-through oilfield boilers producing 65% to 80% steam quality require <1 ppm oil in the
feedwater to minimize boiler coking, etc. This appears to
be the industry standard, although Thermosludge steam
generators can handle oil concentrations of 250 ppm.2
As a pretreatment to steam generation, many produced
waters undergo some degree of softening. Softening
prevents scale deposits on the boiler tubes that cause
fouling, loss of efficiency, and in many cases, equipment
failure. Softening may take place in many ways: strong
cation exchange softening, cation/anion dual ion exchange, or reverse osmosis.
When ion exchange resins are used, the allowable oil
concentration depends on the type of resin used in the
bed. Some resins are more tolerant of oil fouling than
others, but all exhibit reduced ion exchange capability if
fouled by oil. Typical limits to maintain ion exchange
capacity and minimize fouling are oil concentrations of
1 ppm or less. The resin may tolerate higher concentrations than this without permanent damage, but performance will be reduced.
A similar situation exists for reverse osmosis membranes,
which can easily be fouled by oil. Less than 2 ppm oil
concentration is recommended to maintain membrane
integrity.
Note that, while EOR waters have special treatment
requirements, some EOR processes alter the characteristics of produced fluids. For example, caustic/surfactant
flooding can produce very tight emulsions in the produced fluids, which can result in poor dehydration and
poor produced-water quality. If this produced water is a
source water for an EOR process, its treatment requirements may be more complex than a source water that is
not influenced by EOR. Of course, some EOR processes
enhance production operations. Steamflooding, for
example, often raises the temperature of the produced
fluids, simplifying crude dehydration and subsequent
water treatment.
3-7
gd 2 ( w - o)
,
18
3-8
t
= 432 r
p
2/5
3/5
3-9
DEHYDRATION SEPARATORS
In many designs of three-phase separation vessels, the
primary purpose is to separate water from oil. These
vessels are usually designed as crude dehydration vessels
and optimized for crude quality, but their influence on
water quality cannot be underestimated.
In the dehydration of crude oil, both chemical and mechanical processes occur. The mechanical process provides enough residence time for emulsion to be resolved
and the water to drop out of the crude. Traditionally,
vessel designs have been based on oil-phase residence
time.5
3-10
For clean water, water-phase residence time is also important. During water settling, some oil will be drawn
into the bulk water phase. To obtain clean water at the
vessel outlet, this oil must be allowed to return to the oil
phase. Longer effective water-phase residence times
allow more oil to return to the bulk oil phase.
To maximize the water-phase residence time and oil
droplet size, vessel internals (plates, packing, vortex
breakers, etc.) are usually used. The role of the vessel
internals is two- or three-fold. Increasing residence time
by ensuring minimal vessel short-circuiting is usually our
primary reason for installing internals. However, reducing water-phase turbulence and acting as oil droplet
coalescing media are additional benefits.6
Maximizing residence
time is the key to effective
skim tank performance.
3-11
COALESCERS
Coalescers provide a solid surface that can come in contact with and be wet by small oil droplets. These small
oil droplets accumulate and saturate the solid media,
forming a cohesive oil film. When the cohesive forces of
the film are overcome, oil elutes from the media in large
droplets. These larger drops separate significantly faster
than the small droplets in the feed stream in accordance
with Stokes law (Fig. 2). Some coalescers can separate
the enlarged oil droplets and thus can be considered true
separators. Some coalescers perform only droplet agglomeration and must be used with separation equipment downstream. Each type of coalescer plays an
important role in effective separation of oil from water.
Three types of coalescers are currently available: platepack, loose-media, and fixed-media coalescers.10,11 In this
section, we will consider only media coalescers. Platepack coalescers are covered in the next section.
Loose-Media Coalescers
Coalescers provide a
surface for oil droplets to
contact, agglomerate and
grow.
3-12
and pass into the media bed, where they are held on the
surface of the sand grains and coalesce. Oil gradually
saturates the medium and eventually breaks through into
the outlet water stream. The coalesced oil is then separated, usually by a weir or baffle system, and piped
continuously from the vessel.
These coalescers invariably act as filters to some of the oil
and to any suspended solids present. Therefore, they
must be backwashed to minimize fouling. However,
these devices are not designed to remove solids effectively. In most loose-media coalescers, sand grain size
and flux rates are chosen to maximize oil/sand contact
time, not for solids entrapment.
Effective backwashing is critical to optimizing coalescer
performance. Inefficient backwashing leads to residual
oil and solids in the bed, which act as a glue to fresh oil
and solids in the influent stream. This leads not only to
rapid increases in pressure drop but also to the formation
of mud balls, which rapidly deteriorate coalescer performance.
Fixed-Media Coalescers
Fixed-media coalescers provide an oleophillic medium
for oil droplet contact and coalescence. Oil droplet size
changes when the droplets coat the medium and elute or
coalesce within the medium. The coalesced droplets are
then separated by gravity in the coalescer separation
chamber.
Typically, the media come in two distinct configurations:
a sponge type and a fibrous cartridge similar in design to
a filter cartridge. Sponge-type coalescers offer a porous
oleophillic environment for coalescence and are usually
housed in horizontal or vertical separator vessels. Oily
produced water enters the separator and flows through
the sponge, where oil droplets coalesce in the pores and
saturate the surface. These droplets then elute from the
medium and pass into the quiescent separation zone of
the vessel. There, oil is drawn off at the top and clean
water is drawn from the bottom.
3-13
3-14
Corrugated Plate
Interceptors (CPI) are the
most common and
effective plate pack
separators.
3-15
Significant derivatives of the traditional plate-pack separators are the SP-Pack Coalescer and the Vertical Tube
Coalescer. The SP-Pack, a serpentine-path coalescer, uses
free-flow turbulent coalescence to increase oil droplet
size and thereby enhance separation efficiency. The
device itself is essentially a collection of pipes joined by a
series of helical swirl bends that cause the water to flow
in a pattern conducive to coalescence without generating
enough turbulence to shear oil droplets. The primary
role of the bends is to generate this flow pattern, but
evidence shows that they also provide a surface to assist
coalescence.12 This device does not operate as a separator
but merely as a coalescer. Thus, it must be used with
other equipment. This device can be used as a pretreatment device for flotation cells and hydrocyclones. But it
probably is best used in settling tanks where it can act as
a coalescer and inlet flow spreader (Fig. 6).
The Vertical Tube Coalescer operates like a plate pack,
but the plates are replaced with vertical tubes. The
vertical tubes offer a five-fold increase in coalescing area
over traditional plate packs. In addition, because the flow
is across the tubes, oil rises more easily to the separation
weir (as opposed to the PPI, where the oil flow is countercurrent to water flow).13 The tubes are made from
polypropylene and look like a loosely knit cartridge filter
(Fig. 7). Because the material is oleophillic, it easily
attracts small and large oil droplets. The inlet flow
passes through the tubes, where oil coalesces and rises to
the surface to be skimmed off. Solids and sludge fall
through the tubes and are collected in a sump at the
bottom of the vessel. As in the PPI, the vessel itself
consists of an inlet tank arrangement, flow distribution
baffles, the tube tank, and an oil collection system.
FLOTATION
Flotation has been the
industry standard for oil
removal for many years.
3-16
3-17
3-18
3-19
a retention time of 1 minute. The devices also incorporate an inlet box and a discharge box with level control
equipment to ensure operation control. Note that, although mechanical IGF units exhibit excellent performance in steady-state conditions, they are affected by
flow-rate changes. In most successful installations, surge
capacity is available upstream of the IGF unit to minimize flow surges and maximize oil removal efficiency.
IGF Selection
On-site tests should be carried out to determine whether
an IGF unit will successfully treat an existing produced
water. These tests use a bench-scale IGF unit, which
gives an excellent indication of the performance of a fullscale unit. This procedure is recommended if flotation is
being considered for an existing fields water production.
improved eductor type and the single-cell external eductor type. Both devices offer more efficient mixing of gas
and water, which results in more efficient separation. In
the four-cell type, the eductor design and agglomerate
dispersion in the flotation cell are improved. Other
advantages of the four-cell eductor design are its capability to be operated at pressure and the use of a weir/level
control system to optimize skimmings collection and
flow surge capacity. This is typically more efficient than
mechanical skimming because a smaller volume of water
is removed with the floated oil. In addition, no moving
parts lie within the separator vessel, which reduces the
need for vessel entry.
The single-unit design uses a high gas/water ratio at
high velocity to generate very small bubbles, which
improves capture efficiency. The gas/water contact
occurs in an eductor external to the separation vessel.
The gasified influent passes from the eductor into the
separation vessel through a coalescer pack that enhances
gas bubble/oil droplet contact. This, coupled with a
circular cross-sectional cell design, leads to minimal
disturbance in the quiescent flotation zone. The result is
an efficient separator that produces a tight foam that
reduces skimming volume. Again, a weir arrangement is
used to remove the skimmings, eliminating moving
parts.
3-21
Gas Concentration
A high gas concentration is desirable because it will
increase oil removal. High concentrations will increase
the population of gas bubbles available to capture oil
droplets. A high gas concentration can be achieved by
generating small bubbles in a DGF unit or by using an
IGF gas unit with a high gas/water ratio. For a dissolved
unit, the mean gas bubble size typically ranges from 80 to
100 m. For a dispersed unit, the gas bubble size is
typically >100 m. Hence, a DGF unit develops a more
favorable bubble size than an IGF unit. However, this
advantage is offset by the actual gas volume available for
bubble generation. In a DGF unit, this volume is about
0.5 ft3/bbl. It is limited by the solubility of the gas in the
produced water. For an IGF system, however, the
amount of gas available for bubble generation can be as
high as 35 ft3/bbl. This more than offsets the unfavorable
bubble size generated in an IGF unit.
Note that oil droplet size can influence the size of bubbles
generated in a flotation device. Small oil droplets
(<10 m) cause gas bubbles to coalesce and hence reduce
gas concentration and efficiency. This is more critical in
DGF systems where high gas concentrations are achieved
through generation of very small bubbles.
3-22
Temperature
Strickland showed that increasing the produced-water
temperature will improve separation capabilities as a
result of a lower continuous-phase viscosity. However,
experiences with flotation systems in the North Sea
indicate that an upper temperature limit of 180 to 200F
exists. At these elevated temperatures, steam condensing
in the gas blanket of a flotation cell reduces the gas volume that can be induced by the impeller of an IGF unit.
This decreased gas volume reduces gas concentration
and thus oil droplet capture efficiency.
3-23
The total produced-water chemistry will affect the performance of both DGF and IGF processes, but the surface
chemistry of the dispersed oil droplets is of primary
importance. Oil droplets typically have a negative surface charge, which facilitates bubble/droplet attachment
because a positive static charge is imparted to the
bubbles during generation.13
Water-soluble flotation aids are often used to improve oil
removal efficiency. Many types of chemicals can, by
altering the surface chemistry of the dispersed phase,
improve separation performance. Cationic polyelectrolytes are used as coalescing agents to increase droplet
size; amine-based surfactants are used to enhance the
foaming capability of the water; and metal salts are used
to generate flocs to enhance solids separation.
The type of chemistry appropriate for enhancing separation should always be determined by screening potential
candidates in the field. This can be done using a benchscale flotation unit on the water to be treated. This
bench-scale test, if carried out in the field, is an extremely
accurate way to select chemicals. If the chemical is effective in the bench unit, it will be effective in the full-scale
flotation device.
Selecting the correct chemical is critical in many instances
because some surfactants and polyelectrolytes can cause
stable emulsions to form in the oil-rich froth, making
resolution of the oil and water phases very difficult.
Chapter 8 discusses this in more detail.
HYDROCYCLONES
Hydrocyclones have been used for many years to separate solids from liquids and from air. These devices are
used as clarifiers, classifiers, and thickeners in a variety
of industries, including mining.
3-24
The devices typically are small and have a length/diameter ratio of around 5:1. Depending on the design, the
diameter ranges from 0.01 to 0.102 m. These devices are
not suitable for removing dispersed oil from water.
The hydrocyclone used to separate oil from water is
known as a liquid/liquid hydrocyclone (LLHC). This
device has a vastly different geometry from the solid/
liquid hydrocyclone.
Static Hydrocyclones
All static hydrocyclones currently available (Conocos
Vortoil and Hydropack, Amocos Hydroswirl, and Krebs
De-Oiler) are similar in design, and all three have the
same principle of operation: generation of centrifugal
forces by fluid acceleration through a device of complex
geometry. The static hydrocyclone usually consists of
three distinct parts:
1. A cylindrical swirl section with a tangential inlet and
reject stream orifice.
2. A tapering conical body.
3. A cylindrical tail section with clean water outlet.
In all three devices, the feed stream enters the cylindrical
swirl section tangentially. This causes a high-velocity
vortex, which generates forces exceeding 1,000 g. The
fluid accelerates through the conical section, where,
because of its lower gravity, oil moves to a central core.
The majority of separation occurs in this section. The
fluid then passes into the cylindrical tail section, where
3-25
Dynamic Hydrocyclones
Only one dynamic hydrocyclone is currently available for
oil field use: the Dynaclean from Alstholm. This device
operates quite differently from the static units, generating
the separating forces by rotation. The dynamic
hydrocyclone is essentially a rotating cylinder with an
inlet port at one end and an outlet port at the other. The
reject stream outlet is via a conical reject orifice at the
outlet end. An external electrical motor with a variablespeed drive rotates this device (Fig. 15).
The Dynaclean separates oil from the feed stream by
generating a free vortex in which oil migrates to a central
core because of its lower gravity. The feed stream enters
the device axially and then passes through a vane that
rotates at the same speed as the hydrocyclone wall. This
rotating vane imparts the rotational motion to the inlet
fluid. Separation takes place in the hydrocyclone body.
The clean water and the oil-rich reject stream exit the
device concurrently. The residence time for both streams
is a few seconds.
The pressure drop across the device is much lower than
for the static unit because it is caused only by the inlet
and outlet losses and a loss resulting from vortex generation.
3-26
V=
gd 2 ( w o )
18
3-27
ing data for these units have shown a performance improvement exceeding the traditional 35-mm-diameter
designs.
Reject ratio is the ratio of reject flow to inlet flow expressed as a percentage. It influences performance in
operating below and above the optimum ratio.
Operating below the optimum reject ratio results in low
oil removal efficiencies because the separated oil is not
being removed from the hydrocyclone. Operating above
the optimum reject ratio does not impair oil removal
efficiencies but adds to the volume of the reject stream.
This may be important if the stream is to be processed
further. Typical operating reject ratios range from 0.5% to
3%.
Dynamic hydrocyclones are operated slightly differently
from the static variety, and the effects of pressure and
reject ratio on performance are not as pronounced. The
inlet pressure required to drive a rotating hydrocyclone is
less than the 90 psig required to drive a static unit. The
reason is that no pressure drops cause by complex geometry must be overcome. Typically, 50 psig is required to
operate a rotating unit at minimum flow rate. The effect
of reject ratio is not important in rotating hydrocyclones;
the critical parameter is reject flow. The reject flow is
constant across the whole inlet flow range of the device.
Hence, reject flow, not reject ratio, is the optimum parameter.
A parameter that greatly influences oil removal efficiency
is rotational speed. Higher rotational speeds give better
oil removal efficiencies at a given flow rate. However,
this improvement in efficiency is at the expense of higher
inlet pressures. The rotational speed for a dynamic
hydrocyclone usually is between 1,600 and 3,000 rpm.
Typical Performance
Static Hydrocyclones
The Vortoil, a 35-mm unit, has an operating range of 28 to
50 gal/min at 60 to 350 psig. With a standard 4-mm
reject orifice, the optimum reject ratio is 2% in most test
cases.
3-28
Dynamic Hydrocyclones
The Alstholm Dynaclean unit used in Chevron tests was
a Model 2 unit. Its operating range is 30 to 90 gal/min at
50- to 250-psig inlet pressure. The nominal flow rating
for this device is 73 gal/min at 2,500 rpm. The rotational
speed varies from 1,600 to 3,000 rpm. The device consistently achieved oil removal efficiencies of 90% at maximum rotational speed and nominal flow rate. Reductions in separation efficiency were seen at higher flow
rates and lower rotational speeds. The Dynaclean unit
separates small oil droplets more efficiently than the
static units and will give higher removal efficiencies for
droplets smaller than 15 m in diameter. Fig. 16 compares typical static and dynamic cyclone performance.
Applications to Date
Most hydrocyclones in use today are permanent installations on offshore platforms. The space and weight advantages of LLHCs over plate-pack separators and
flotation units are most useful, and savings in platform
3-29
Hydrocyclone Selection
With the evolution of less expensive cyclone designs and
low-pressure second-generation cyclones, this technology
is also becoming applicable in onshore operations. Several pieces of information are required to select a cyclone,
including available driving pressure, water temperature,
maximum and minimum flow rates, steady-state and
upset inlet oil concentration, desired outlet oil concentration, existing chemical treatments, and, if possible, an
inlet oil droplet size distribution. The last item is extremely valuable information for predicting cyclone
performance that is not available in most situations.
Armed with the above information, the cyclone manufacturers should be able to predict cyclone performance and
to provide a cost estimate for your application.
With a new facility in the process design stage, the manufacturers predicted performance criteria should be used
if backed up by field performance data from similar
operating conditions. If not, then the origin of the data
for performance prediction should be established. Our
experiences indicate that manufacturers predictions of
performance are not always accurate. In many cases, the
actual cyclone performance exceeded manufacturers
predictions.
With an existing facility, on-site evaluation of cyclone
performance should be standard procedure. Small test
skids are available from each manufacturer. These skids
are easy to use and will yield useful performance and
control data. If possible during this field test, droplet size
and oil removal information should be used to characterize cyclone performance. This information is valuable in
designing and operating upstream facilities to minimize
droplet breakup and to determine whether a downstream
residence tank will act as a useful polishing treatment
stage.
3-30
FILTERS
In general, most filters are not used as oil/water separators, nor are they designed to be used in this manner.
Filters are usually designed to remove solids from water.
However, some filters can remove oil from water and are
more tolerant to oily water service.
Many types of filter are in use today. Most are covered in
the filtration section of this handbook. Some useful
guidelines about operating and selecting filters for oilfield use are given below.
Nutshell Filters
These types of filters are designed with produced-water
use in mind. They are more tolerant to oil than any other
type of filter in oilfield use and are reasonable oil separators. Typically, these filters do not act as true separators
but as oil accumulators. The oil in the feed stream entering the filter is retained within the filter bed and is removed during backwashing. One of the three commercial variants, however, has the option of using an oil
take-off valve for any free oil that floats to the top of the
filter.
3-31
Integrated Treatment
Systems = Cost effective
operation.
3-32
Integrated Treatment
System = Optimized
Design + Optimized
Operation.
Another important aspect of the ITS approach is understanding the effect of recycle streams on final water
quality. The recycle stream that is most important to the
water treatment process is the oil recovered in the water
treating facilities. This recovered oil is often in the form
of IGF skimmings, PPI skimmings, settling-tank skimmings, or hydrocyclone reject streams. In most systems,
the recycle stream consists of an oil/water mixture and is
usually recycled back into the dehydration stream. While
intuitively this seems to be an ideal place to recycle,
problems occur if the recycle stream contains such chemicals as flotation aids or coagulants. These chemicals tend
to stabilize emulsions in the dehydration system, which
result in interface pad buildup in the dehydration vessels. This may lead to poor oil quality, but almost certainly to poor water quality because the interface pad
sloughs into the water phase, leading to dirty water.
