Professional Documents
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Contents
Introduction
Produced Waters:
1. Generally are corrosive as a result of elevated tem-
perature and high salinity. Potential problems from
handling produced waters
2. Usually contain dissolved gases (oxygen, carbon
dioxide, and/or hydrogen sulfide), which increase include their corrosivity,
corrosiveness. variable composition,
3. Will vary in terms of physical and chemical properties tendency to carry or form
with time, location, and field operations (wells shut solids, and oil content.
in, brought on line, being worked over, stimulated,
etc.).
4. Typically contain dissolved iron, which causes the
water to be chemically unstable, leading to scale and/
or precipitate formation and interaction with other
waters or chemical additives.
5. Contain suspended solids, including clays and other
formation fines, iron sulfides, paraffins, and asphal-
tenes that are coated with oil, which causes them to
agglomerate.
6. Contain various amounts of free oil and dissolved
organic compounds.
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 or-
ganic 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 oxy-
gen to facilitate bacterial growth.
Filtration
1. Economical water injection requires that lives of the
injection wells to be maximized. Economical justifica- Economical justification
tion of filtration must consider more than the capital
for filtration must
and costs of the filters. Filtration costs must be com-
pared with costs for drilling new wells, working over consider its costs versus
or redrilling plugged wells, or stimulating partially the benefits of increased
plugged wells. An effective stimulation treatment injector life and improved
does more than just increase injectivity one time only.
waterflood sweep
The number of times an injector can be stimulated
successfully must also be considered. This includes efficiency.
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 se-
cured from regulatory agencies to drill new wells.
Regulations are becoming more restrictive for dis-
posal wells. A proper decision to install filters must
have input from reservoir, production, gas and chemi-
cal, and design and construction engineers, as well as
from environmental coordinators.
2. The need to maintain profile control (sweep) by
removing the suspended solids that plug tight zones
is another factor to include in considering filtration.
Cations
Sodium, Na+
• Is the principal monovalent cation in most waters. Cations are positively
• All commonly occurring sodium compounds are charged ions that moved
soluble, although sodium chloride may precipitate towards the cathode in an
from highly concentrated, nearly saturated brines.
electrolysis cell.
• Should be determined analytically, not calculated by
difference, as was common in many “older” analyses.
• Is the primary cation contributor to total dissolved
solids (TDS) and ionic strength. Sodium ions are the
• Used in cation/anion balance as a quality-control major cations in normal
check. produced or connate
waters.
Potassium, K+
• Is usually present at lower concentrations than so-
dium.
• High levels may indicate sample contamination from
drilling or completion fluids.
• All commonly occurring potassium compounds are
soluble.
• May be combined with and reported as equivalent
amount of sodium ions.
Calcium, Ca2+
• Usually is the principal divalent cation.
• Contributes to and may be reported as water hard-
Calcium and magnesium
ness.
are the principal
• Combines with sulfate or carbonate ions to form
suspended solids or adherent scale deposits. “hardness ions” in
produced waters.
Neutral Silica
Components Bacterial Content
Oil-in-Water
Total Residue
Total Dissolved Solids
Suspended Solids
Amount
Type
Particle Size Analysis
Barium, Ba2+
• Is frequently found in produced waters but at a lower
concentration than calcium or magnesium.
• Combines with sulfate ions to form extremely in-
soluble barium sulfate deposits that are difficult to
remove.
• May indicate the presence of other radioactive alka-
line earth cations (e.g., radium).
Strontium, Sr2+
NORM (naturally
• Usually is associated with but at lower concentrations
than barium. occurring radioactive
material) is usually
• Forms insoluble strontium sulfate or mixed
strontium/barium sulfate precipitates. radioactive divalent
cations included in
Iron, Fe sulfate scales.
• Usually is determined and reported as soluble iron
and total iron (soluble + insoluble).
• May occur naturally in some waters and formations
but frequently indicates corrosion of producing and
treating equipment.
Soluble iron may be an
• Is present initially in the reduced form, Fe2+ or Fe(II), indication of corrosion.
in produced water.
• Reduced iron, Fe2+ or Fe(II), is more soluble than
oxidized iron, Fe3+ or Fe(III).
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.