This interface pad, a very good emulsifying agent, will
cause a very stable emulsion to form, thereby further
decreasing the performance of the water treating equipment. To improve performance, we may be tempted to
increase the dose of any water treating chemical in the
system, which in turn will lead to excess chemical in the
recycle stream, which degrades dehydration, etc.
In essence, we create a spiral of degradation, which
results in poor facilities control and poor water quality.
The solution is to select water treatment chemicals that
minimize the effect of emulsion stabilization and are
3-33
3-34
PROCESS/EQUIPMENT SELECTION
Using an ITS approach is the preferred way to handle
produced- water treatment. In the ITS philosophy, each
unit operation is considered an integral part of the whole
treatment process. Consequently, the impact of chemical
pretreatment and waste-stream handling will be considered during selection of oil/water separating equipment.
Several facilities templates are available in the ITS philosophy for selecting oil/water separation equipment.
Chapter 3: Oil-Water Separation
3-35
3-36
On-Line Methods
Currently, no on-line methods exist to measure oil-inwater concentrations in an operating oilfield repeatedly,
accurately, and cost-effectively. Some on-line monitors
are commercially available, but they have less-than-ideal
operating accuracies and are prone to high maintenance.
These monitors use a variety of techniques to measure oil
concentrations, and all are prone to problems. However,
new monitors using the techniques described below are
being developed, and initial laboratory results are encouraging. Technical Memorandum TM91001083 in the
Appendix includes a description of this testing.
Four basic on-line techniques are used to measure oil-inwater concentrations: infrared light scattering,
infrared absorption, ultraviolet absorption, and ultrasonic.
3-37
angle, the oil droplet density, and the droplet particle size
relative to the wavelength of the light. Hence, wavelength is critical to accurate measurement of oil concentration. Most manufacturers choose 8,800 Angstoms
because that value maximizes oil droplet detection and
minimizes the effects of water color and solubles. This
type of instrument typically operates at 0 to 200 ppm.
This technique has proved to be one of the most accurate
on-line methods. However, it still suffers from inaccuracies, notably loss of accuracy at small droplet sizes
(<10 m) and loss of repeatability when samples contain
free gas.
Direct Absorption
This technique uses the principle of absorption of
infrared light by discontinuities in the fluid stream.
Usually, a sample is drawn from the process stream into
the units sample cell, where the amount of infrared light
absorbed by the oil is measured. The wavelength of the
light is specifically chosen to maximize sensitivity to oil.
The wavelength for all commercial units is 34,000 Angstroms. A second wavelength of 36,000 Angstoms, which
is insensitive to oils, is also used to detect solid materials.
This enables a net oil concentration to be measured.
Unlike systems that extract oil from water with a halogenated hydrocarbon solvent to avoid the high absorbance
of the water itself, this system compares the absorbance
of the oily water with that of a de-oiled reference stream.
This reference stream, ultrafiltered process water, provides a background base absorbance. The difference in
absorbance between the reference and sample streams is
linearly proportional to oil content. This type of analyzer
has an operating range of 0 to 2,000 ppm.
This technique is fairly accurate over a wide range of
droplet sizes, but it is very sensitive to temperature
changes. Controlling the flow rate of the sample is also
critical for repeatable, accurate results. Two negative
3-38
Ultraviolet Absorption
This instrument measures oil concentration much like the
infrared absorption units, but it uses ultraviolet light at
2,540-Angstom wavelength. Most devices of this type are
dual wavelength: one to measure oil concentration and
one, a reference, to compensate for solids and optical
anomalies. At this reference wavelength, oil does not
absorb significant ultraviolet energy; hence, the oil component in the total absorption spectrum can be isolated.
The operating range of ultraviolet absorption oil in water
monitors is 0 to 100 ppm.
3-39
These devices are accurate, but also complex and maintenance-intensive. The use of a reference wavelength is
also prone to error because very small oil droplets interfere with ultraviolet absorption by solids. This leads to
an increase in background absorption, which in turn
leads to underestimated oil content.
Laboratory Methods
Laboratory methods of oil-in-water determination are the
most common form of monitoring separator performance. The methods are outlined in the Analytical and
Test Methods section (pp. 2-75 to 2-88).
As outlined in this section, the methods themselves
define oil. Some methods include soluble hydrocarbon
species in the oil concentration measured. It is important
to note that all the equipment and separation processes
discussed in this chapter are designed to remove only
free oil.
3-40
REFERENCES
1. Determination of Best Practicable Control Technology Currently Available to Remove Oil from Water
Produced with Oil and Gas, Brown and Root Inc.,
report prepared for Offshore Operators Committee
(USA), March 1984.
2. Somani, A. H. et al.: Produced Water Treatment
Technologies for Reuse or Disposal, ZhouZhou
(Oct. 26-30, 1987).
3. Hinze, J. O.: Fundamentals of the Hydrodynamic
Mechanism of Splitting in Dispersion Processes,
AIChE J. (Sept. 1955).
4. Arnold, K. and Stewart, M: Surface Production Operations, Gulf Publishing Co., Houston (1986) I, 215.
5. Three-Phase Separator Design, IHRDC Bookware Series,
Paragon Engineering Services, Houston.
6. Designs for Water Quality Improvement, Oilfield
Water Quality Improvement Training Manual, C. E.
Natco (1985).
7. Stires, J.: Design of a High Rate, High Volume Oil/
Water Separator, JPT (Nov. 1982).
8. Bradley, B. W.: Qualitative Separation = Theory +
Judgement, OGJ (Oct. 14, 1985).
9. Dodge, F. T.: Scale Model Study of Oil/Water Separation in Wash Tank for Duri Steam Flood Gathering
Station, Southwest Research Inst., San Antonio, TX
(April 1983).
10. Bradley, B. W.: Two Oil Field Water Systems, R. E.
Krieger Publishing, Malabar, FL (1987).
11. Patton, C. C.: Applied Water Technology, Campbell
Petroleum Series, Norman, OK (1986) Chap. 6.
12. Jones, P. S. et al.: Evaluation of Static and Dynamic
Hydrocyclones for Removal of Oil from Produced
Water, Murphy Coyote Lease, TM89000928 (JuneJuly 1989).
13. Murti, D. G. K., Al-Maskati, A. H., and Sood, L. K.:
Improved Disposal-Water Treatment at Bahrain Oil
Fields, SPE Production Engineering (Nov. 1988).
Chapter 3: Oil-Water Separation
3-41
3-42
GLOSSARY
Coagulation The neutralization of surface charge on
an oil droplet or small solid particle.
Coalescence The rupturing of the interfacial film
between agglomerated oil droplets which results in
the formation of one large droplet from several
smaller droplets.
Dehydration The resolution of crude oil into its oil
and water components.
Demulsifier Chemical used to enhance/effect crude
oil dehydration. This is usually a blend of organic
components in a solvent.
E. O. R. Enhanced Oil Recovery
Emulsification Generation of emulsion. Requirements
are oil + water + emulsifier + agitation. All must be
present to form an emulsion.
Emulsion A stable mixture of oil and water.
Filter Backwashing The washing of a filter to remove
solids accumulated during the filtration cycle. This is
usually carried out when the filter reaches a given
pressure drop indicating that it is totally full of
solids.
Flocculation The agglomeration of neutrally charged
oil droplets or solids.
Flotation Aid/Reverse Demulsifier Chemical used to
enhance the performance of a flotation device. This is
usually a cationic polyelectrolyte.
Ion Exchange Substitution of Sodium and Hydroxide
ions for Calcium, Magnesium and Carbonate ions in
water. This softens the water reducing the ability of
the water to scale at elevated temperatures.
Mudballing The agglomeration of sand and oil in a
media filter. Mudballing is an indication that filter
backwashing is inefficient or that the feed oil concentration is to high for the filter to deal with.
Permeability The ability of a reservoir rock to allow
flow through it. Higher permeability = easier injection. Units of permeability are Darcys or Millidarcys.
Steamflood Injection of steam into a reservoir as a
secondary recovery process.
3-43
3-44
APPENDIX
3-45
C H A P T E R
4
Filtration
Chapter 4: Filtration
4-1
C H A P T E R
5
Scaling and
Water Formed Solids
5-1
5-2
INTRODUCTION
This chapter focuses on common oilfield scales, emphasizing their prediction, prevention, and removal. In
addition to the material in this chapter, several useful
papers are included in the Appendix. Interested readers
may contact CPTC for copies of references not included
in the Appendix.
5-3
Common Scales
Table 1 lists the most common water-formed scales in
oilfield waters. This table includes the primary variables
that affect their solubility. Table 2 lists the common
causes for the formation of these deposits and possible
chemical solvents to remove them.
A few general remarks about the most common scales are
given below. Scales formed in oilfield operations are
usually a mixture of two or more of these scales and
organic solids (asphaltenes, paraffins, etc.). Refs. 1
through 3 provide further details.
Calcium Carbonate
Calcium carbonate, the most common scale in oil- and
gasfield operations, occurs in every geographic area.
Calcium carbonate precipitation occurs when calcium ion
is combined with either carbonate or bicarbonate ions as
follows:
++
Ca + CO 3 CaCO 3 (s)
Ca
pH is an important factor
in calcium carbonate
solubility.
++
(1)
(2)
Eq. 2 shows that the presence of CO 2 increases the solubility of CaCO3 in brine. Increasing the concentration of
CO2 in solution shifts this reaction to the left, resulting in
less calcium carbonate scale. Increasing CO2 also makes
the water more acidic (decreases the pH). Often, calcium
carbonate scaling occurs with a pressure drop (e.g., at the
wellbore of a producer). This reduces the partial pressure
of CO2, thereby increasing the pH and decreasing the
CaCO3 solubility.
An unusual and very important property of calcium
carbonate is that its solubility decreases with increasing
temperature.
Calcium Sulfate
The precipitation of calcium sulfate is given by the reaction
Ca ++ + SO =4 CaSO 4 (s)
5-4
(3)
Table 1
Deposit
Chemical
Formula
Mineral
Name
Calcium
Carbonate
CaCO3
Calcite
Calcium
Sulfate
CaSO4 2H 2O
CaSO4
Gypsum
Anhydrite
Barium
Sulfate
BaSO4
Strontium
Sulfate
Partial
Pressure CO2
X
Barite
SrSO4
Celestite
Iron
Carbonate
FeCO3
Siderite
Iron Sulfide
FeS
Trolite
Iron Oxide
Fe2 O3
Fe3 O4
Hematite
Magnetite
X
X
X
X
Sodium
Chloride
NaCl
Halite
Magnesium
Hydroxide
Mg(OH)2
Brucite
Silicates
Variable
Corrosion
X
X
H2S
Oxygen
X
X
X
X
5-5
5-6
Table 2
Deposit
Mineral Name
Removal
Chemical
Calcium
Carbonate
CaCO3
Calcite
15% HCL
Calcium Sulfate
CaSO 4 2H 2 O
CaSO 4
Gypsum
Anhydrite
Same as Above
Converting
Solutions, EDTA
Type Dissolvers
Barium Sulfate
BaSO4
Barite
Mixing of Brines
Strontium Sulfate
SrSO4
Celestite
Iron Carbonate
FeCO3
Siderite
Same as Above
Sequestered
Acid
Iron Sulfide
FeS
Trolite
Same as Above
Iron Oxide
Fe2O3
Fe3O4
Hamatite
Magnetite
Same as Above
Sodium Chloride
NaCl
Halite
Evaporation of Water
Water or 13%
HCL
Magnesium
Hydroxide
Mg(OH)2
Brucite
15% HCL
Silicates
Variable
HCL:HF Acid
Mixtures
Barium Sulfate
This scale is especially troublesome. It is extremely
insoluble and almost impossible to remove chemically.
Fig. 1 compares the solubilities for common oilfield scales
in distilled water. Barium sulfate scaling is likely when
both barium and sulfate are present, even in low concentrations.
++
(4)
5-7
tion (high sulfate concentration) for secondary oil recovery causes the scale problem. As the waterflood matures
and the seawater breaks through, these incompatible
waters mix and the barium scale forms.
Generally, barium sulfate solubility increases with
temperature and salinity. Similar to gypsum, BaSO4
solubility increases with an increase in total pressure and
is largely unaffected by pH.8,9
Strontium Sulfate
Strontium sulfate is similar to barium sulfate, except
fortunately its solubility is much greater.
Sr++ + SO 4 SrSO 4 (s)
(5)
Iron Compounds
The oxidation state of
iron is important in the
form these scales take.
5-8
Solubility Calculations
Solubility calculations may be performed to determine
the theoretical amount of scale-forming ions that can be
kept in solution. Comparison with the actual concentration of the scaling ions in solution indicates the scaling
tendency or the likelihood of scale formation.
Note that these calculations only provide a guideline and
are not necessarily exact. Simplifying assumptions have
been made in the derivation of all predictive equations;
the solubility of inorganic compounds in naturally occurring waters is a complex phenomenon.
Scaling tendency is a
measure of the driving
force or likelihood of
scale deposition.
Saturation Index
Consider for example a water containing barium and
sulfate. The theoretical solubility product, Ksp , is given
by
)(
++
=
K sp = C Ba
C SO 4 (at saturation)
(6)
5-9
IP
K sp
(7)
(8)
Undersaturated; no scaling.
2. SI = 0-1:
5-10
5-11
SCALE PREVENTION
Avoid Mixing Incompatible Waters
One primary cause of scale formation is the mixing of
two or more incompatible waters. The individual waters
may be quite stable at all system conditions and present
no scale problem. However, once they are mixed, reactions between the ions dissolved in the individual waters
may form scales. When this occurs, the waters are said to
be incompatible.
The scaling tendency calculations discussed above may
be applied to the projected mixture of waters. We highly
recommend that such a calculation be performed before
two or more water sources are mixed in the field. The
best policy is simply to avoid mixing waters if at all
possible.
5-12
Water Dilution
Sometimes precipitation can be halted in a scaling water
by deliberately mixing it with another usually fresher
water so that the mixture is stable (recognizing the incompatibility restrictions noted above).
pH Control
A decrease in pH will increase the solubility of iron
deposits and carbonate scales. This method must be used
with caution because it tends to make the water more
corrosive. Adjusting the pH has little impact on sulfate
scales.
This approach is generally practical only if a minor shift
in pH will be sufficient to solve a scale problem. Precise
pH control is required and is often difficult to attain in
the oil field.
Removing scale-forming
ions like Ca++ is normally
practical for water fed to
steam generators.
5-13
Addition of Chelators
Certain chemicals like EDTA (ethylenediaminetetraacetic
acid) will prevent scale deposition by reacting
(complexing or chelating) with scaling ions to form a
water-soluble complex. This effectively removes the ion
from solution.
The basic disadvantage of using these chemicals as scalecontrol agents is their inefficiency. Generally, the dosage
of chelant must be equimolar to the scaling ion. For
example, an equimolar ratio of Na4 EDTA to Ca++ is
equivalent to a mass ratio of about 10 to 1. Another
possible disadvantage is that chelator solutions can be
corrosive (see Chapter 6). Generally, chelators are used
for the chemical removal of some scales (see the Scale
Dissolvers section) rather than as scale preventers. An
important exception is the inclusion of chelators in acid
treatments. Chemicals such as sodium citrate, sodium
gluconate, and EDTA are often included to prevent the
precipitation of iron compounds released by the acid
treatment.
Environmental Controls
Another approach is to control the temperature and
pressure to avoid creating scaling conditions. The process usually dictates these parameters; the operator has
limited ability to make the required adjustments.
SCALE INHIBITORS
Principle of Use
Scale inhibitors are chemicals that delay or prevent scale
formation when added in small concentrations in normally scaling water. Use of these chemicals is attractive
(compared with chelation agents) because a very low
dosage (several ppm) can be sufficient to prevent scale
for extended periods of time for either surface or down-
5-14
hole treatments. The precise mechanism for scale inhibitors is not completely understood but is thought to include two possibilities25:
1. Scale inhibitors may adsorb onto the surface of the
scale crystals just as they start to form. The inhibitors
are large molecules that can envelop these microcrystals and hinder further growth. This is considered to be the primary mechanism.
2. In some cases, the chemical may simply prevent the
precipitate from adhering to the solid surfaces.
Scale inhibitors that actually prevent precipitation are
clearly preferable for water injection operations. Suspended solids (nonadherent scales) are not acceptable.
Because these chemicals function by stopping the growth
of scale crystals, the inhibitor must be present before the
onset of precipitation. This suggests two basic rules in
applying scale inhibitors:
1. The inhibitor must be added upstream of the problem
area.
2. The inhibitor must be present in the scaling water on
a continuous basis to halt the growth of each scale
crystal as it precipitates.
To be effective, inhibitors
should be added at a
sufficient dosage
upstream of the problem
area.
Phosphonates.
Phosphate esters.
Polymers.
5-15
degradation. They can decompose (hydrolysis or reversion) rapidly, particularly at low pH or high temperature.
On the other hand, organic-based inhibitors usually are
conveniently packaged as a concentrated liquid and are
inherently more stable chemically. Ref. 2 provides further details on inorganic polyphosphates.
Table 3 summarizes the attributes of each type of scaleinhibitor chemistry. One key variable is system temperature. The phosphate esters can be very cost-effective but
are not recommended for temperatures above 175F
where they may hydrolyze in a few hours. The
phosphonates are good to perhaps 300F. Polymers like
acrylates can be used up to 400F. An important factor
for high-temperature applications is how long the inhibitor must function. Cheaper, less stable inhibitors may be
acceptable for short durations, but not for squeeze treatments where the chemical must survive in the formation
for months.
Table 3
Scale Inhibitors
Hydrolytic
Stability
Temperature
Stability
Detectability
Inorganic
Polyphosphonates
Poor
Poor
Good
Organic Phosphate
Esters
Good
Fair
Good
Organic
Phosphonates
Excellent
Good
Very Good
Organic Polymers
Excellent
Excellent
Difficult
Type
5-16
5-17
5-18
5-19
Batch Treatments
Batch treating a producer by periodically pouring scale
inhibitor down the annulus is the simplest downhole
application technique. This method has two major drawbacks.
5-20
Table 4
Batch Treatment
Continuous Recirculation
Simple
Poor Control
More Complex
Good Control
Squeeze Treatments
Complex
Continuous Recirculation
An improved, but more complex, method is to pump the
scale inhibitor downhole continuously. Fig. 4 illustrates
three continuous placement methods35,36: annulus flush,
coiled tubing, and downhole chemical injection pump
(DHCIP). Table 5 compares their characteristics.
The main advantage of these methods is the increased
control in injecting the treatment chemical. The scale
inhibitor can be injected into the produced water as far
down as the bottom of the tubing and at the optimum
concentration on a continuous basis. However, these
methods do not prevent scale deposition in the perforations or in the formation itself.
All techniques have the disadvantage of requiring extra
equipment (capital and operating costs) compared with
batch treating. The increased complexity means that
such systems require attention (maintenance) to operate
Chapter 5: Scaling and Water Formed Solids
5-21
Table 5
Characteristic
Annulus Flush
Coiled Tubing
DHCIP
Production Loss
(Recycle)
Yes
Yes
Yes
No
Yes
Yes
Capital Cost
Low
High
High
Risk of Mechanical
Failure When
Installed
Low
High
Medium
Should Monitor,
Poor Mixing,
Chemical Build-up
Unproven
Technology,
Plugging DHCIP
Intake
Special Problems
5-22
5-23
Chemical (thermal) stability. The inhibitor is retained inside the reservoir for weeks or months before
it is released into the produced water. The chemical
must not degrade during that time.
Detectability. The treatment is monitored by the
measured concentration of scale inhibitor in the
produced water; the end of the squeeze is determined
when the concentration falls below the acceptable
level. Thus, there must be an accurate and convenient
analytical method to determine these residual concentrations.
Phosphonate scale inhibitors are the most common
choice for squeeze treatments because they have good
thermal stability and because we can use a standard test
to measure their concentration in brine.40 As mentioned,
the phosphate esters suffer from relatively poor thermal
stability, and most polymers are not used in squeeze
treatments because their concentration in oilfield brines is
very difficult to determine accurately. Some polymer
products (such as ESL) circumvent the detection problem
by incorporating a phosphorous group into the molecule.
This permits analysis by the conventional method for
phosphonates. Some recent laboratory work reported in
the literature41 suggests that the phosphonates also are
preferred because of their better retention/release characteristics compared with esters.
the literature suggest that the placement and desorption of the scale inhibitor can be kinetically controlled
and hence is sensitive to flow rate.42,45
Amount of scale inhibitor. The more chemical used,
the longer the squeeze life. However, increasing the
inhibitor by itself usually gives a diminishing return
on squeeze life. For example, doubling the scaleinhibitor concentration alone typically increases the
squeeze life, but by less than a factor of two.
Overflush volume. The overflush volume needs to be
large enough to drive the scale inhibitor several feet
into the reservoir. This smears out the chemical,
giving it an adequate chance to adsorb or precipitate,
and decreases the high concentrations that return
initially. A rule of thumb is to make the overflush
volume about twice the inhibitor slug volume.
Minimum effective concentration. The squeeze life
can be improved considerably if the inhibitor concentration can safely be allowed to fall to lower values.
This option may be available at production wells
where the scaling tendency is low.
Repeated treatments. The squeeze life tends to improve with subsequent squeeze treatments because
they take advantage of the chemical left behind in the
formation by earlier squeezes.49
Retention/release characteristics. The way that the
inhibitor is retained and subsequently leached into
the produced water can greatly affect squeeze life. As
a general rule, squeeze life is longer for treatments
that rely on precipitation than those that rely on
strictly adsorption.44 In these precipitation squeezes,
calcium is introduced either into the inhibitor slug
itself or in a preflush or overflush. One danger of the
precipitation squeeze method is that the calcium/
inhibitor salt may form too quickly and cause formation damage.
Ref. 42 describes a Chevron mathematical model for the
adsorption squeeze method and explains some trends
seen in the adsorption squeezes performed at Ninian
field.38,39 This model and some literature data suggest
A Chevron mathematical
model for the adsorption
squeeze method explains
trends seen in data from
Ninian field.
5-25
5-27
SCALE REMOVAL
Scale removal is the last
resort for fixing a
deposition problem.
If preventive steps fail to halt undesirable scale deposition, chemical and mechanical methods are available to
remove this material.
Note that scale removal is the last resort for curing a
precipitation problem. Preventing scale deposition is
much preferable.
Scale Identification
One key in scale removal is first to identify the composition of the deposit. A suggested procedure for qualitatively identifying scales in the field include (Table 6):
Table 6
Component
Magnetic
CaCO3
Reaction
Acid Color
Smell
Strong
Yellow
H2S
Weak
Yellow
Weak
Yellow
Very Strong
Yellow
Soluble in
Water
Very Strong
CaSO4
BaSO4 and
SrSO4
FeS
Weak
Fe2O3
Fe3O4
FeCO3
NaCl
Strong
Yes
Sand,
Silt Clay
5-28
Chemical Removal
General Comments
When using chemical solutions to remove scale deposits,
you should:
Incorporate scale prevention into the program so that
the problem does not recur. In particular, we usually
follow a scale-dissolver treatment with a scale-inhibitor squeeze to prevent future scaling.
Bring the solvents back to the surface immediately
following treatment. The injected chemicals may
become supersaturated and reprecipitate if left in the
formation.
Chapter 5: Scaling and Water Formed Solids
5-29
Calcium Carbonate
The most common method to dissolve calcium carbonate
scale is with HCl. Acid concentrations normally range
from 5% to 15% HCl. A 15% HCl solution can dissolve a
maximum of 1.84 lbm of CaCO3 per 1 gal of acid.
(9)
(10)
=
EDTA 4 + Ca ++
Ca EDTA
(11)
5-30
Calcium Sulfate
Calcium sulfate is largely insoluble in acid. The maximum solubility of CaSO4 is less than 2% in HCl at ambient conditions.
Chelating agents are often used for gypsum removal.
The comments made about calcium carbonate removal
apply to gypsum removal. EDTA has successfully
treated gypsum-scaled production wells at Chevrons
Virden field in Manitoba, and Amoco reports successful
field tests in Levelland field in Texas.53,54
Our laboratory results agree with the literature that
important parameters chelating agent treatment design
are:53-59
Product concentration. The higher the concentration,
the greater the capacity to dissolve scale (up to a
point--about 40% product concentration). At concentrations much higher than this, the capacity actually
diminishes because there is not enough water to hold
the dissolved material in solution.
Soak time. Sufficient time must be allowed for the
reaction to complete. We usually allow a 1-day contact time, but longer may be necessary in some cases.
Temperature. The reaction rate increases significantly
with temperature. It is preferable to have a temperature above 150F. We allow several days for soak time
at Virden because the reservoir temperature is only
80F.
Agitation. The dissolution rate increases substantially with agitation.
Surface area. The treatment is more effective if the
scale has a large surface area. This makes it much
easier for the chemical to come in contact with and
rapidly dissolve the scale. Consequently, dissolvers
can effectively remove gypsum in the formation
matrix (high surface area), but they rarely remove
gypsum on tubing. The ideal application is the removal of a small quantity of scale near the production
wellbore that is causing severe formation damage.
5-31
Beside chelators,
converters are another
option to remove gypsum.
(12)
(13)
Barium Sulfate
Barium sulfate is very difficult to remove chemically and
until recently was removed only by mechanical means.
5-32
Two vendors (Unichem and Baker Performance Chemicals) now market proprietary scale dissolvers. These
dissolvers are chelant-type materials, so the general
comments made earlier about the design of a treatment
program apply. In particular, these products are expensive and react slowly with scale. Their best application is
to remove scale in the perforations or the reservoir rock
matrix near the wellbore.56,57
The vendors report successes with removing near-wellbore formation damage from barium sulfate scale in
some North Sea fields.58 CEPS and our laboratory tests
with these products substantiate that they can dissolve
appreciable amounts of barium sulfate.59,62
Iron Compounds
HCl usually is used to dissolve iron compounds. This
should include a corrosion inhibitor to prevent excessive
pipe corrosion. It should also include an iron-stabilizing
agent to prevent reprecipitation of iron compounds once
the acid spends and the pH increases.
The iron dissolved during acidizing can exist either as the
ferrous (Fe++) or the ferric (Fe+++) ion, depending on the
presence of oxidizing agents (air). As the acid spends
and the pH increases, ferric ions (the less soluble form)
will begin to precipitate as ferric hydroxide [Fe(OH)3] at a
pH of around 2.2. Once the pH rises to 3.2, almost all the
ferric ion will have precipitated.63 Iron stabilizers are
added to prevent this ferric hydroxide precipitation.
There are two types of iron stabilizers63,64:
1. Chelating agents. These products tie up the ferric
ions in a water-soluble complex, thereby preventing
their precipitation. Citric acid, acetic acid, nitriloacetic acid (NTA), and EDTA are common examples.
2. Reducing agents. These chemicals convert ferric ions
to the more soluble ferrous oxidation state. Erythorbic acid is perhaps the most common reducing agent
used for this purpose.
Ferrous ions are quite soluble up to neutral conditions.
Precipitation of ferrous ions is less of a problem because
even the spent acid usually has a pH well below 7.
5-33
Mechanical Removal
Downhole Cleanout
In downhole cleanout, scale is removed from the tubing,
perforations, formation face, and sometimes the formation matrix.
If the scale in the tubing is severe, the tubing may be
pulled and treated on the surface. Chemical means may
suffice for lighter scaling.
A number of downhole tools casing brushes, surge/
swab tools, and suction and circulation washers remove deposits from the formation face or perforations.
5-34
5-35
5-36
REFERENCES
1. Patton, C. C.: Applied Water Technology, first edition,
Campbell Petroleum Series, Norman, OK (1986)
Chap. 3.
2. Cowan, J. C. and Weintritt, D. J.: Water-Formed Scale
Deposits, Gulf Publishing Co., Houston (1976).
3. Ostroff, A. G.: Introduction to Oilfield Water Technology,
National Association of Corrosion Engineers, Houston (1979) Chap. 3.
4. Carlberg, B. L. and Matches, R. R.: Solubility of
Calcium Sulfate in Brine, paper SPE 4353 presented
at the 1973 SPE Oilfield Chemistry Symposium,
Denver, May 24-25.
5. Vetter, O. J. G. and Phillips, R. C.: Prediction of
Deposition of Calcium Sulfate Scale Under DownHole Conditions, JPT (Oct. 1970) 1299.
6. Waldram, I. M.: Natural Radioactive Scale: The
Development of Safe Systems of Work, JPT (Aug.
1988) 1057-1060.
7. Smith, A. L.: Radioactive Scale Formation, JPT
(June 1987) 697-706.
8. Blount, C. W.: Barite Solubilities and Thermodynamic Quantities up to 300C and 1400 Bars, American Mineralogist (1977) 62, 942-57.
9. Templeton, C. C.: Solubility of Barium Sulfate in
Sodium Chloride Solutions from 25C to 95C,
J. Chem. and Eng. Data (Oct. 1960) 5, 514.
10. Vetter, O. J. G., Vandenbroek, I. and Nayberg, J.:
SrSO4: The Basic Solubility Data, paper SPE 11803
presented at the 1983 SPE International Symposium
on Oilfield and Geothermal Chemistry, Denver,
June 1-3.
11. Jacques, D. F. and Bourland, B. I.: A Study of Solubility of Strontium Sulfate, JPT (April 1983) 292-300.
12. Jacques, D. F., Gollberg, J. B., and Whiteside, W. C.:
Strontium Sulfate Solubility and the Effects of Scale
Inhibitors, paper presented at the NACE Middle East
Corrosion Conference/79, Bahrain, April 15-17.
5-37
5-38
5-39
5-41
54. Schutte, R. W.: Designing Gyp Scale Removal Treatments Based on Chemical Characteristics to Optimize
Field Performance, paper SPE 16888 presented at the
1987 SPE Annual Technical Conference and Exhibition, Dallas, Sept. 27-30.
55. Shuler, P. J.: Gypsum Scale Removal and Inhibition,
Virden Field, Manitoba, COFRC Technical Memorandum TS87000551 (June 3, 1987).
56. Treatment Chemicals for Oil and Gas Production, International Drilling Fluids (vendor brochure).
57. Oilfield Scale Dissolution and Control, second edition,
Akzo Chemicals (vendor brochure) (May 1988).
58. Clemmit, A. F., Ballance, D. C., and Hunton, A. G.:
The Dissolution of Scales in Oilfield Systems, paper
SPE 14010 presented at the 1985 SPE Offshore Europe
Conference, Aberdeen, Sept. 10-13.
59. Hall, B. E.: Solvent for Barium Sulfate and Calcium
Carbonate, Technical Memorandum PSD 870013 or
COFRC OR88000258 (Dec. 1, 1987).
60. Hoerauf, R. C.: New Two-Step Xylene-Scale Treatment Removes Calcium Sulfate, Oil & Gas J.
(Aug. 22, 1988), 56-59.
61. Smith, C. F., Noland, T. J., and Crenshaw, P. L.: Removal and Inhibition of Calcium Sulfate Scale in
Waterflood Projects, JPT (Dec. 1968) 1246-56.
62. Shuler, P. J.: Performance of Barium Sulfate Scale
Dissolvers - Rangely Field, preliminary report,
Technical Service Project 46,557, TS88001118.
63. Smith, C. F., Crowe, C. W., and Noland, T. J.: Secondary Deposition of Iron Compounds Following Acidizing Treatments, JPT (Sept. 1969) 1121-29.
64. Dill, W. and Smolarchuk, P.: Iron Control in Fracturing and Acidizing Operations, J. Cdn. Pet. Tech. (MayJune 1988) 75-78.
5-42
GLOSSARY
anhydrite calcium sulfate mineral or scale that contains no water.
black water water that contains suspended iron sulfide scale.
calcium sulfate converters chemicals that convert
calcium sulfate scale deposits to a an acid soluble
form.
cathodic protection a method wherein a metals surface is made the cathode of an electrochemical cell
thereby shifting the its corrosion potential towards a
less oxidizing potential and reducing its corrosion
rate.
celesite name for strontium sulfate mineral.
chelating agent an organic compound in which atoms
form more than one coordinate bond with metals in
solution.
chelation the formation of a soluble complex between
an ion and another species. One way to prevent or
remove scale is to tie-up (chelate) the offending cation
with an added chemical.
citric acid chemical that ties-up (chelates) with iron to
keep it in solution.
corrosion the deterioration of a material, usually a
metal, and its properties by chemical or electrochemical reaction with its environment.
crevice corrosion localized corrosion of a metal surface at, or immediately adjacent to, an area that is
shielded from full exposure to the environment because of close proximity between the metal and the
surface of another material.
EDTA ethylenediaminetetraacetic acid. A common
chelating agent that is used to keep iron in solution,
or as a remover agent for scale deposits.
erosion destruction of materials by the abrasive action
of moving fluids, usually accelerated by the presence
of solid particles.
5-43
pitting corrosion localized corrosion of a metal surface that is confined to a small area and takes the form
of cavities.
polyphosphates an older class of scale inhibitors.
These are not commonly used because of their inherent instability. These are solids characterized by
containing phosphate groups.
red water water that contains suspended iron oxide
solids.
reducing agent compound that reduces the oxidation
state of a species. The most common example is a
chemical that reduces ferric iron (+3 charge) to ferrous
iron (+2 charge).
saturation index a measure of the driving force for
scale deposition to occur.
scale inhibitor squeeze process whereby a scale
inhibitor is applied inside the reservoir.
solubility the maximum amount of dissolved ions
that will remain in solution.
stainless steel an iron-based alloy containing at least
10.5% Cr.
supersaturation ratio the ratio of the product of the
scaling ions concentrations to their solubility product.
A supersaturation ratio greater than one indicates
their is a positive tendency for scale deposition.
5-45
5-46
APPENDIX
5-47
5-48
C H A P T E R
6
Corrosion Effects
6-1
6-2
INTRODUCTION
This chapter is intended to be an introduction to corrosion control alternatives available for water treatment
systems. It is not a comprehensive corrosion control
guide. The Chevron Corrosion Prevention Manual, Coatings Manual, and Pipeline Manual provide more specific
information and additional references. Our intent is not
to reproduce here the information available in these
manuals (copies of the Tables of Contents are included in
the Appendix). We strongly recommend that you have
easy access to these manuals, available from Technical
Standards Division, Chevron Research and Technology
Company (CRTC), San Ramon, 510/842-8503.
Other chapters in this handbook discuss the injection of
treating chemicals and corrosion associated with bacteria.
6-3
GENERAL CORROSION
Corrosion of metals is an
electrochemical reaction
which requires an
electrolyte, an anodic
surface, a cathodic
surface, and a metallic
connection between them.
O 2 + H 2 O + 2e = 2OH
6-4
LOCALIZED CORROSION
As the name suggests, localized corrosion occurs at very
localized spots, resulting in rapid penetration of pipe and
vessel walls. As in general corrosion, two coupled reactions occur. The anodic reaction is localized while the
cathodic reaction may occur over much larger areas of
the surrounding surface, with electron flow through the
connecting metal.
Localized corrosion rarely causes water quality problems.
The extent of the corrosion is very small compared with
general corrosion. We address localized corrosion here
because, if not controlled, it places very real limits on the
operating life of water treating equipment. Here we
discuss the types of localized corrosion seen most often in
produced-water treating systems. For information on the
less common types (stress corrosion cracking, intergranular corrosion, corrosion fatigue, selective dealloying) see
the Corrosion Prevention Manual, Sections 120 and 300.
Pitting
Mild steel in oilfield brines will usually show a combination of general and pitting corrosion. Stainless steels
show predominantly pitting corrosion.
Pitting occurs when a protective film (a passive layer, an
applied coating, or an inhibitor film) breaks down in
localized areas. The presence of halides, sulfides, or
deposits often causes passive layers to break down.
Coatings breakdown may be caused by holidays in the
manufactured coating, mechanical damage, or physical
6-5
Crevice Corrosion
Crevice corrosion results from local differences in the
environment seen by the metal e.g., under washers,
under deposits, or in other areas where small stagnant
volumes exist. Crevice corrosion is enhanced by tighter
crevices, higher temperatures, higher chloride levels, and
traces of oxygen. Crevice corrosion occurs more readily
than pitting corrosion. We must consider the prevention
of crevice corrosion when designing and constructing
treating equipment.
Galvanic Corrosion
Different alloys generate different potentials when immersed in an electrolyte. If the potentials developed by
two alloys that are electrically connected are sufficiently
different, galvanic currents may flow between the alloys.
One alloy becomes cathodically polarized and is protected; the other becomes anodically polarized and is
sacrificed.
Galvanic series have been published for materials in
several environments to show the materials in electrical
contact that will be protected or sacrificed. In general,
6-6
CORROSION RATE
Corrosion rates in water treating systems range from
negligible to hundreds of mils per year (1 mpy = 0.001
in./yr). Corrosion allowances vary but almost always
refer to acceptable general corrosion rates. When pitting
is considered, maximum allowable measured corrosion
rates should never exceed 5 mpy and should normally be
1 mpy or less. The penetration rate by localized corrosion is generally 5 to 20 times greater than a measured
general corrosion rate.
6-7
Although oxygen
solubility is low, water
treatment facilities handle
large volumes of water, so
the total amount of
oxygen available to
corrode equipment can be
significant.
6-8
heavily on flow conditions. At little or no flow, corrosion rates are high in stagnant areas. At moderate
flow rates, iron carbonate films are deposited. These
films are protective to some extent but may cause
localized corrosion. At high flow rates, iron carbonate
films are removed, and corrosion rates increase.
CO2 often enhances corrosion by other species, such
as oxygen, chloride, and H2S. CO2 also contributes to
sulfide stress corrosion cracking.