• Composed primarily of calcium and magnesium ions
Calcium and magnesium but includes any other di- and trivalent cations.
are the principal hardness • Indicates relative carbonate scale formation potential.
ions and form an
• Frequently precipitated in boilers, steam generators,
insoluble scum with and highly alkaline waters.
soaps. • May be determined directly by titrimetric chemical
analysis or calculated by conversion of di- and tri-
valent cation concentrations to chemically equivalent
amounts of calcium carbonate (CaCO3).
Anions
Chloride, Cl-
• Major anion in many waters.
Anions are negatively • High concentrations increase water corrosivity.
charged ions that move
• Stable anion, useful for identifying and tracing water
towards the anode in an flow.
electrolysis cell.
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
− −
Cl(‰)= 0.9996∗ (Cl + 0.4437∗ Br + 0.2794∗ I )
-
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”
• Major component (along with carbonates and bicar-
Organic acids can be a bonates) of alkalinity in some produced waters.
carbon and energy source • Generally are low-molecular-weight (C2 to C4) ali-
for bacterial activity. phatic acids or naphthenic acids (saturated acids with
five- and six-membered rings of carbon atoms).
Alkalinity
• Measure of ability to combine with or consume hy-
drogen 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, phos-
phate) 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. Dissolved oxygen is a
• Recommended levels 20 parts per billion (ppb) to major contributor to the
minimize corrosion. corrosivity of oilfield
• Oxidizes soluble iron to precipitate iron oxides. waters.
• Can oxidize dissolved sulfides to form colloidal
sulfur.
• Promotes growth of aerobic, slime-forming bacteria.
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 biomass can plug and foul injection wells,
Bacteria must not only be surface treating facilities, and downhole equipment.
present, they must also be • An estimate of the type and number of bacteria is
necessary to assess the presence and severity of bacte-
active within the system
rial problem and to suggest remedial actions.
to cause problems.
• SRB and SPB generate toxic and corrosive hydrogen
sulfide.
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.
pH
• Defined as the negative logarithm of the hydrogen ion
activity (concentration). Neutral waters have a pH
• Affects solubility of carbonate, hydroxide, and sulfide of 7. Acid waters have
precipitates or scales. pH’s less than 7. Alkaline
• Corrosion rate increases as pH decreases. or basic waters have pH’s
• Low pH may indicate presence of corrosive acid greater than 7.
gases, CO2 and H2S.
• Usually determined by the amount and type of weak
acids and bases present (or organic acid/organic acid
anion).
• May change rapidly in a poorly buffered system from
loss or gain of acid gases.
• Best measured in place in a pressurized system or in
the field immediately after sampling.
• Laboratory-measured pH may differ significantly
from field measurements because of changes in acid
gas concentration, hydrolysis reactions, precipitation
of basic and acidic components, or bacterial degrada-
tion of organic material.
Temperature
• Must be measured in the field.
• Strongly affects corrosion rates, precipitate solubili-
ties, 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 unchang-
ing.
• Is an indirect measure of water quality (high turbidity
indicates low water quality).
Density
• Is defined as weight per unit volume.
Density and specific • Specific gravity is the ratio of the sample density to
gravity are numerically water density, each at some specified temperature.
equal only when the • Densities greater than pure solvent indicate the pres-
reference water has a ence of dissolved and suspended solids.
density of exactly • Correction factor used for some concentration conver-
1.0000 g/mL. sions.
• Can be used as a quality-control parameter because
density and total dissolved solids content are related.
Conductivity
• Measure of the dissolved ionic components.
• Resistivity (reciprocal of conductivity) used for well
logging.
• Can be a quality-control parameter because conduc-
tivity is related to ionic concentration.
Sampling
Sample location and identification, as well as sampling
Steps in chemical procedures and preservation techniques, are as important
analysis: as the choice of analysis procedure. The sample must
represent the operating system at some set of conditions.
1. sample preparation The sample should be uniquely identified, and the loca-
2. sample preservation tion and operating conditions at the time of sampling
3. chemical analysis should be recorded. Finally, multiple samples may be
4. reporting necessary: field analysis and specially preserved samples
for unstable components, unpreserved samples for stable
components, and separate samples for specialty analyses.
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, pres-
sure, 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 operat-
ing conditions.
Some system components or properties change rapidly
with time and cannot be adequately preserved or stabi-
lized for later laboratory determinations. These compo-
nents 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 com-
ponents are reasonably stable and do not need special
preservation techniques. A complete analysis involves
field analysis for some components and laboratory analy-
ses with an unpreserved sample and with several spe-
cially treated samples for the remainder.
All liquid samples for analysis or preservation should be
field-filtered as soon after sampling as possible. The Filtration in the field is an
purpose is to remove dispersed oil and suspended solids essential step in sampling
(scale deposits, corrosion products, formation fines, etc.)
present in the original sample. Chevron personnel devel- and sample preparation.
oped an automatic pressure filtration apparatus4 suitable
for field filtration. Carpenter and Campbell5 gave spe-
cific details for field sampling and filtration. Multiple
filtrations may be necessary if dispersed oil concentra-
Sample Location
Field, lease, well, section, state, country,
gathering station, tank battery, pipeline,
pit, etc.
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 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 wash-
ing 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.
Unpreserved Sample
A filtered sample with no preservatives or conditioners is
used for silica analysis. If the silica is expected to be Dilution is commonly
supersaturated at lower temperatures after sampling, the
used to preserve a
sample should be diluted with a known volume of silica-
free deionized water. The filtered sample also is used for supersaturated solution of
the common and stable anions (chloride and sulfate) and silica.
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, labora-
tory alkalinity, carbonate and bicarbonate alkalinity, and
nonvolatile acid content. These measurements are made
to check field analyses and to indicate possible gas ex-
change reactions, bacterial activity, or precipitation and
hydrolysis reactions that might have occurred between
sampling and laboratory analysis.
Oil-in-Water Content
Separate samples, in individual glass bottles, are needed
for each oil-content determination (oil-in-water analysis). Currently, there is no
If total oil content (free or dispersed oil plus dissolved
analytical procedure that
oil) is desired, the sample is not filtered. Prefiltration will
remove dispersed oil and allow estimation of dissolved is specific for oil. Oil, by
oil. Water samples containing large amounts of dis- definition, is whatever is
persed oil may need to be filtered several times to re- detected by a specified
move all the free oil. The filter may become saturated
analytical method.
with oil and permit excess oil to bleed through. If the
Analytical Methods
Analytical methods for cations, anions, and dissolved
gases are summarized in Table 3; Table 4 lists the meth-
ods for neutral components and properties. The follow-
ing 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 — In gravimetric analysis, the
Gravimetric analysis is desired chemical component is reacted completely with
an excess of another chemical to form an insoluble com-
usually very accurate. It is
pound of definite and known composition. The insoluble
used to prepare and compound is removed by filtration, washed to remove
determine analytical impurities, dried or ignited to a fixed composition, and
standards. It is a weighed on an accurate and sensitive analytical balance.
From the precipitate weight and composition, we can
laboratory method.
calculate the amount of the original component. For
example, we can determine barium ions by adding an
excess of sulfate ions to precipitate insoluble barium
sulfate and then digesting, filtering, washing, and drying
the precipitate.
+ −
Ba + SO 4 → BaSO 4
2 2
Wt. Ba 2 + =
(Wt. BaSO 4 )∗ (Mol. Wt. Ba)
(Mol. Wt. BaSO 4 )
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
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 read-
outs.
Analytical Report
Information from sampling and analysis is usually pre-
The analytical report is sented in a Water Analysis Report. The amount of infor-
the final step in the mation presented and the report format vary among
laboratories. In general, a report should contain suffi-
sampling and analysis
cient information to identify the sample point and system
procedure. The reliability conditions at the time of sampling. It should list the
of the data in the report components or properties determined and the units of
depends upon all of the concentration or measurement for each component or
property, respectively. Additional sections may present
preceding steps in the
solubility calculations, graphical display of water
procedure. composition, and water type or classification.
Date: Operator:
Sample designation:
Local contact:
Address: Phone:
Field: State:
Country: Location: Sec: Twp:
Rge:
Producing Producing
Intervals: Formation:
Sampled by:
EW2
W2 = W1 ∗
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.
Multiplier ∗ Multiplier ∗
Symbol Atomic Weight Product
2∗ Na = 2∗23 = 46
1∗ S = 1∗32 = 32
4∗ O = 4∗16 = 64
Sum = Molecular = 142
Weight of Na2SO4
Atomic or Equivalent
Molecular Weight,
Substance Weight Valence mg/meq.