6-9
6-10
Effect of pH
Pourbaix Diagrams Pourbaix diagrams show the
thermodynamic stability of various metals in various
environments. The diagrams say nothing about the
rates of corrosion reactions; they show only tendencies. They also show regions of stability of a metal
and its oxides. Areas where the metal and its oxides
are not stable are generally regions of high corrosion
rates. With iron, the oxides are more stable at a
higher pH, so corrosion rates are generally lower
from pH 7 to 13. Above pH 13, corrosion rates again
increase. Corrosion rates increase with decreasing pH
below 7.
pH Buffering Weak acids, such as carbonic acid and
acetic acid, provide a pH buffering capacity that often
leads to higher corrosion rates than could be expected
from the solution pH alone.
Effect of Temperature
Increasing temperature (in the normal range of water
treating systems) generally increases corrosion rates,
particularly in corrosion caused by dissolved acid gases.
Although oxygen solubility decreases with temperature,
corrosion rates in open systems increase with temperature. If the temperature is not uniform, hotter areas are
generally anodic to cooler areas.
6-11
Effect of Deposits
Adherent Deposits Adherent deposits often form
protective barriers to corrosion. The best example is
the polarization (reduction in current requirement)
that occurs on cathodically protected steel in seawater. At high initial current densities, a dense layer of
adherent calcium carbonate, which helps protect the
metal, is deposited.
Nonadherent Deposits Nonadherent deposits, in
many instances formed from corrosion products,
provide stagnant areas that can lead to rapid pitting.
Pigging is used primarily to remove deposits and to
allow uniform access from the environment to the
metal. Nonadherent deposits also provide protection
for bacteria, which increase pitting tendencies.
Nonadherent iron sulfide deposits are cathodic to
iron, especially in the presence of oxidizers. The
galvanic cell created can cause rapid penetration of
pipes and vessels.
Periodic scrapping (pigging) to remove these deposits
from within pipelines is an important part of effective
corrosion control in water handling systems. Pigging
minimizes the stagnant areas, removes bacteria colonies, and allows chemical inhibitors to come in contact with the metal surface.
MONITORING
The monitoring methods can be characterized by the time
required for measurement and the type of corrosion
detected. The monitoring methods are useful for detecting significant changes in corrosion rates, but they should
not be used to determine exact corrosion rates. More
than one monitoring method should always be used to
overcome the limitations of each method. Coupons should
always be included in the monitoring program.
For more information on specific equipment and for
ordering information, see the Corrosion Prevention
Manual, Section 400.
6-12
Inspection
The most reliable corrosion monitoring method is periodic inspection. All parts removed from a water treatment system should be inspected. If possible, the parts
should be sandblasted to reveal hidden pitting. For
cracking or fracturing, failure analysis should be used to
determine the cause and cure. (Successful failure analysis depends on a failure experts prompt study of failed
parts that have not been altered in any way.) A
boroscope can be used to inspect piping in place. In a
large pipeline, electronic inspection pigs can be used.
Note the type of corrosion product. For example, a red
corrosion product on an iron-containing alloy is probably
hematite. Hematite indicates that oxygen may be entering the system. Black deposits are usually either magnetite or iron sulfides. A drop of HCl will cause iron sulfides to bubble and evolve H2S. Magnetite is attracted to
a small magnet. If wet magnetite is removed from a
system and exposed to air, it will rapidly convert to
hematite, so parts must be inspected immediately. Iron
sulfides also oxidize rapidly, and large quantities can
spontaneously ignite upon drying under some conditions.
6-13
Iron Counts
The dissolved iron concentration in a water stream can
sometimes be correlated to the corrosion rate upstream.
The surface area of corroding pipe and the flow rate are
used to calculate a general corrosion rate. This method is
of little use in streams containing oxygen or sulfides
because iron compounds will precipitate.
Organic corrosion inhibitors contain surfactants and act
as detergents. These inhibitors will clean fouled surfaces,
so initial iron counts after a treatment starts will be quite
high.
Electrical Resistance
Electrical resistance probes, such as the RohrbachCosasco Corrosometer, measure the gradual increase in
electrical resistance of a thin wire as it loses metal by
general corrosion. The probes are usually designed for a
response time of at least a few hours and a probe life of
several months or even years. The probes generate an
electrical signal, providing a continuous record of corrosion rates.
Pitting corrosion cannot be distinguished with a singleprobe instrument. Various types of probes are available
that respond to pitting in different ways. Wire-loop
probes are more sensitive to pitting damage than cylindrical probes are. Wire-loop and tube-loop elements are
also subject to being electrically shorted by a bridge of
iron sulfide deposits.
Most resistance probes include a coated reference element to compensate for temperature changes. In rapidly
changing temperatures, the reference element temperature will not be able to track the test element, leading to
errors in readings.
6-14
All-welded cylindrical probes have no seals at the connection end, so they are less likely to leak. They also are
always in electrical contact with the pipe wall, possibly
leading to galvanic interactions. The welds may be
preferentially attacked in some systems.
Because the resistance probe is expected to corrode, the
body itself and the backup seals must be corrosionresistant to prevent leaks when the probe fails.
Linear Polarization
Tretolites PAIR and Rohrbach-Cosascos Corrater measure instantaneous corrosion rates using the linear polarization method. These instruments also generate a continuous record of corrosion rates. They have a response
time of minutes, but the probes should not be used for
more than about a week and readings should be correlated to exposure time. Again, pitting corrosion is not
well detected.
These electrochemical instruments are limited to conductive electrolytes. At a corrosion rate of 2.5 mpy, the
solution conductivity must be at least 100 to 250
micromhos/cm for accurate readings. In low-conductivity brines, a three-electrode instrument should be used,
while either two- or three-electrode systems are suitable
for high-conductivity brines. The probes are easily
fouled by high oil concentrations.
Galvanic Probes
The Fincher galvanic probe system is similar to the linear
polarization instruments, except the driving voltage is
derived from the galvanic interaction between two dissimilar metals. The same concerns apply to these instruments as to linear polarization probes, but they have the
advantage of not requiring power. The usual metals are
mild steel and brass. The same technique is used by the
Tretolites Zero Resistance Ammeter oxygen monitoring
instrument.
6-15
Hydrogen Monitors
Hydrogen patch probes and finger probes are used in
sour systems to measure the rate of evolution of atomic
hydrogen. The patches are installed on the external side
of pipes or vessels. As atomic hydrogen diffuses through
the pipe, it recombines and generates a high pressure of
molecular hydrogen. Finger probes, constructed of thinwalled tubing, are inserted into the flow stream. The
finger probe is more rapid because the hydrogen permeates a smaller distance.
Ultrasonic Surveys
In this method, an ultrasonic source is connected to the
outside of a pipe or vessel, and the time required for a
reflection from the other side is measured. Generally,
several points in a system are clearly marked so that the
same point is tested in each of a series of surveys. The
disadvantages of this method are that only a very small
fraction of the piping or vessel may be tested and that
severe pits may be missed entirely.
CORROSION PREVENTION
Corrosion prevention should begin in the early design
stages of a water handling facility with the proper choice
of materials of construction. In terms of installed cost,
ease of installation, and temperature and pressure requirements, the construction material of choice is usually
mild carbon steel. Coatings, cathodic protection, and
chemical treatment are then used to control corrosion. In
most water injection systems, however, the volume of
water handled is quite large, so chemical treatment for
corrosion control becomes very expensive.
6-16
6-17
Inhibitors
Organic Inhibitors Organic corrosion inhibitors
almost exclusively have nitrogen-containing functional groups. Several classes of chemicals may be
used, including low-molecular-weight amines for
vapor-phase inhibitors, filming tertiary and quaternary amines for water service, and imidazolines for
sour applications. The nitrogen-containing organic
inhibitors are rarely useful in oxygenated waters.
Vapor phase inhibitors, such as morpholine and
cyclohexylamine, have boiling points near that of
water. Thus, wherever water condenses, the inhibitor
condenses. The inhibitor acts by neutralizing acid
gases, such as CO2 and H 2S. Because these neutralizing inhibitors react stoichiometrically, treatment levels
may be quite high in some systems.
Water-phase inhibitors may be either water-soluble or
water-dispersible. Intended for systems with no oil
phase, water-soluble inhibitors generally are somewhat less effective than water-dispersible inhibitors.
Water-dispersible inhibitors, formulated with a hydrocarbon carrier, are only slightly soluble in water.
These chemicals tend to have better film persistency
than water-soluble chemicals.
Inorganic Inhibitors In oxygenated freshwater
systems near neutral pH, inorganic inhibitors are used
to promote the formation of passive films on steel
surfaces. These chemicals include chromates,
manganates, phosphates, sulfates, borates, vanadates,
and nitrites. Applications for inorganic inhibitors are
rare in the oil field; most systems should be maintained in an oxygen-free condition.
Alloys
This section is intended only as an introduction to the
wide variety of corrosion-resistant alloys. For more
information, consult the Corrosion Prevention Manual.
6-18
6-19
resistance increasing with nickel content. Molybdenum containing alloys (316, 317) have improved
resistance to chlorides and crevice corrosion.
2. Ferritic stainless steels are magnetic chromium- containing alloys produced by slow cooling. They can be
moderately hardened by cold working but not by heat
treatment. These metals are usually resistant to chloride cracking. AISI designations are, for example, 405,
430, and 446.
Thirteen percent
Chromium stainless steel
has achieved widespread
use in the oil industry.
Chevron has extensive
experience with this
material.
6-20
Hastelloy C (54%Ni/15%Cr/16%Mo/4%W/5%Fe) is
resistant to oxidizing media and mixed acids. It has
outstanding resistance to pitting and crevice corrosion.
Copper Alloys Copper is resistant to corrosion in
oxygen- free water but is susceptible to high-velocity
(>5 ft/sec) water containing oxygen. It is also susceptible to complexing agents like ammonium ions that
can cause rapid stress corrosion cracking. Copper is
resistant to seawater, and alloys above 60% copper do
not biofoul. Copper is not resistant to oxidizing acids
and will react with H2S. Brasses (copper/zinc alloys)
show more resistance to flowing water (up to 8 ft/sec)
but are subject to dezincification (selective leaching of
zinc), especially in stagnant areas and under deposits.
Aluminum Alloys Aluminum forms a tightly
adherent passive oxide layer that is resistant to sulfides and CO2. Aluminum is an amphoteric metal;
this passive film is stable near neutral pH but dissolves in either acids or bases. It is susceptible to
pitting in the presence of chlorides, crevice corrosion
and underdeposit attack, and attack by dissolved
copper that plates out and forms galvanic cells. Several aluminum alloys are available with superior
resistance to chlorides.
Cathodic Protection
Internal cathodic protection is often used in tanks and
vessels. Cathodically protecting the inside of pipes is
impractical. Protective current may be derived from
Chapter 6: Corrosion Effects
6-21
possibility of calcium carbonate scaling. If the stripping gas contains CO2, the pH may be lowered
enough to cause corrosion. If the stripping gas contains H2S, corrosion rates may be affected. The pH
should be kept low when H2S is stripped. The best
way is to use a stripping gas with a high concentration of CO2. Steam stripping is limited to waters with low total dissolved solids to prevent scaling.
Steam stripping can reduce oxygen levels to 6.5 ppb.
Vacuum de-aeration generally leaves 0.33 to 0.65 ppm
oxygen.
For further information, see NACE Standard RP-02-78,
Design and Operation of Stripping Columns for Removal
of Oxygen From Water or Chapter 3 of this handbook.
Oxygen Scavengers The three most common oxygen scavengers are sulfite ion (from sodium sulfite,
sulfur dioxide, or ammonium bisulfite), hydrazine,
and sodium hydrosulfite (dithionite). All three require a catalyst and at least several minutes of reaction time. The catalyst is a transition metal ion, such
as nickel or cobalt, at about 0.1 mg/L. Theoretically,
7.88 ppm of pure sodium sulfite is required to remove
1 ppm of oxygen. The residual level of scavenger is
maintained at 1 to 10 ppm. Hydrazine is usually
limited to high-temperature systems (above 200F);
sulfite may decompose to sulfur dioxide and H2S.
Hydrazine is a toxic liquid with a flash point of 35F.
It is usually supplied as a less explosive 35% solution.
In practice, 1.5 to 2.0 ppm of hydrazine is required per
1 ppm of oxygen, with residuals of 0.1 to 0.5 ppm.
Required residence time becomes very long below 150
to 200F.
The catalyst may be inactivated by precipitation with
sulfide ion or complexing with a chelant. The presence of alcohols, phenols, or amines can slow the
reaction by reacting with intermediate free radicals.
Corrosion inhibitors may interfere with the reaction
by either mechanism. In some cases, adding sulfite
results in sufficient sulfate to increase the activity of
sulfate reducing bacteria.
6-23
Coatings
Coatings provide barriers to corrosion. A large variety of
coating materials, application systems, and curing techniques are available. The Chevron Coatings Manual
covers the options in great detail.
Because no coatings are perfect, small holidays exist that
may be the site for accelerated pitting. Cathodic protection is often used to protect these holidays. The coating
protects most of the metal and significantly reduces the
protective current required. In congested areas or highresistivity electrolytes, coatings are necessary to reduce
current requirements sufficiently that interference is not a
problem.
Surface preparation is essential in applying a good coating. If the surface is not prepared correctly, the coating is
wasted and may cause more harm than good (localized
corrosion, flaking, etc.). The coating must be properly
mixed and applied according to manufacturers specifications. The coating must cure under the proper
temperature and humidity conditions for the proper
length of time. Inspection at each stage is recommended.
Linings
Two types of linings are common.
1. Concrete-lined pipe has been used successfully in CO2
floods and in flowlines and larger water service. For
more information on concrete linings, see the Piping
Manual.
6-24
2. Plastic linings are often used to repair severely corroded pipe. The old pipe serves as an installation
guide for new plastic pipe pulled through the line.
For more information on plastic liners, see the Corrosion Prevention Manual and the Pipelines Manual.
6-25
6-26
GENERAL REFERENCES
NACE Publications
1. Corrosion Data Surveys.
2. Standard RP-01-69, Control of External Corrosion on
Underground or Submerged Metallic Piping Systems.
3. Standard RP-01-75, Control of Internal Corrosion in
Steel Pipelines and Piping Systems.
4. Standard RP-04-75, Selection of Metallic Materials to
be Used in All Phases of Water Handling for Injection
into Oil Bearing Formations.
5. Standard RP-05-75, Design, Installation, Operation,
and Maintenance of Internal Cathodic Protection
Systems in Oil Treating Vessels.
6. Standard RP-07-75, Preparation and Installation of
Corrosion Coupons and Interpretation of Test Data in
Oil Production Practice.
7. Standard RP-02-78, Design and Operation of Stripping Columns for Removal of Oxygen From Water.
8. Standard RP-01-81, Liquid Applied Internal Protective
Linings and Coatings for Oil Field Production Equipment.
9. Standard MR-01-75, Sulfide Stress Cracking Resistant
Material for Oil Field Equipment.
Books
1. BETZ Handbook of Industrial Water Conditioning, J.J.
Maguire (ed.), Betz Laboratories, Trevose, PA (1980).
2. Munger, C. G.: Corrosion Prevention by Protective
Coatings, NACE, Houston (1984).
3. Corrosion Inhibitors, C.C. Nathan (ed.), NACE, Houston (1981).
4. CO2 Corrosion in Oil and Gas Production - Selected
Papers, Abstracts, and References, L.E. Newton and R.H.
Hausler (eds.), NACE, Houston (1984).
5. Ostroff, A.G.: Introduction to Oilfield Water Technology,
NACE, Houston (1979).
6. Uhlig, H.H.: Corrosion and Corrosion Control, John
Wiley and Sons Inc., New York City (1971).
Chapter 6: Corrosion Effects
6-27
6-28
APPENDIX A
INDEX TO CHEVRON
CORROSION PROTECTION MANUAL
6-29
6-30
APPENDIX B
INDEX TO CHEVRON COATINGS
MANUAL
6-31
6-32
APPENDIX C
INDEX TO CHEVRON PIPELINE MANUAL
6-33
6-34
C H A P T E R
7
Microbiological Problems in
Production Operations
7-1
7-2
INTRODUCTION
Microbiological and bacterial activity can have beneficial
or detrimental effects on producing operations. Examples of beneficial effects in reservoir engineering are
seen in microbially enhanced oil recovery (MEOR) processes. In MEOR, bacterial activity (1) produces gases
that increase reservoir pressure and/or reduce oil viscosity, (2) breaks down heavier crude oil fractions to affect a
lower viscosity, or (3) forms in-situ surfactants to lower
interfacial tensions and improve recovery.
In microbial profile modification (MPM), bacterial activity within the reservoir is deliberately augmented to form
biofilms and extracellular polymeric substances (EPS).
These substances can plug watered-out zones or adjust
permeability profiles for improved sweep efficiency and
oil recovery.
In producing operations, though, most of the effects of
bacterial activity are detrimental. This activity can be
within the reservoir or in downhole and surface equipment for production, treating, or injection. These detrimental effects range from shorter operating lives for
equipment to increased costs for oil production and
water treatment; from loss of reserves to degradation of
crude oil and natural gas quality and value. This chapter
discusses (1) the detection of microbial activity as the
cause of, or at least a contributing factor to, production
problems, (2) control procedures to eliminate or reduce
microbial activity, and (3) monitoring procedures to
determine the efficacy of control procedures.
Beneficial Effects
Microbially enhanced
oil recovery MEOR
Microbial profile
modification MPM
Detrimental Effect
Plugging and fouling
Corrosion chemical
Consumption damage.
7-3
Table 1
Formation of hydrogen
sulfide by sulfate
reducing bacteria is a
major cause of reservoir
souring.
The amount of sulfide produced by a single sulfatereducing bacterium has been estimated to be 1.0 x 10-16
moles of sulfide per day.1 Although the amount of H2S
produced by an individual bacterium is low, the number
of SRB in a single milliliter of water or on a square centimeter of surface may be in the millions or even billions.
Microbially produced H2S concentrations may reach
hundreds of parts per million in the gas phase of the
produced fluids. Biogenic (produced by bacteria) H2S
degrades the quality of the produced hydrocarbons. H2S
has other detrimental effects that are discussed in the
following sections.
7-5
1. Depolarization of the cathode reaction in the corrosion process because of intensified consumption of
hydrogen by bacteria.
2. Formation of patchy biofilms that enhance corrosion
through differential corrosion cells.
3. Generation of H2S that depolarizes the anode in the
corrosion reaction.
4. Formation of iron sulfide surfaces that increase the
rate of one or more of the corrosion reactions.
Microbiologically
influenced corrosion
(MIC) is particularly
harmful because it is a
form of localized
corrosion and causes
rapid pit formation.
5. Formation of organic acids that are corrosive in themselves, provide an additional source of hydrogen ions
for the cathode reaction, destroy protective films, or
provide usable organic carbon sources of other microbial reactions.
With MIC, the corrosion problem is enhanced because
invariably the corrosion process is localized. Pit penetration can cause equipment failures within a very short
time period. MIC frequently occurs where the corrosive
agent is generated. It can also occur away from the
generation site where the corrosive agent has migrated.
H2S produced by SRB and/or low-molecular-weight
organic acids produced by acid-producing bacteria (APB)
are the metabolic products usually involved in MIC. The
actions of SRB and APB are discussed in detail later.
Environmental Concerns
7-6
Like reservoir souring, the cause of environmental problems is the production of H2S by bacteria. However,
unlike souring, environmental problems can occur wherever SRB are present - in the reservoir, production string,
separating and treating system, or injection system.
Environmental and safety concerns are related to the
extreme toxicity of H2S. The threshold limit value (TLV)
for H2S is 10 ppm for 8-hour time-weighed-average
exposure. H2S is extremely flammable with flammability
limits of 4.3% to 45.5%. It is heavier than air and tends to
accumulate in low areas. H2S is easily recognized in low
concentration by its characteristic rotten egg smell. High
concentrations deaden the olfactory senses and can cause
unconsciousness and death before its odor is noticed.
Chemical Consumption
Bacterial activity can increase operating costs by consuming or degrading treatment chemicals. Treatment chemicals may stimulate bacterial activity. Some bacteria use
treating chemicals as a carbon and/or energy source for
metabolism.
Polymers used for scale control, diverting agents, or
fracture fluid thickeners are frequently biodegradable.
Phosphorus-containing scale inhibitors and nitrogencontaining oxygen scavengers may provide the trace
nutrients required for bacterial growth. Biomass formed
by bacteria may absorb treating chemicals or prevent
such chemicals as corrosion inhibitors and biocides from
reaching the surfaces they are designed to protect.
Larger dosages or more expensive formulations that can
penetrate the biofilms are required.
Water Chemistry
Bacterial activity affects water chemistry in a number of
ways. The formation of acids (e.g., CO2 and H2S) can
lower the pH and decrease the buffer capacity of the
solution. The concentrations of these two species also
increase in the associated gas phase. On the other hand,
Chapter 7: Microbiological Problems in Production Operations
7-7
Formation Damage
MICROBIOLOGICAL ENERGETICS
Bacteria require energy to
live and grow
(dissimilation) and to
multiply by the synthesis
of cell material
(assimilation).
7-8
Table 2
Oxidation-Reduction Reaction
Aerobic Glucose
C 6 H 12 O 6 + 6O 2 = 6CO 2 + 6H 2 O
;
G = 687 kcal
Aerobic Acetate
CH 3 COO + 2O 2 = 2CO 2 + 2H 2 + 2H 2 O ;
G = 204 kcal
Anaerobic Acetate
CH 3 COO + SO 24 + 3H + = 2CO 2 + H 2 S ;
G = 38.0 kcal
Fermentation Reaction
Glucose
C 6 H 12 O 6 + 4H 2 O = 2CH 3 COO + 2HCO 3 + 4H + + 4H 2 ;
G = 66.7 kcal
Note: G = G @ pH = 7
7-9
7-10
MICROORGANISMS INVOLVED IN
MICROBIAL PROBLEMS
Bacteria are scientifically classified by genus and species.
The genus refers to a group of related bacteria; the species refers to different bacteria within a genus. The types
of bacteria and microorganisms that contribute to or
influence problems in producing operations are described here in a functional sense in terms of activity or
metabolic products, rather than by strict microbiological
classifications. Particular bacterial species are given
sometimes. The bacterial classifications are written in
italics.
In the field, a number of different types of bacteria are
usually involved; laboratory studies frequently focus on
one type. The differences in behaviors of bacterial consortia vs. pure cultures are also discussed in this section.
Finally, a distinction in bacteria and microbial activity
and processes dependent on the location of the bacteria free floaters in the water stream or attached bacteria - are
addressed.
7-11
SRB can also be classified into one of two groups, depending on their action upon the organic substrate used
as an energy/carbon source. Bacteria in the first group
incompletely oxidize the substrate to acetate and no
further. Higher-organic-acid anions are the food source
for these bacteria; acetate is the metabolic product. These
bacteria grow relatively rapidly. Under optimum conditions, their doubling time is about 3 hours.
The second group of SRB completely oxidize organic
substrates to CO2. Because these bacteria can use acetate
as a substrate, they are frequently called acetate utilizers. They grow much more slowly than the incomplete
oxidizers; their doubling times usually exceed 15 hours.
Frequently, the completely oxidizing SRB coexist with the
7-12
7-13
Table 3
SRB Species
Incomplete Oxidizers
Desulfovibrio
desulfuricans
vulgaris
gigas
salesigens
sapovorans
thermophilus
africanus
baculatus
Desulfotomaculum
orientis
ruminis
nigrificans
antarticum
Desulfobulbus
propionicus
Complete Oxidizers
Desulfobacter
postgatei
Desulfovibrio
baarsii
Desulfotomaculum
acetoxidans
Desulfococucus
multivorans
niacini
Desulfosarcina
variabilis
Desulfobacterium
phenolicium
Desulfonema
limicola
Optimum
Temp., C
Hydrogen
Compounds Oxidized
Fatty
Acetate
Acids
Lactate
30
30
30
30
30
70
30
30
+
+
+
+
+
C4 C6
-
+
+
+
+
+
+
+
+
3035
37
55
30
+
+
+
+
+
+
+
3038
C3
30
(+)
3038
(+)
C3 C18
35
C4, C5
35
30
(+)
(+)
C3 C14
C3 C14
+
-
30
(+)
C3 C14
30
(+)
C4
30
(+)
C3 C12
7-14
Table 4
Sulfate Reduction
Lactate Substrate
2CH 3 CHOHCOO + SO 24 + 2H + = 2CH 3 COO + 2CO 2 + H 2 S + 2H 2 O
G = 39.9 kcal
Acetate Substrate
CH 3 COO + SO 24 + 3H + = 2CO 2 + H 2 S + 2H 2 O
G = 13.6 kcal
Hydrogen Substrate
4H 2 + SO 24 + 2H + = H 2 S + 4H 2 O
G = 36.3 kcal
Respiration
Acetate Substrate
CH 3 COO + 2O 2 + H + = 2CO 2 + 2H 2 O
G = 204. kcal
G = G at pH = 7. Thermodynamic values from Reference 2.
Acetate may be a
metabolic product of
bacterial activity or it may
be a substrate for
bacterial activity.
7-15
Slime-Forming Bacteria
Slime-forming bacteria
produce large amounts of
extracellular polymeric
substances that lead to
plugging and pitting
corrosion.
7-16
Iron Bacteria
These heavy slime formers can oxidize soluble iron
[Fe(II)] to insoluble iron [Fe(III)] using dissolved oxygen
as the oxidizing agent. The insoluble iron (1) contributes
to plugging and fouling; (2) provides anaerobic niches for
other bacteria, including SRB; and (3) enhances corrosion
from differential oxygen concentration cells. These
bacteria are aerobic but can grow with <0.5 ppm oxygen.
They are usually found in fresher waters and in open
systems. Types of iron bacteria commonly encountered
are Siderocapsa, Gallionella, Crenothrix, and Sphaerotilus
(also called filamentous bacteria). Iron bacteria are difficult to culture. Direct microscopic techniques are recommended for detection.
7-17
Sulfur-Oxidizing Bacteria
Sulfur oxidizing bacteria
oxidize hydrogen sulfide
either incompletely to
sulfur or completely to
sulfuric acid.
Categories of Bacteria
By Location
Planktonic floaters
Sessile attached
By Habitat
Monocultures single species
Consortia mixed cultures
Planktonic Bacteria
Planktonic bacteria are
free floating in the liquid
phase.
7-18
Sessile Bacteria
Sessile bacteria are attached to surfaces. They are responsible for most problems encountered in oilfield operations. These bacteria may attach to metallic surfaces
(piping, tanks, tubing, casing), nonmetallic surfaces
(plastic pipe), or minerals (filter media or formation
material).
7-19
DETECTION OF BACTERIA
The objective of this part of water quality monitoring is
to determine the following:
1. Are bacteria present?
2. What types of bacteria are present?
3. How many bacteria of each type are present?
4. Are the bacteria present as planktonic (floating)
bacteria or as sessile (attached) bacteria?
This type of monitoring is first used to determine
whether bacteria are present and could be contributing to
production problems. If they are present, monitoring
should help determine whether the control methods
being used effectively eliminate or reduce the bacteria.
Microbiological sampling
and analysis require
technique, equipment,
and experience that is
uniquely different from
chemical sampling and
analysis.
7-20
Table 6
Microbiological Analysis
7-21
Planktonic Bacteria
1. Withdraw a liquid sample from the flow stream with
a sterile syringe and place it in a sterile container.
2. Culture or examine this sample at the time of sampling or as soon as possible afterward by techniques
described in following sections. Maintain anaerobic
conditions when sampling for SRB.
7-22
Culturing Methods
A special preparation of carbon and energy sources,
nutrients, and salts in sterile water is inoculated with the
sample. Active bacteria or bacterial colonies, if present,
cause some measurable change (e.g., cloudiness, turbidity, or color change) in the culture medium as the bacteria
grow and multiply under proscribed environmental
conditions. By varying the type of media and protocol,
Culturing methods
bacteria are grown in a
specific nutrient broth.
Direct methods count
bacteria directly or
detect the presence or
the consumption of
some chemical
compound that is
uniquely associated
with the bacteria or
their metabolism.
7-23
Culturing Methods
Broth Bottles
Solid Culture Media
Pour Plate
Spread Plate
Agar Deep
Melt Agar Tube
7-24
Broth Bottles
Culturing with broth bottles (bug bottles) is probably the
most common method in oilfield situations. The culturing medium is made up and enclosed in a small bottle
sealed with a rubber septum. A sterile, disposable syringe is used to introduce the sample into the sealed
bottles. By using different broths, we can observe the
different types of bacteria.
For oilfield use, API RP 386 has been the standard for
media for SRB and general bacteria counts. This standard is now considered outdated and greatly deficient in
formulations and practices. RP 38 does not consider
sessile bacteria and uses a lactate-based medium for SRB
detection and enumeration. As discussed earlier, some
SRB that are complete oxidizers can utilize acetate but
not lactate. These SRB would not be detected by the
media specified in RP 38. Also, these media can give a
false positive reaction for SRB if Clostridia are present.
Clostridia can produce H2S from the yeast extract in the
media.
Many advances in media have been made since RP 38
was published. RP 38 is currently being revised; reissue
is on hold, pending possible publication of a NACE
standard or test method.
Broth bottles can be made up and prepared by the user or
are available from a number of suppliers. In either case,
experience has shown that using a sterilized portion of
the test water as the background solution and augmenting this with additional nutrients and chemicals specific
to the bacteria being studied provide the most suitable
media. Postgates4 monograph is the standard for techniques and media for SRB. Another useful reference is
Mittleman and Geeseys8 book. It contains a number of
media for bacteria of interest, as well as sampling and
culturing techniques for planktonic and sessile bacteria.
Some suppliers can provide assembled kits with various
7-25
Bottle Number
1
2
3
4
5
6
Dilution Factor
1/10
1/100
1/1000
1/104
1/105
1/106
Bacteria/mL
in Original Sample
Number
Log Number
110
1
10100
2
1001000
3
100010,000
4
10,000100,000
5
100,0001,000,000
6
7-26
Pour-Plate Method
The sample, or dilutions thereof, is mixed with molten
agar containing the desired media. The temperature of
the molten agar (45C) may inactivate some mesophilic
bacteria.
Spread-Plate Method
The sample is inoculated onto the surface of a solidified
media containing agar. Microbiologists use this method
in laboratories. It requires an anaerobic tent and an
incubator for SRB and other anaerobic bacteria. Because
of the low melting temperature of agar, the method is not
suitable for thermophilic bacteria. It also is usually not
suitable for field culturing.
A variation of the spread-plate method is the agar deep
method furnished by Bioscan Laboratories. This method
uses an RP 38-type agar media inoculated with a pipe
cleaner wetted with the sample. The sample may be
diluted before it is incorporated into the agar to simulate
the serial dilution method with broth bottles. The
Bioscan broth contains sulfite as a reducing agent (to give
a media with a low pH for anaerobic bacteria). Therefore, it may give false positive tests for SRB from sulfitereducing bacteria that would not be active in a sample
that does not contain sulfite.
7-27
Direct Methods
Direct methods count bacteria directly or detect the
presence or consumption of some chemical compound
that is uniquely associated with the bacteria or is involved in the microbiological metabolism.
Table 10 lists the methods discussed in this section.
Table 10
Direct Methods
ATP Assay
Epifluorescence/Cell Surface Antibody
APS Reductase Antibody
Phospholipid Signature
Radio-Respirometry
Chemical Analysis
ATP Assay
7-28
This method measures the amount of adenosine-5'triphosphate (ATP) obtained from bacterial cells. ATP, a
carrier of chemical energy in metabolism, is a component
of all living bacteria. Therefore, ATP assay does not
specify the type of bacteria present. ATP is extracted
from the bacterial cells and detected by reacting with an
enzyme (firefly luciferase) in the presence of oxygen and
measuring the amount of emitted light with a special
photometer. ATP is quickly lost from bacterial cells when
bacteria die, so the method detects only live bacteria.
Samples for analysis must be processed and preserved at
the sampling point to retain ATP. The method is relatively insensitive; i.e., ATP from a large number of cells
must be present to be detected. Samples with high solids
content or high levels of sulfides or biocides require
pretreatment to reduce interferences. The method also
requires specialized reagent, equipment, and standardization procedures performed by experienced personnel.
7-29
Phospholipid Signature
This procedure identifies the distinct signature of phospholipids unique to each strain of bacteria. It uses difficult procedures and expensive equipment in a controlled
laboratory environment. The method is good for qualitatively identifying bacterial types and strains but is not
calibrated for quantitatively measuring numbers of
bacteria. Its use is confined to research studies for identifying bacteria.
Radio-Respirometry
Radio-respirometry
measures bacterial
activity rather than
bacterial numbers.
7-30
method uses radioactive materials and specialized equipment (scintillation counter). It also requires specialized
procedures to obtain reproducible results.
Chemical Analysis
The presence and activity of bacteria can sometimes be
inferred by changes in water chemistry, i.e., the appearance of products of bacterial metabolism or the disappearance of compounds used by bacteria. Thus, the
presence and activity of SRB can be inferred by a decrease in sulfate levels, an increase in sulfide levels, and a
decrease in low-molecular-weight fatty acids, such as
acetate, propionate, or butyrate across the system.
Table 11 gives an example of this method from the Minas
field in Indonesia. The characteristics of the produced
water at the Central Gathering Stations where oil and
water are separated are compared with those at selected
injection wells remote from the stations. Although it is
impossible to assign the water from any one station to a
particular injection well, trends in chemical levels are
apparent. H2S levels are generally low at the stations but
increase as the water flows to the injection wells and
becomes cooler. The exception is Well 2D24, where the
water temperature remains high (82C). Sulfate levels
follow an inverse relationship, decreasing from stations
to wells.
Table 11
Central Gathering
Station
H2S, mg/L
SO2
4 , mg/L
pH
Temperature, C
Water Injection
Well
H2S, mg/L
SO2
4 , mg/L
pH
Temperature, C
GS-I
Trace
27.8
7.5
81
GS-II
0.3
26.4
7.6
85
GS-III
0.1
17.
7.5
82.5
GS-IV
<0.1
35.
7.2
79
GS-V
0.15
55.
7.3
81
GS-VI
0.4
26.
7.3
78
6F52
2.
14.
7.3
77
3E86
3.
19.8
7.4
78
2D24
nil
23.
7.4
82
10D15
5.
13.
7.3
78
6A59
3.4
24.4
7.6
72
7B89
7.7
16.4
7.6
78
7-31
Measurement of the
sulfur isotope ratio can
determine if hydrogen
sulfide was produced by a
microbiological or a
chemical reaction.
7-32
weight of 32) 95% and S34 4.2%. The lighter isotope, S 32,
is more reactive in microbiological reactions. Thus, in the
biogenic production of H2S by SRB, the H2S product is
enriched in S32 and the remaining unreacted sulfate is
enriched in S34. In practice, to increase precision, the
amount of each isotope is determined by a mass spectrometer and the results are presented as a S34 ratio, in
parts per thousand, , defined as
S 34 S 32 sample
S = 34 32
1 1000
S S standard
34
(1)
7-33
7-34
7-35
7-36
7-37
Ultraviolet (UV) radiation is nonselective and kills bacterial cells by preventing cell division. The UV light must
touch the bacteria to kill them; it does not impart
bacteriocidal properties to the irradiated water. The
effectiveness, or percent kill, depends on the exposure
time and the intensity of the UV light that the bacteria
see. In high-flow-rate systems, then, high-intensity UV
light is needed.
Anything that prevents exposure of bacteria to the UV
light or decreases the intensity of the light decreases
treatment effectiveness. This includes suspended solids,
dispersed oil, soluble materials that absorb the UV radiation, biofilms, and opaque films on the UV lamp sources.
UV radiation is particularly suitable for treating planktonic bacteria in clean water at the point of irradiation. It
has no residual effect and is not effective for bacteria
downstream of the source. UV radiation is readily absorbed by biofilms and thus is not effective for sessile
bacteria.
Types of Biocides
A variety of organic and inorganic chemicals and chemical combinations have been used or proposed as biocides.
Table 12 lists some classes of chemicals and the specific
chemicals that used as biocides. The most widely used
are the oxidizing biocides typified by chlorine, hypochlo7-38
Table 12
(2)
Types of Biocides
Oxidizing
Chlorine, hypochlorite, chlorine dioxide, bromine,
hydrogen peroxide, ozone
Inorganic
Copper, mercury, silver, and arsenic compounds,
chromates
Aldehydes
Formaldehyde, glutaraldehyde, acrolein
Organics
Amines, chlorinated phenols, quarternary
ammonium compounds, carbamates, guanides,
isothiazolins, phosphonium salts
7-39
7-40
concentration (hundreds of ppm) to be effective. Glutaraldehyde is frequently blended with quaternary ammonium compounds to increase biocide effectiveness. All
aldehydes are reactive with and consumed by sulfides.
Systems with high sulfide concentrations would have
high chemical consumption.
A wide variety of organics and combinations of organics
are used as biocides. Most organic biocides contain
nitrogen, sulfur, phosphorous, or halogens atoms within
their structures. Common organic biocides include
quaternary ammonium compounds, amines, chlorinated
phenols, and isothiazolin. Biguanides, nitrogen-containing compounds, are effective at low to medium temperatures (<170F). They are widely used in West Africa and
Papua New Guinea.
A relatively new biocide based on a phosphonium sulfate
formulation and produced by Albright & Wilson, Ltd.15
has been used against sulfate reducers in the North Sea.
The chemical supplier is registering the compound with
the U. S. Environmental Protection Agency for use as a
biocide in the United States.
Phosphonium sulfate
biocides are available for
use in Australia.
Biocide Selection
We should consider four guiding principles when selecting and using biocides to control microbiological activity.
1. The biocide must reach and come in contact with the
bacteria in a high enough concentration and long
enough to achieve an effective kill.
2. Apart from the protective aspects of the biofilm,
sessile bacteria may be inherently less susceptible to
biocides than the corresponding planktonic bacteria.
3. Biocide effectiveness varies from one bacterial type to
another.
4. Any chemical used as a biocide must be compatible
with all other chemicals present in the system or
added as a treatment chemical.
7-41
The selectiveness of
biocides can lead to a
survival of the fittest
mode of bacterial growth
in a water treating system.
7-42
Biocides must be
compatible with all other
treating chemicals.
7-43
(3)
where control number and sample number are the number of viable bacteria in the unexposed control and the
exposed sample, respectively. The results can also be
expressed as the log reduction of bacteria defined as
(Control Number)
Log Reduction = log10
(Sample Number)
(4)
(5)
7-44
Table 13
Percent Kill
90
99
99.9
99.99
99.999
99.9999
Log Reduction
1
2
3
4
5
6
Bottle Reduction
1
2
3
4
5
6
Biocide effectiveness is
frequently measured in
terms of percent kill.
7-45
where the log reduction, defined in Eq. 4, is experimentally measured during a series of time-kill tests, and the
doubling time is the time required for the specific bacterial species to grow by a factor of two. Table 14 shows
the minimum time needed for bacteria to recover from
various degrees of kill imposed by application of biocides
when the sessile bacteria have doubling times of 30
minutes and 2 hours, respectively. Using the minimum
recovery time as an estimate of slug frequency, we can
estimate the relative cost-effectiveness of time-concentration combinations of various biocides. Note that this
comparison is only an estimate; any conclusions drawn
from it should be verified by a field test of the biocides.
Table 14
Biocide Effectiveness
Percent Kill
90.
99.
99.9
99.99
99.999
99.9999
7-46
(6)
Log
Reduction
1
2
3
4
5
6
2 hours
6.6
13.3
19.9
26.6
33.2
39.9
7-47
Table 15
Biocide
Biocides Tested
Composition
ADBAC
Table 16
Biocide Effectiveness
Planktonic SRB
Log Reduction
Sessile SRB
Log Reduction
Biocide, ppm
Product
3 h.
7 h.
1 h.
4 h.
ADBAC, 40
12
2
1
1
DBNPA, 50
0
0
1
1
Glutaraldehyde, 100
2
3
2
4
Glutaraldehyde/
34
5
4
5
quat, 80
Isothiazolone, 200
0
0
0
1
Note: Desulfovibrio desulfuricans, Mid Continent Strain A,
pH 68, 25C
From Reference 13
Table 17
7-49
Table 18
7-50
Figure 1
7-51
7-52
Types of biocide
applications:
continuous
batch
Biocide Toxicity
By their very nature, biocides must be toxic to bacteria
and other microorganisms. However, their toxicity to
higher life forms is of prime importance in protecting the
environment. This is true whenever water is discharged.
It is also important whenever there is a spill, a leak, or
accidental contact with biocide-treated water.
Before discussing the toxicity of specific biocides, we
should define a few important terms. Toxicity is the
potential or capacity of a test material to cause detrimental effects on living organisms. Toxicity may be acute as
the result of a relatively short-term exposure (2 to 4 days
7-53
for most toxicity testing) or may be chronic if the exposure is for relatively long times (times of up to 10% or
more of the lifetime of the test species).
An aquatic toxicity test (also called a bioassay) is used to
assess the potential for damaging toxic effects of a test
material on specific aquatic organisms:
Various instrumental
procedures have been
proposed as substitutes
for the time-consuming
bioassay procedure.
7-54
No-observed-effect concentration (NOEC; highest toxicant concentration where the measured response of
the test system shows no statistically significant
difference from the control system.
7-55
7-56
REFERENCES
1. Jrgensen, B. B.: A Comparison of the Methods for
the Quantification of Bacterial Sulfate Reduction in
Coastal Sediments. III. Estimation from Chemical and
Bacteriological Field Data, Geomicrobiol. J. (1978) 1,
11.
2. Brock, T. D. and Madigan, M. T.: Biology of Microorganisms, fifth edition, Prentice Hall, Englewood Cliffs,
NJ (1988).
3. Cord-Ruwish, R., Kleintz, W., and Widdel, F.: Sulfate-Reducing Bacteria and Their Activities in Oil
Production, JPT (1987) 39, 97.
4. Postgate, J. R.: The Sulfate-Reducing Bacteria, second
edition, Cambridge University Press, Cambridge
(1984).
5. NACE TPC Publication 3, Microbiologically Influenced
Corrosion and Biofouling in Oilfield Equipment, Natl.
Assn. of Corrosion Engineers, Houston (1990).
6. RP 38, Recommended Practice for Biological Analysis of
Subsurface Injection Water, American Petroleum Institute, Philadelphia (March 1982).
7. NACE Item #54278, Review of Non-Conventional and
Supplementary Methods for the Detection of SulphateReducing Bacteria in Oilfield Waters, Natl. Assn. of
Corrosion Engineers, Houston (1989).
8. Mittleman, M. W. and Geesey, G. G.: Biological Fouling
of Industrial Water Systems: A Problem Solving Approach,
Water Micro Associates, San Diego, CA (1987).
9. Horacek, G. L.: Field Experience with an SRB Rapid
Detection Test Kit, SPEDE (Dec. 1992) 275.
10. Orr, W. L.: Geological and Geochemical Controls on
the Distribution of Hydrogen Sulfide in Natural Gas,
Advances in Organic Geochemistry 1975, Proc., Intl.
Meeting on Organic Geochemistry Madrid (Sept. 1619, 1975).
11. Scott, P. J. B. and Davies, M.: Survey of Field Kits for
Sulfate-Reducing Bacteria, Materials Performance
(1992) 31, 64.
7-57
7-58
GLOSSARY
Abiotic not produced by bacteria or living organisms.
Acetate utilizers SRB capable of completely oxidizing
acetate to CO2 and H2O.
Acid producing bacteria (APB) type of bacteria capable of breaking down complex organic compounds
to simpler, low-molecular-weight fatty acids, such as
formic, acetic, propionic, and butyric.
Acridine orange a fluorescent compound used in the
epifluorescent method for total cell counts.
Acute toxicity toxicity occurring during relatively
short-term (2- to 4-day) exposures.
Adenosine-5'-phosphosulfate (APS) reductase enzyme
an enzyme specific to SRB used for detection and
enumeration in the Conoco RapidChek kits.
Adenosine-5'-triphosphate (ATP) a nucleotide that
acts as a carrier of chemical energy in microbiological
reactions.
Aerobe an organism that grow in the presence of
oxygen.
Aerobic in the presence of oxygen.
Anaerobe an organism that grow in the absence of
oxygen.
Anaerobic in the absence of oxygen.
AO see acridine orange.
APB see acid-producing bacteria.
API American Petroleum Institute.
APS see adenosine-5'-phosphosulfate (APS) reductase
enzyme.
Assimilation anabolism, the incorporation or conversion of nutrients into cell material.
ATP see adenosine-5'-triphosphate.
Autotroph organism able to use CO2 as the sole carbon
source.
7-59
7-60
7-61
7-63
7-64
C H A P T E R
8
Chemical Injection
8-1
8-2
INTRODUCTION
In most oil fields, the water that must be processed in the
water treatment system contains a variety of chemicals
that have been injected into or added to the water:
1. Chemicals added to the water in the treatment system
itself as part of the treatment processes (improving
oil/water separation or filter backwash) or to maintain the system (scale, corrosion, and bacteria inhibitors).
2. Chemicals used in general oilfield operations that end
up in the produced water (scale, corrosion, and bacteria inhibitors).
3. Chemicals associated with other field operations that
generate wastewater streams that we often dispose of
by adding them to the feed to the water treatment
system (spent acid, workover fluids, cleaning solutions, tank bottoms, etc.).
Besides injected chemicals, oilfield waters contain natural
components, some dissolved and some suspended. The
result of this mixture of natural components and injected
chemicals is a dynamic water system with constantly
changing chemistry. When changes in water chemistry
are excessive and/or abrupt, as might occur when a
chemical slug is injected into the water, the system goes
into an upset, the mechanical components of the water
treatment system (filters, oil/water separators, etc.) no
longer function properly, and the quality of the water
coming from the system deteriorates. Because of the
complexities of the water chemistry and the effects of
interactions of chemicals, injected or present in the water,
correcting such upsets may require days.
This chapter discusses the types and functions of chemicals, naturally present or injected, that end up in the
treatment water and their potential interactions. We
suggest ways to minimize the interactions and procedures for avoiding system upsets caused by upsets in
water chemistry.
8-3
Catio ns
H yd rogen
Sod ium
Po tassium
C alcium
M agnesium
B ariu m
Strontiu m
Iron
H+
N a+
K+
C a ++
M g ++
B a ++
Sr ++
Fe ++
A nio ns
C hloride
C lC O =3
C arbonate
B icarbonate
H yd roxid e
H C O 3
OHSO =4
Sulfate
From o rg anic acids su ch as:
A cetate
C H 3C O O Prop ionate
C H 3C H 2C O O N eu tral Com po n ents
Silica
SiO 2
B acteria
O il
Susp end ed solid s such as:
Fo rm ation fines
Paraffins
A sphaltenes
Scale prod ucts
C orro sion prod ucts
D issolv ed G ases
O xy gen
C arbon Dio xid e
H yd rogen sulfid e
8-4
O2
CO2
H 2S
8-5
Scale Inhibitors
Three classes of water-soluble compounds are used to
inhibit the formation of scale:
1. Organic phosphonates.
2. Phosphate esters.
3. Polymers (polyacrylates, polyacrylamides, and
phosphino-substituted polycarboxylic acid).
These chemicals are added to the produced water by a
well squeeze or direct addition. Because of their water
solubility, the portion that is not lost by adsorption onto
scale and other solids will show up in a produced-water
treatment system.
Corrosion Inhibitors
The compounds used as corrosion inhibitors in oil production operations can be classified as:
8-6
1. Amides/imidazolines.
2. Salts of nitrogenous molecules with carboxylic acids.
3. Quaternary nitrogen compounds.
4. Polyoxyalkylated amines, amides, and imidazolines.
5. Nitrogen heterocyclic compounds.
6. Special inhibitors containing phosphorous, sulfur,
and/or oxygen.
The first two classes are the most common; the last is the
least common. The oil/water relative solubilities and
dispersibilities of these inhibitors depend on the group
lengths and types on the molecules, the organic acid used
in the compound formation, and the solvents and surfactants used in the formulation. The oil-soluble (waterdispersible) corrosion inhibitors find greatest application
in oil-producing operations. Thus, only a small part of
these compounds will end up in the produced water.
Biocides
Two general classes of biocides are used in the oil field:
1. Strong oxidizers, including chlorine, sodium hypochlorite, and chlorine dioxide.
2. Organic-based biocides, including quaternary ammonium salts, aldehydes (formaldehyde, acrolein, and
glutaraldehyde), quaternary phosphonium salts,
thiocarbamate, and isothizaoline.
These biocides are highly water-soluble but very reactive.
The strongly oxidizing chlorine compounds are also very
corrosive and are consumed through a variety of reactions with organic materials, metals, sulfides, etc. The
other biocides, although not as strong oxidizing agents,
are reduced by reactions with organic and inorganic
substances in produced-water systems. In some cases,
these substances are chemicals added to the treated water
for other purposes (e.g., oxygen scavengers).
Emulsion Breakers
These chemicals are added to improve oil/water separation:
8-7
Reverse Breakers
These chemicals are added to help remove oil droplets
from water. The most common compound classes are:
1. Low-molecular-weight polyamines.
2. Polyamine quaternary ammonium compounds.
These water-soluble compounds are often formulated
with aluminum, iron, or zinc chlorides. About half the
added chemical ends up in the treated water.
8-8
Antifoamers
These chemicals are used to control foam formation in
oil/water separators, de-aerators, and similar units. The
most common are:
1. Silicones.
2. Polyglycol esters.
Their low water solubility causes them to end up mostly
in the oil phase.
Surfactants
Nearly all oilfield chemicals are formulated with surfactants to increase solubility or dispersibility in the carrier
solvent or in water. However, surfactants are generally
are not used alone except for cleaning tanks, vessels, and
decks (particularly offshore). Three common watersoluble surfactants used for these purposes are:
1. Alkyl aryl sulfonates.
2. Ethoxylated alkylphenols.
3. Ethoxylated alcohols.
Paraffin Treating
Chemicals used to inhibit or remove paraffin deposits are
very water-insoluble. The following inhibitors are used
to prevent the forming and accumulation of paraffin
deposits:
1. Vinyl polymers.
2. Sulfonate salts.
3. Alkyl polyether and aryl polyether mixtures.
8-9
Oxygen Scavengers
To control corrosion, dissolved oxygen is generally removed from oilfield waters, including seawater and
other injection waters, by a combination of mechanical
and chemical addition methods. The chemicals usually
are compounds of sulfur:
1. Ammonium sulfite or bisulfite.
2. Sodium sulfite or bisulfite.
3. Sulfur dioxide.
The sulfur part of these water-soluble compounds is
oxidized to sulfate ion by reaction with dissolved oxygen.
Sulfide Scavengers
In some situations, chemicals are used to remove H2S
from produced water. The most common chemicals for
this purpose are:
1. Aldehydes.
A. Formaldehyde.
B. Glutaraldehyde.
2. Strong oxidizers.
A. Chlorine dioxide, gaseous and stabilized liquid.
B. Hydrogen peroxide.
These aldehydes and oxidizers also are biocides. In some
sour water systems where bacteria are a problem, some
of the chemical added to the water is intended to be
consumed in reactions with H2S and some functions as a
biocide. In other situations, the chemical is injected only
to scavenge H2S.
8-10
Hydrate Inhibitors
When hydrates are a problem in gas production, chemicals are sometimes added to the associated water to
inhibit hydrate formation. These water-soluble chemicals
can end up in the produced water.
1. Methanol.
2. Ethylene glycol.
Acids
1. Hydrochloric acid.
2. Hydrofluoric acid.
3. Formic acid.
4. Acetic acid.
5. Fluoroboric acid.
6. Citric acid.
8-11
Fracturing Fluids
1. Polymers (natural and synthetic).
A. Hydroxy alkyl celluloses.
B. Guar gums.
2. Alcohols.
3. Kerosene.
4. Emulsifiers (cationic surfactants).
5. Bridging agents.
A. Oil-soluble resins.
Additives
1. Corrosion inhibitors.
A. Substituted acetylenic alcohols.
B. Alkyl pyridine quaternaries.
2. Antisludging agents.
A. Alkyl benzene sulfonate.
3. Anti-paraffin-deposition agents.
A. Vinyl acetate resins.
4. Demulsifiers (see emulsion breakers).
5. Scale inhibitors (see scale inhibitors).
6. Solvents (refinery aromatic and aliphatic cuts).
7. Dispersing agents.
A. Alkylphenol ethoxylates.
8. Flushes.
A. Clay dispersion and swelling-control agents.
(1) Ammonium chloride.
(2) Potassium chloride.
(3) Poly quaternary ammonium compounds.
(4) Hydroxy aluminum.
B. Mutual solvents.
(1) Oxyalkylated alcohols.
8-12
Workover Fluids
Like the stimulation chemicals, these chemicals or their
reaction products find their way into the produced water
and the water treating system as they flow back from the
well with the produced fluids. They also appear if the
well is backflowed following the workover and the fluids
are collected, dumped into a pit or tank, and then added
to the feedwater to the water treating system. They also
cause severe upsets to the system.
Weighted Brines
1. Sodium chloride.
2. Calcium chloride.
A. Ammonium chloride.
B. Potassium chloride.
C. Calcium bromide.
D. Zinc bromide.
8-13
B. Guar gums.
C. Polysaccharides.
CHEMICAL INTERACTIONS
As noted, the ways in which chemicals are used in oil
fields vary greatly. Some are injected continuously.
Others are injected periodically in slugs. Consequently,
chemical interactions may be short term (during and for
a short period following the slug). Or the chemical
interactions may be long term or continuous (during the
continuous injection of one or more interacting chemicals).
8-14
8-15
Table 2
Phase
Ionic Character
Scale Inhibitors
Phosphonate
Phosphate Ester
Polymer
Water
Water
Water
Anionic
Nonionic
Anionic or Nonionic
Corrosion Inhibitors
Amine
Quaternary Amine
Amide
Amidoamide
Oil
Water
Oil
Oil
Cationic
Cationic
Nonionic or Cationic
Nonionic or Cationic
Biocides
Quaternary Amine
Phosphonium Salt
Aldehyde
Chlorine
Thiocarbamate
Isothiazoline
Water
Water
Water
Water
Water
Water
Cationic
Cationic
Nonionic
Nonionic
Anionic
Cationic
Oil
Oil
Oil
Oil
Nonionic
Nonionic
Anionic
Nonionic
Reverse Breakers
Polyamine
Polyamine Quat. Amm.
Water
Water
Cationic
Cationic
Water
Water
Water
Water
Oil
Oil
Nonionic
Nonionic
Emulsion Breakers
Phenol Formaldehyde Resin
Glycol Esters
Alkyl Arylsulfonate
Oxyalkylated Glycols
Antifoamers
Esters
Silicones
8-16
Table 2 (continued)
Chemical
Phase
Ionic Character
Anionic
Nonionic
Nonionic
Paraffin Treating
Vinyl Polymers
Sulfonate Salts
Polyethers
Oil
Oil
Oil
Nonionic
Anionic
Nonionic
Oxygen Scavengers
Sulfite Salts
Sulfur Dioxide
Water
Water
Sulfide Scavengers
Aldehydes
Water
Nonionic
Hydrate Inhibitors
Methanol
Ethylene Glycol
Water
Water
Nonionic
Nonionic
Gas Dehydration
Glycols
Water
Nonionic
Water
Water and Oil
Water
Water and Oil
Water
Oil
Water
Nonionic
Cationic and Anionic
Nonionics
Nonionic and Anionic
Nonionics
Surfactants (cleaners)
Alkyl Aryl Sulfonates
Ethoxylated Alkylphenols
Ethoxylated Alcohols
Well Stimulation
Acids
Frac Fluids
Additives
Corrosion Inhibitors
Acetylenic Alcohols
Surfactants
Mutual Solvents
Diverters
Viscosifiers
8-17
Surfactant Interactions
The most common interactions between injected oilfield
chemicals involve surfactants (surface active agents).
Many injected chemicals are classified as anionic, cationic, or nonionic surfactants. We will briefly describe
the chemistry of surfactants here because of their importance to oilfield chemistry.
With few exceptions, surfactants are molecules made up
of a hydrophilic (water-soluble) segment and an
oleophilic (oil-soluble) segment. The hydrophilic segment of an anionic surfactant is negatively charged in
water. Examples are carboxylates, sulfonates, sulfates,
phosphates, and phosphonates. Cationic surfactants are
positively charged at the hydrophilic segment of the
molecule. This positive charge is associated with a quaternary nitrogen (i.e., a nitrogen atom covalently bound
to four substituents). Examples are quaternary ammonium salts. As the name indicates, nonionic surfactants
do not have a charged segment. The hydrophilic segment is a polymer of ethylene oxide.
8-18
8-19
8-20
Reverse Demulsifiers
Underdosing reverse demulsifiers usually results in
inefficient operation of separation equipment. In flotation and plate-pack separation, the oil droplets need to be
as large as possible to maximize separation efficiency. If
the reverse demulsifier is underdosed, optimum droplet
coagulation/coalescence will not occur; thus, separation
efficiency is reduced. In a flotation system, the reverse
demulsifier also acts as a foaming agent, which is needed
to minimize the skimmed liquid volume. If the chemical
is underdosed, foaming may not occur and a large volume of oily water has to be skimmed to maintain oil
8-21
removal efficiency. This generates a waste-stream volume significantly greater than the oily foam skimmed
from an optimized vessel.
Overtreating with a reverse demulsifier can cause a
number of problems. Of primary concern is the formation of a separated oil stream that is essentially a stabilized emulsion. This stabilized emulsion can be the
skimmings from a flotation cell, the separated oil from a
plate-pack separator, or the reject stream from a liquid/
liquid hydrocyclone (see Chapter 3). Overdosing with
the reverse chemical can make this waste stream virtually
untreatable (see Chapter 10). Inevitably, this waste
stream is not dry oil but an oil/water mixture.
The ratio of water to oil can be 1:1 up to 10:1; hence,
further separation of the phases (additional equipment,
chemicals, and costs) is required to recover the oil and
dispose of the water. If this mixture is stabilized by
excess chemical, it will have to be treated as a separate
stream. Recycling this waste stream into upstream separation equipment will cause problems. The mixture will
build up an interface emulsion pad that will eventually
cause primary dehydration problems.
Another problem with overdosing reverse demulsifiers
relates specifically to induced-gas flotation (IGF) systems.
In IGF systems, the gas is induced by a rotor and diffused
into the water by a diffuser basket. The diffuser basket
ensures uniform distribution of gas bubbles into the
flotation cell. The holes in the basket are susceptible to
fouling with corrosion products and scale and must be
cleaned.
Excess reverse demulsifier will increase the fouling
process by acting as a glue for solids particles and
stabilized emulsions in the water, which then adhere to
the basket and plug the diffuser holes. This buildup not
only impedes flotation performance but also reduces
efficiency of oil droplet coagulation because the chemical
is expended flocculating solids, not oil droplets. In this
operating mode, determining an optimum chemical dose
is very difficult. At this point, the flotation cell should be
cleaned out and returned to service, and the chemical
should be optimized.
8-22
8-23
Biocide Reactions
By their very nature, biocides are very reactive. They are
often used in relatively high concentrations (in the case of
aldehydes) and are very water-soluble.
The strong oxidizers include chlorine and hypochlorite
compounds (both of which function as oxidizing biocides
in water as the hypochlorite ion) and chlorine dioxide.
These compounds are excellent biocides, but their associated corrosive properties limit their use and concentration. As strong oxidizers, they will react with organic
material in the water and reducing agents, such as sulfitebased oxygen scavengers. Oxygen scavengers will be
consumed preferentially by residual chlorine or hypochlorite ions in the water before being available for
reaction with dissolved oxygen.
The aldehyde and amine-type biocides operate by a
different biocide mechanism than strong oxidizers do.
They attack and poison the bacterial cell walls. The
amines also have surface active properties to loosen the
bacteria colonies and byproducts from surfaces. Sulfitebased oxygen scavengers react with aldehydes, which are
reducing agents. The aldehydes also react with H 2S in
sour water systems. We should consider these interactions when determining where these two types of chemicals will be injected in a water handling or treatment
system.
Another potential interaction involving aldehydes could
occur when acids are dumped into the treatment plant
feedwater. In the presence of strong acids, like hydrochloric, aldehydes condense with a variety of compounds
containing the -NH2 group (the functional group of many
corrosion inhibitors).
8-24
precipitate as the pH rises again; and increase the suspended solids in the water by loosening deposits from
the equipment surfaces.
8-25
8-26
GLOSSARY
Anionic chemical a chemical having a negative
charge.
Antifoamer a chemical used to control foam formation
in oil/water separators, de-aerator and similar units.
Cationic chemical a chemical having a positive
charge.
Coagulant and flocculant a chemical used in gas
flotation unit and media filter to separate oil and
suspended solids from produced water.
Demulsifier (emulsion breaker) a chemical used to
improve oil/water separation or help remove water
droplets from oil.
Gas dehydration chemical a chemical used to remove
water from the natural gas.
Hydrate inhibitor a chemical added to the associated
water to inhibit hydrate formation in gas production.
Nonionic chemical a neutral chemical having no
charge.
Oxygen scavenger a chemical used to remove oxygen
of the production system.
Reverse Demulsifier (Reverse breaker) a chemical
used to help remove oil droplets from water.
Stimulation acid an acid used in well stimulation.
Sulfide scavenger a chemical used to remove hydrogen sulfide of the production system.
Surfactant a surface active agent.
Viscosifier a chemical used to control viscosity.
8-27
8-28
C H A P T E R
9
Water/Formation
Rock Interactions
9-1
9-2
INTRODUCTION
Many formation rocks, particularly sandstones, are
subject to formation damage when they come in contact
with waters having chemical properties significantly
different from the natural connate water of the formation.
Formation damage is usually indicated by a permeability
reduction in the rock owing to chemical and physical
changes of the rock minerals. These changes cause clay
and other particles to swell and/or migrate, some minerals in the rock to dissolve, or plugging solids to precipitate. As a result, the small flow channels within the rock
porosity are blocked off. Formation damage may cause
only a small drop in or up to a total loss of permeability.
Oilfield operations (drilling and completion, workovers,
stimulation jobs, waterflooding, water disposal) can
damage the formation around the wellbore. Any operation in which the formation rock comes in contact with a
foreign fluid can damage some formations. While this
chapter focuses on the effects of water injection, the
causes of formation damage and the methods of preventing water/formation rock interactions generally apply to
other oilfield operations.
9-3
9-4
Mica Alteration
Micaceous minerals, such as micas and illites, are normally not considered expandable, but they can undergo
alterations that cause their structures to expand.4 Micaceous minerals are layered, much like smectites, except
the layer charge is substantially higher and the seat of the
charge is closer to the surface. Thus, the mineral is much
more difficult to expand, and the interlayer cations are
nearly nonexchangeable. Interlayer cation sites are filled
almost exclusively with potassium ions. Interlayer sites
are very specific to potassium because potassium ions
have a low hydration energy and fit nicely in the hexagonal holes between the layers. This allows the structure to
remain collapsed with a 10-Angstrom basal spacing.
Injecting non-potassium
brines into a mica-rich
reservoir can result in
formation damage.
9-5
Differential Dissolution
Differential dissolution is
a damage mechanism in
which less soluble
migrating fines are
released by the
dissolution of more
soluble rock components.
9-6
9-7
Precipitation
In some circumstances, a dissolved constituent in an
injection water can precipitate from the water by reacting
with minerals in the injected formation rock. An example
is the precipitation of dissolved iron ions by reaction with
alkaline minerals, such as calcite and dolomite. The
problem is worsened by the presence of dissolved oxygen in the water. The precipitated iron compounds
(mostly iron hydroxide) may plug the pore space and
damage permeability.
The permeability of susceptible reservoirs can be damaged many ways during water injection. The key to
maximizing injection efficiency is to prevent damage,
instead of using remedial treatments after the fact. When
planning of each stage of a water injection project, we
should consider the risks of formation permeability
damage.
Designing preventive methods for a particular formation
is best done with the knowledge and understanding of
the operating damage mechanisms. However, this information is frequently unavailable and usually requires
extensive laboratory investigation. In addition to identifying the clay types and other minerals in a formation,
9-8
9-9
To determine the minimum salt concentration and composition, we must make some laboratory measurements
on representative field cores. Technical Memorandum
TM88000115, Procedure for Determining Effects of Salt
Water Concentration on Permeability of Sands, is included in the Appendix. This memorandum outlines the
recommended procedure for conducting these measurements. The laboratory measurements are carried out by
flowing different concentrations of a particular salt solution through each of several representative core plugs
and measuring the stable single-phase permeability to
each solution.
We start by flowing the most concentrated salt solution to
a stable permeability. Then we successively flow solutions that are about half the concentration of the previous
solution. In each case, we record the stable permeability
for each solution. Fig. 1 shows plots of typical stable
permeability data for two very different sands.
At the higher salt concentrations, the curves are flat; at
some lower concentrations, however, each curve forms a
shoulder with the permeability declining more steeply as
the salt concentration approaches zero. Using curves for
several representative core plugs, we can select the minimum concentration of salt necessary to prevent damage
in that particular rock. As usual, the smectitic sand
required a much higher concentration of salt to prevent
permeability damage than the kaolinitic/illitic sandstone
did.
Fig. 2 shows similar data obtained on plugs from the
same sands using potassium chloride rather than sodium
chloride solutions. A comparison of the results in Figs. 1
and 2 for potassium and sodium salts shows that lower
concentrations of potassium salts are required to prevent
permeability damage effectively.
9-10
9-11
9-12
Similar laboratory tests are recommended with representative core samples to identify possible water/formation
rock interactions using actual field waters being considered in an injection project.
Three options to
minimize potential
damage include selecting
the least damaging brine,
modify injected water
chemistry, or treat the
near wellbore formation.
9-13
9-14
REFERENCES
1. van Olphen, H.: An Introduction to Clay Colloid Chemistry, Interscience Publishers, New York City (1963).
2. Kia, S. F., et al.: Effect of Salt Composition on Clay
Release in Berea Sandstone, SPEPE (Nov. 1987) 27783.
3. Muecke, T. W.: Formation Fines and Factors Controlling Their Movement in Porous Media, JPT (Feb.
1979) 144-50.
4. Reed, M. G.: Formation Permeability Damage by
Mica Alteration and Carbonate Dissolution, JPT
(Sept. 1977) 1056-60.
5. Reed, M. G.: Gravel Pack and Formation Sandstone
Dissolution During Steam Injection, JPT (June 1980)
941-49.
6. Scheuerman, R. F. and Bergersen, B. M.: InjectionWater Salinity, Formation Pretreatment, and WellOperations Fluid-Selection Guide, JPT (July 1990)
836-45.
7. Hesterberg, D. and Reed, M. G.: Volumetric Treatment Efficiencies of Some Commercial Clay Stabilizers, paper SPE 18466 presented at the 1989 SPE
International Symposium on Oilfield Chemistry,
Houston, Feb. 8-10.
9-15
9-16
GLOSSARY
clay stabilizers chemicals that prevent clays in the
reservoir from migrating and thereby reducing permeability.
clays, expanding types clays that have an ability to
swell and increase in volume. This tendency is promoted by contacting them with fresh water.
deflocculation the process by which clays dislodge
themselves from the pore walls and become mobilized.
differential dissolution process in which less soluble
migrating fines are released by the dissolution of
more soluble rock components.
formation damage decrease in reservoir permeability.
hydroxyaluminum chemical that is one class of clay
stabilizers.
mica alteration injecting potassium-free water can
lead to the substitution of potassium in mica minerals
with sodium. This process can destabilize the mica
and cause formation damage from released particles.
migration the movement of fines and clays. A common formation damage mechanism.
organic polyquarternary amine one class of clay
stabilizer chemical.
9-17
9-18
APPENDIX
9-19
9-20
C H A P T E R
10
Handling Separated Wastes
10-1
10-2
INTRODUCTION
During treatment of oilfield waters whether for waterflooding, EOR, steam generation, or just separation of oil
and gas from produced water waste streams are generated when unwanted constituents are separated from the
water. These waste streams are generally made up of
multiple phases of water, suspended solids, and oil (and
sometimes gas) in varying proportions. The water and
oil phases contain various dissolved inorganic and/or
organic species. These waste streams, in turn, may require further processing before disposal. Environmental
regulations and economics are major factors in controlling the method of handling, processing, and disposing
of the separated wastes.
This chapter discusses the origin and methods of handling separated wastes from the treatment of oilfield
waters. Note that many of the procedures and much of
the technology presented are not routine oilfield practice.
The procedures are presented as recommendations where
routine practices might be improved, particularly where
they affect oilfield water treatment and disposal of the
resulting waste streams. In addition, this chapter reviews
the environmental aspects of handling the separated
wastes, including the criteria for land and injection well
disposal.
Fig. 1 shows the overall, but simplified, process of generating waste streams in a water treating system. The
water to be treated, water in, is shown as being made
up of water, oil, solids, and/or gas. The water out is
shown as containing oil and solids, presumably of acceptable concentrations (quality) for the water to be disposed
10-3
10-4
Table 1
Waste Streams
Separated
Solids
Tank Bottoms
Filter
Backwash
Pit Bottoms
Sand Pan
Solids
Hydrocyclone
Separated
Solids
Separated Oil
Produced
Crude
Pit Sludges
Separated
Gases
Produced Gas
H2S and CO2
Separated
Water
Water Softener
Spent Brine
Water from
Batch Treating
Tanks
Oil/Water
Separation
Skimmings
Hydrocyclone
Separated Oil
Tank
Skimmings
10-5
10-6
The system
accumulation waste
stream should be
minimized, otherwise
water quality will suffer.
It is generally better to
minimize stream recycles
and treat each waste
stream separately.
10-7
10-8
10-9
10-10
These two principles complement each other. The opposite of point-source treating is combining all waste
streams into one large volume and then attempting to
treat the combined wastes together.
Treating a waste stream as close to its source as possible
allows the treatment to be designed specifically for that
stream for maximum treatment efficiency. Effects of
changes in flow rate and water chemistry and interactions with chemical additives in other waste streams are
minimized. Likewise, changes can be monitored and
responded to more effectively.
Keeping the treatment volume as small as possible keeps
the process equipment small. Not all wastes require the
same treatment. One waste stream may require only
chemical treatment with increased residence time in a
tank; another may require filtration or ion exchange.
Mixing the streams could require that the combined
volume be chemically treated and filtered.
In addition, if a single waste stream can be classified as
hazardous, the total combined stream must be classified
as hazardous. Keeping the waste streams small facilitates
monitoring and permits the use of special equipment that
works better on a small scale. For example, plate-inframe and cartridge filters are more practical on a small
scale.
10-11
solids and filter elements are disposed of together. Drycake filters yield a disposable solid product that, although not totally dry, contains much less water and
hydrocarbons than the backwash from ordinary filters.
The solids in the disposable product are a mixture of the
separated solids and a filter aid, such as diatomaceous
earth or perlite. The water from the filters (the filtrate)
may be recycled back to the water treating system, usually downstream of other filters and oil/water separation
equipment, if no chemical incompatibilities or other
interactions are caused. If chemical incompatibilities or
interactions could occur, the filtrate must be chemically
treated before being recycled, or it must be disposed of
separately (injection well, etc.).
Continuous or batch treatment of emulsions separates oil,
water, and solids by chemicals, heat, and residence time.
The recovered oil can be added to the crude oil from the
field if its quality is high enough not to affect the basic
sediment and water (BS&W) content negatively. Otherwise, it could require additional treatment and separate
handling. The solids and water require filtration either
by addition to the feed to the large filters in a water plant
(if the chemicals added to break the emulsion are shown
to not cause problems with the filter operation) or by
separate filtration.
Fig. 4 is a schematic of a generalized waste stream treatment process. The waste stream could be any combination of water, oil (hydrocarbons), and solid phases, such
as IGF skimmings, filter backwash, tank bottoms, and
sludge. The phases are effectively separated into three
streams by the tailored, continuous, or batch treatment of
the specific waste stream with chemicals, heat, or residence time.
The treatment is assumed to yield oil clean enough to be
added to the produced crude without upsetting the
BS&W limits.
Two alternatives are shown for a water stream assumed
to contain very little oil that requires filtration before
subsurface injection. If returning the water to the water
treating system does not negatively affect system operation, the water stream is combined with the water before
10-12
10-13
10-14
10-15
Excessive hardness.
Extremely tight oil/water/solids emulsions carried by the water.
2. Oil sludge tightly emulsified with water and solids
recovered from:
Pits.
Separator skimmings.
Other tank skimmings.
3. Filtered or settled solids still containing some oil
and water recovered from:
Pits.
Tank bottoms.
Dry-cake and other filters.
These wastes are the separated and concentrated wastes
that must be disposed of economically and in accordance
with environmental regulations. An excellent reference
on the subject of waste management relative to environmental regulations is the API environmental guidance
document, Onshore Solid Waste Management in Exploration
and Production Operations.1 Although written with respect to solid wastes, the document summarizes environmental regulations and discusses liquid wastes.
Federal
1. Resource Conservation and Recovery Act (RCRA).
10-16
State (California)
1. Health and Safety Code, Division 20, Chapter 6.5,
Hazardous Waste Control, Chapter 6.8, Hazardous
Substance Account.
2. Water Code Division 7, Water Quality.
3. California Environmental Act (CEQA).
4. Toxic Well Control Act (TWCA).
5. Toxic Pits Cleanup Act (TPCA).
6. Implementing regulations relative to the above
e.g., California Code of Regulations, which implements CEQA.
Local
1. Various county and city ordinances regarding hazardous wastes.
The federal and state agencies charged with implementing these laws are:
Federal
1. Environmental Protection Agency (EPA).
State (California)
1. State Department of Health Services (DHS) Toxic
Substances Control Division.
2. State Water Resources Control Board (SWRCB).
3. Regional Water Quality Control Boards (RWQCB).
10-17
Wastes are regulated by federal and state agencies. Because California regulations are generally more stringent
than federal regulations, we use them in the following
discussion. California regulations are good examples of
the regulations other states already follow or will follow
soon. California generally sets the direction other states
follow.
1. Toxicity.
2. Ignitability.
3. Corrosivity.
4. Reactivity.
These tests must be conducted by a Certified Hazardous
Waste Testing Laboratory following the procedures
specified in the CCR.
In addition, if the waste contains at least 1 of 791 chemicals listed in CCR, Title 22, Article 9, it is assumed to be
hazardous. Each of these 791 chemicals, including both
organic and inorganic compounds, is considered toxic,
ignitable, corrosive, and/or reactive. Article 9 lists various wastes by their common names that come under
the provisions of this section of the code if they contain a
hazardous material. Of note, relative to oilfield water
treating, are:
Acid and water.
Corrosion inhibitors.
Oil and water.
Tank bottom sediments.
Tank cleaning sludges.
10-18
Waste chemicals.
A copy of CCR, Title 22, Articles 9 and 11, is included in
the Appendix.
When any potential for groundwater contamination
exists, the RWQCB becomes involved, and additional
tests may be required even if the waste is not classified as
hazardous. The California Water Code gives the RWQCB
authority in governing discharges to land, including the
classification and regulation of waste disposal. These
boards have a separate classification of wastes that dictates the type of facility where the waste can be disposed
of on land:
1. Hazardous Wastes Wastes that are hazardous
according to the DHS definitions described above
(CCR, Title 22, Articles 9 and 11). These can only be
disposed of in a Class I facility.
2. Designated Wastes Wastes that are:
A. Nonhazardous but consist of or contain pollutants
that could be released at levels exceeding applicable water quality objectives or that could cause
degradation of the waters of the state.
B. Hazardous wastes that have been granted a variance by the DHS. These can be disposed of only in
a Class I or Class II facility.
3. Nonhazardous Solid Wastes Wastes that are degradable and nondegradable solids, semisolids, and
liquids (garbage, paper, trash, and demolition and
construction wastes) and similar wastes that do not
contain Designated Wastes. These can be disposed of
in permitted landfills.
4. Inert Wastes Wastes that do not contain any of the
above or any significant amount of degradable waste,
including clean earth, concrete, inert plastics, tires,
and similar materials. These may be disposed of in
unclassified landfills.
Local governments (cities and counties) may become
involved and require additional tests or handling practices.
10-19
10-20
10-21
REFERENCE
1. Onshore Solid Waste Management in Exploration and
Production Operations, Order No. 811-10850, Publications and Distribution Section, API, 1220 L St. NW,
Washington, DC 20005 (202/682-8375).
10-22
GLOSSARY
anionic surfactants soaps that inherently have a
negative charge.
BS&W bottom sediment and water.
cationic surfactants soaps containing a positive
charges.
Class I wells hazardous waste disposal wells. Subject
to the most stringent conditions.
Class II wells designated for the injection of produced
water.
Class III wells designated for waters used for extraction of minerals.
Class IV wells for disposal of hazardous and radioactive wastes.
Class V injection wells not covered by any other
category.
dry-cake filter filter device that captures solids to
form a moist cake.
EOR enhanced oil recovery.
filteraid solid materials added to stream to enhance
capture of suspended materials in filter.
heavy metals larger, multicharged cations. Some like
arsenic and mercury have a low permissible limit in
discharged water.
IGF skimmings Induced gas flotation skimmings; oilrich reject stream from a device that removes residual
dispersed oil from water.
landfarms locations where dispose of solid wastes by
mixing and burying with clean soil.
PCBs polychlorinated biphenyls. Hazardous compounds containing chlorine and two benzene rings.
perlite solid material used as a filter aid.
point source treating treating a waste stream at the
point it is generated.
water softeners devices that remove calcium and
magnesium from a water.
Chapter 10: Handling Separated Wastes
10-23
10-24
APPENDIX
10-25
10-26
Index
Symbols
4,6-diamino-2-phenylindole (DAPI) 7-29
A
acetate utilizer 7-12, 7-24
acetic acid 5-33
acid producing bacteria (APB) 7-6, 7-17
acid wastes 10-10
acid-insoluble suspended solids 2-65
acid-soluble suspended solids 2-65
acids 9-7
organic 7-6, 7-8, 7-17
volatile fatty 7-17
acridine orange (AO) 7-29
acrolein 7-40
acrylate coagulants 8-18
acrylate polymers 8-18
acute toxicity 7-53
adenosine-5'-phosphosulfate (APS) reductase enzyme 7-29
adenosine-5'-triphosphate (ATP) 7-28
aerobic 7-10, 7-12
agar deep method 7-27
aldehydes 1-17, 7-40, 8-24
aliphatic acids 2-10, 2-11
alkalinity 2-3
alkyl aryl sulfonate surfactants 8-18
aluminum 6-7, 6-20, 6-21, 8-8
amine 6-9
amine-type biocides 8-24
amines 6-18, 6-23
ammonium bisulfite 6-23
anaerobic 7-10, 7-12
analytical methods 2-20
scale inhibitors 5-17
anhydrite 5-7
anionic 8-14
anionic surfactant 8-18
anionic surfactants 10-10
anionic-cationic interaction 8-23
anions 8-4
anodic 6-4, 6-5, 6-6, 6-11
antifoamer solubility 8-9
antifoamers 1-17, 8-9, 8-14
API Environmental Guidance Document 10-16
API separators 3-9
aquatic toxicity test 7-54
Index
I-1
B
backwash 10-9
backwashing 3-31
bacteria 6-3, 6-9, 6-10, 6-12, 6-23, 8-10, 8-24
acid producing 7-6, 7-17
autotrophic 7-9, 7-17
heterotrophic 7-8, 7-12
iron 7-17
lithotrophic 7-8
mesophilic 7-27
planktonic 7-18, 7-19, 7-21, 7-22, 7-25, 7-38, 7-41, 7-42,
7-45, 7-47, 7-49, 7-55
sampling methods 7-21
sessile 7-19, 7-21, 7-22, 7-25, 7-38, 7-41, 7-42, 7-45,
7-46, 7-47, 7-49, 7-56
slime forming 7-16
sulfate reducing 7-5, 7-6, 7-8, 7-11, 7-13, 7-15, 7-17, 7-19,
7-22, 7-24, 7-25, 7-30, 7-32, 7-33, 7-49
sulfide producing 7-13, 7-30, 7-32
sulfite reducing 7-27
sulfur oxidizing 7-17, 7-18
thermophilic 7-27
bacteria detection
culturing methods 7-23
direct methods 7-23, 7-28
bacterial activity 10-9
barium 2-7
barium sulfate 5-7, 5-11, 5-32, 8-15
batch frequency 7-46
batch treatment 7-53, 10-11
bench scale flotation units 3-24
best available practical technology 3-6
bicarbonate 5-4
bioassay 7-54
biocide effectiveness 7-44
biocide resistance 7-42
biocide selection 7-41
biocide solubility 8-7
biocide testing 7-49
biocide treatment procedures 7-53
Biocides 1-12
biocides 1-11, 1-12, 1-13, 1-17, 6-3, 6-10, 7-38, 8-5, 8-7,
8-10, 8-13, 8-14, 8-24, 10-7
inorganic 7-40
organic 7-41
oxidizing 7-38, 7-40
I-2
biofilm 7-4, 7-8, 7-19, 7-22, 7-34, 7-38, 7-41, 7-42, 7-46,
7-47, 7-49, 7-56
biomass 2-12
bisulfide 2-11
black water 2-8, 5-9, 7-8
bottle reduction 7-46
bottle reductions 7-44
broth bottles 7-25
BS&W 10-12
bug bottles 7-25
C
calcium 2-7
calcium carbonate 5-4, 5-10, 5-30, 6-9, 6-12, 6-19, 6-23, 8-15
calcium sulfate 5-4, 5-31, 9-8
calcium sulfate (anhydrite) 8-15
calcium sulfate (gypsum) 8-15
calcium sulfate converters 5-32
calcium sulfite 8-18
California regulations 10-17, 10-19
carbon adsorption 1-13, 1-18
carbon dioxide 2-10, 5-4, 6-8, 6-18, 6-21, 6-22, 6-23, 6-24, 7-7
carbonate 2-5, 5-4
carboxylates 8-18
cathodic 6-4, 6-5, 6-8, 6-12
cathodic protection 6-9, 6-16, 6-21, 6-24
cation-anion interactions 8-15
cationic 8-14
cationic polyelectrolytes 3-24
cationic surfactants 8-18, 10-10
cations 2-7, 8-4
celestite 5-8, 5-11
cell surface antibody methods 7-29
chelating agents 6-11
chelation 5-14, 5-30, 5-31, 5-33
chemical additives 1-5, 10-7, 10-10, 10-11
chemical analysis 7-31
chemical cleaning 7-36
chemical compounds 8-5
chemical concentration units 2-41
chemical consumption 7-7
chemical incompatibilities 10-12
chemical interactions 5-18, 8-14
chemical solubility 8-5
chemicals 8-11, 10-12
residual 8-6
chloride 2-5
chlorine 7-37, 7-39, 7-53, 8-24
chlorine dioxide 1-17, 6-3, 6-8, 6-10, 6-24, 7-37, 7-53, 8-24
chlorinity 2-9
chlorinity, 2-9
chromium 6-4, 6-7, 6-19
Index
I-3
D
de-oilers 8-20
deflocculation 9-3, 9-5, 9-9
dehydration 3-33
demulsifier 3-34
bottle testing 8-21
chemistry 8-19
I-4
E
EDTA 5-14, 5-30, 5-33
eductor IGF 3-20
effect of deposits 6-12
effective concentration, median (50%) (EC50) 7-54
effective oil field water treatment 10-3, 10-9
electrochemical methods 2-25
electron acceptor 7-9, 7-10
electron donor 7-9
emission spectroscopy 2-26
emulsifying agent 3-33
emulsion 3-10, 3-33, 10-12
Index
I-5
F
federal regulations 10-16
fermentation 7-9, 7-16
fibrous coalescers 3-14
filter backwash 1-4, 1-8, 10-7, 10-10, 10-12
filter backwash chemicals 8-5
filter media cleaning 10-10
filter vessels 10-9
filteraid 10-12
filters 10-7
filtrate 10-12
filtration 1-7, 1-9, 1-16, 10-11, 10-12
fines
injection 9-6
Fines; injection 9-4
firefly luciferase 7-28
fixed media coalescers 3-13
flame photometry 2-26
flocculant solubility 8-8
flocculants 8-14, 8-20
flocculation 3-32
flotation 1-14, 1-16, 3-16, 3-32, 8-21, 10-7
dissolved 3-17
dissolved gas 3-17
eductor induced 3-17
retention time 3-20
rotor induced 3-17
skimmings 3-19
flotation aids 3-24, 3-33
flotation cell 3-34, 8-22
flotation cell skimmings 10-7
fluorescein diacetate (FDA) 7-29
fluorescence spectroscopy 2-26
I-6
G
galvanic 6-3, 6-6, 6-8, 6-12, 6-15, 6-17, 6-21, 6-22
gas concentration 3-22
gas dehydration chemicals 8-11, 8-14
gas flotation units 8-9
gas flotation vessels 10-9
gas production 8-11
gas stripping 1-17
gas/liquid contact time 3-21
gas/water ratio 3-21
genus 7-11
geochemical thermometer 2-12
glutaraldehyde 7-40
glycol 8-11
grains per gallon (gpg) 2-38
gravimetric analysis 2-22
gravimetric factor 2-31
gravity separation 3-32
Gulf of Mexico 7-55
gypsum 5-7, 5-11, 5-31
H
hardness 2-3
Hastelloy 6-20
hazardous wastes 10-19
heat 10-12
heavy metals 10-20
heterotrophic bacteria 7-8, 7-12
hydrate inhibitor solubility 8-11
hydrate inhibitors 8-11, 8-14
hydraulic eductor units 3-20
hydrazine 6-23
hydrocarbon-soluble suspended solids 2-65
hydrocyclone 3-33
operating pressure 3-27
hydrocyclones 3-24
hydrogen 6-4, 6-16
hydrogen peroxide 6-8, 7-37
hydrogen sulfide 1-5, 1-6, 2-10, 5-8, 6-8, 6-9, 6-10, 6-13,
6-18, 6-21, 6-22, 6-23, 6-24, 7-5, 7-6, 7-7, 7-11, 7-15,
7-16, 7-17, 7-33, 8-10
(TLV) 7-6
Hydropack 3-25, 3-29
Index
I-7
Hydroswirl 3-25
hydroxyaluminum 9-14
hypochlorite 7-37, 7-39, 7-53, 8-24
I
IGF selection 3-20
IGF skimmings 3-33, 10-10, 10-12, 10-14
ignitability 10-18
in-line probes 7-52
incompatible waters 1-6, 1-11, 5-3, 5-12
incomplete oxidizers 7-12, 7-13, 7-15
indirect recycling 10-10
induced gas flotation 1-8, 3-18
infrared light scattering 3-37
inhibitor 6-6, 6-25
inhibitors 6-3, 6-18
injected water 10-15
injection water 1-9, 9-3, 9-13
injection well
plugging 1-11, 9-3, 9-6, 9-7, 9-9
injection well disposal 10-3
injectivity impairment 3-4
injectivity loss 3-3
inlet oil concentration 3-23
inorganic biocides 7-40
inorganic metal salts 8-8
inspection 6-13, 6-17, 6-24
integrated treatment systems 3-32
inter wastes 10-19
interface pad 3-33
ion chromatography 2-29
ion exchange 3-7, 10-11
ion selective electrode 2-27
ionic character 8-14
ionic properties 8-14
IR absorption 3-37
iron 2-7, 8-8
iron and calcium silicates 8-18
iron bacteria 7-17
iron carbonate 5-12, 6-6, 6-9, 8-15
iron counts 6-14
iron deposits 5-8, 5-12, 5-29, 5-33
iron oxide 2-8
iron oxides 6-3, 6-4, 6-8
iron sulfide 1-5, 2-8, 5-8, 7-6, 7-8, 8-15
iron sulfides 6-3, 6-4, 6-8, 6-13
isotope 7-32
J
Jackson Turbidity Units (JTU) 2-42
I-8
K
Kuparak Field 7-5
L
laboratory methods 3-40
landfarms 10-14
lethal concentration, median (50%) (LC50) 7-54
linear polarization 6-15
linings 6-24
liquid-liquid hydrocyclone 8-22
lithotrophic bacteria 7-8
log reduction 7-44, 7-46
loose media coalescers 3-12
luciferin-luciferase firefly reaction 7-28
M
magnesium 2-7
magnesium hydroxide 8-18
maximum droplet size 3-9
mean gas bubble size 3-22
mechanical design 7-35
media
fibrous cartridge 3-13
sponge type 3-13
media filtration 3-32, 8-9
melt agar tube method 7-27
mesophilic bacteria 7-27
methanogens 7-32
mica alteration 9-5, 9-13
microbial profile modification (MPM) 7-3
microbial reservoir souring 7-4
microbially enhanced oil recovery (MEOR) 7-3
microbiologically influenced corrosion (MIC) 7-5, 7-11, 7-32, 7-50
Microtox 7-55
migration 9-3, 9-5, 9-9
mild steel 6-5, 6-7, 6-8, 6-15
milliequivalents per liter (meq/L) 2-38
milligrams per liter (mg/L) 2-37
milligrams per liter (or parts per million) 2-39
milligrams per liter as calcium carbonate 2-39
Minas Field 7-31
mixing incompatible waters 8-15
molality (m) 2-41
molarity (M) 2-40
mole 2-39, 2-40
molecular weight 2-22
monel 6-20
monitoring 6-17
mudballing 3-31
Index
I-9
N
naphthenic acids 2-10
National Association of Corrosion Engineers Standard 2-65
neutral components 8-4
nickel 6-4, 6-10, 6-19, 6-20, 6-23
Ninian Field 7-5
no-observed-effect concentration (NOEC) 7-54
nonhazardous solid wastes 10-19
nonionic 8-14
normality 2-40
normality (N) 2-40
NTA 5-33
nutshell filters 3-31
O
obligative anaerobe 7-12
offshore discharge 3-6
oil droplet coagulation 8-22
oil droplet size 3-9, 3-22, 3-33, 8-21
oil field chemicals, types 8-5
oil field waters
natural components 1-5, 8-4
oil soluble 8-7
oil/water separation 8-5, 8-20
oil/water separation equipment 10-12
on-line monitors 3-37
onshore systems 3-12
organic acids 2-10, 7-6, 7-8, 7-17
organic biocides 7-40, 7-41
organic polyelectrolytes 8-8
organic polyquaternary amine 9-14
overdosing 3-33, 3-34
oxidation-reduction 7-9
oxidizers
complete 7-12, 7-15
incomplete 7-12, 7-13, 7-15
oxidizing agent 7-9
oxidizing biocides 7-38, 7-40
oxygen 1-5, 1-6, 1-11, 2-4, 6-3, 6-4, 6-6, 6-7, 6-8, 6-9, 6-10,
6-11, 6-13, 6-14, 6-17, 6-18, 6-21, 6-22, 6-23, 9-8
oxygen scavenger solubility 8-10
oxygen scavengers 8-7, 8-10, 8-13, 8-14, 8-24
oxygen scavenging 1-17
ozone 7-37
P
PAIR 6-15
paraffin deposits 8-9
paraffin dissolvers 8-10
paraffin treating 8-9
I-10
Q
qualitative identification 2-66
quality control 2-37
quaternary amines 1-17
quaternary ammonium salts 8-18
Index
I-11
R
radium 2-7
RapidChek 7-29
reactivity 10-18
recirculation loop 7-50
recycle streams 3-33
recycling 10-7
red water 2-8, 5-9
reducing agent 5-33, 7-9, 7-11
Regulations 1-12
regulations 1-7, 1-9, 3-3, 10-14
reject ratio 3-28
reject stream 3-27
remedial treatments 9-8
requirements for discharge 3-6
requirements for enhanced oil recovery (EOR) 3-6
requirements for injection 3-3
reservoir souring 7-4
residence time 3-10, 10-12
resistance 6-14, 6-17
resistivity 2-21
restricted wastes 10-20
retrofitting 3-36
reverse breakers 8-8, 8-14, 8-20
reverse demulsifiers 8-19, 8-21
reverse osmosis 3-7
rock analyses 9-9
S
salinity 2-3
salinity, 2-9
salinity of produced water 3-22
sample identification 2-17
sampling 2-3
sampling methods
bacteria 7-21
sampling procedures 2-16
sand filters 10-9
saturation index 5-9, 5-10
scale 10-7
scale formation 1-13, 8-15
scale identification 5-28
scale inhibitor
application 5-18, 5-20
batch treatments 5-20
continuous recirculation 5-21
evaluation 5-18
selection 5-17
squeeze 5-22, 5-24
squeeze model 5-25
scale inhibitor solubility 8-6
I-12
scale inhibitors 1-11, 1-12, 1-17, 1-18, 6-11, 8-5, 8-6, 8-14,
8-23, 10-7
phosphate esters 5-15, 5-24
phosphonates 5-15, 5-24
polymers 5-15, 5-24
polyphosphates 5-15
scale mixtures 8-15
scale precipitation 8-15
scaling 10-9
scaling tendency 5-9, 5-10, 5-11, 5-12
scanning electron microscopy 2-67
scraping 7-36
seawater 6-8, 6-10, 6-12, 6-17, 6-20, 6-21, 8-10
separated gases 10-5
separated oil 10-5
separated solids 10-5
separated water 10-5
separation equipment 8-21
separators 10-7
serial dilution 7-26
sessile bacteria 7-19, 7-21, 7-22, 7-25, 7-38, 7-41, 7-42,
7-45, 7-46, 7-47, 7-49, 7-56
settling time 3-8
sewer system 1-7
side stream loop 7-50
silica 2-21
skimmings 1-5, 1-15
slime forming bacteria 7-16
sludge 10-7, 10-12
sludges 10-14
slug treatment 7-53
sodium 2-5
sodium chloride 8-15
sodium sulfite 6-10, 6-23
softening 3-7
solid culture media 7-26
solids 1-10
solids generation 10-9
solids stabilized emulsions 8-23
solubility 5-3, 8-9
solubility calculations 2-47, 5-9, 5-11
solubility of surfactants 8-19
soluble iron(II) 2-13
solvents 8-5
sour water 8-10
souring 7-4
SP-Pack 3-16
species 7-11
specific gravity 2-9
specific resistivity 2-21
spools 6-13
spread plate method 7-27
Index
I-13
T
tank bottoms 1-5, 1-15, 8-23, 10-7, 10-10, 10-12, 10-14
tanks 10-9
TDS 2-5
temperature 2-9, 6-11, 6-17, 6-24
thermophilic bacteria 7-27
I-14
U
U.S. Environmental Protection Agency 2-69
ultrasonic 3-37, 6-16
ultraviolet radiation 7-38
unwanted wastes 10-9
UV absorption 3-37
V
velocity 6-17, 6-21
vertical tube coalescer 3-16
vessel internals 3-11, 3-36
viable cell counts 7-29
viscosifiers 8-13
volatile acids 2-20
volatile fatty acids 7-17
voltammetric analyses 2-28
Vortoil 3-25, 3-28
W
waste stream 3-31
waste streams 8-22, 8-23
waster disposal 10-15
water analysis
reasons for 2-3
water characteristics
handling and treatment 1-5
open waters 1-6
produced waters 1-5
source wells 1-6
water chemistry 7-7, 8-3, 10-11
water dispersible 8-7
water phase residence time 3-34
water quality 1-10, 1-13, 10-7
Index
I-15
X
x-ray diffraction (XRD) 2-66
x-ray fluorescence (XRF) 2-66
Z
zero discharge 10-14
zinc chlorides 8-8
I-16