H+ 1 +1 1
Na+ 23 +1 23
Ca2+ 40 +2 20
Cl- 35.5 -1 35.5
−
HCO 3 61 -1 61
2−
CO 3 60 -2 30
CaCO3 100 2 50
(mg / L)
ppm = .
(density, kg / L)
or
(mg / L)
wt.% = 0.0001∗ .
(density, kg / L)
(mg / L)
meq / L = .
(milliequiv. wt.)
(ppm)
epm =
(eq. wt.)
CaCO 3 + 2H + → Ca 2 + + CO 2 + H 2 O
and
(mg / L)
N = 0.001∗
(eq. wt.)
(mg / L)
M = 0.001∗
(mol. wt.)
or
A dditional definitions:
J = milliequivalent weight, mg
R = solution density, kg/L
S = (R − TDS∗1E − 6) , weight of solv ent in 1-liter of solution, kg
TDS = num ber of equiv alent/m ole
Revised: February 4, 1991
(NTU) as the preferred expression of turbidity. Formazin
standards are still used, but using NTU indicates the
manner in which the turbidity is measured.
Density, g/mL, or Specific Gravity — Density is the
weight in grams of 1 mL of solution (numerically equal
to the weight in kilograms of one liter of solution). Spe-
cific gravity is the ratio of the weight of a specific volume
of solution to the weight of the same volume of distilled
water. Because both water and solution volumes are
temperature-dependent, the temperatures at which the
density or specific gravity was measured should be
specified. The terms “density” and “specific gravity” are
frequently used interchangeably. This substitution is not
completely accurate. The density of distilled water, at all
reasonable pressures, is always less than one, so specific
gravities are always numerically greater than densities.
For many systems, though, the substitution is acceptable
because the density of water at ambient temperatures is
within 0.5% of 1 g/mL.
Specific Conductivity, mho/cm or µmho/cm — Conduc-
tivity is a measure of the ability of an ionic solution to The now-preferred term
conduct an electric current. The standard unit of conduc-
for specific conductivity
tance is specific conductance, k, defined as the reciprocal
of the resistance, at a specified temperature, of a solution is simply conductivity.
contained between two parallel electrodes, each 1 cm2 in
cross section and 1 cm apart. The unit of k is reciprocal
ohms (mhos) per cm. Conductance is sometimes stated
in siemens/cm, the SI unit, where 1 mho = 1 siemen.
Most solutions have a limited power to conduct a cur-
rent, so specific conductivities are frequently reported in
µmhos/cm.
Specific Resistivity, ohm-m — Resistivity, the opposition The now-preferred term
of an ionic solution to carry an electric current, is equal to for specific resistivity is
the reciprocal of the conductance. The unit of specific
resistivity used in water analysis usually is ohm-meter. simply resistivity.
Solubility Calculations
Water analysis reports frequently include solubility
Solubility calculations calculations for calcium carbonate, calcium sulfate,
will tell if a precipitate barium sulfate, and sometimes strontium sulfate, the
most common precipitates in oilfield waters. Service
will form — they cannot
companies performing chemical analyses usually have
tell how fast a precipitate their own computer programs, some proprietary and
will form. some not, for these calculations. Patton10 (Pages 65-79)
describes some of the simple predictive calculations.
Solubility calculations are based on equilibrium, thermo-
dynamic data and ignore how fast a precipitate will form
(kinetics). Even when calculated solubilities are exceeded
for some components in solution, precipitates do not
appear in many systems because of tendencies to form
supersaturated solution or the presence of scale inhibi-
tors (added or naturally occurring). Solubility calcula-
Reliable solubility
tions are based on the chemical analysis of a specific
calculations at any point sample. A solubility calculation can be extrapolated to a
in a system requires system only if the sample and chemical analysis truly
accurate chemical analysis represent the system at its operating conditions. A com-
mon oversight is to use a laboratory-measured pH for a
at the same point.
carbonate scale calculation. The laboratory pH is usually
higher than the field pH because of loss of carbon diox-
ide. Thus, calculation based on the laboratory pH will
underestimate the solubility of carbonate scales at system
conditions. Another oversight concerns the interpreta-
tion of reported alkalinity. Many oilfield waters contain
components other than carbonate/bicarbonate that can
contribute to alkalinity. Assuming that all the alkalinity
of such waters results from carbonate/bicarbonate will
underestimate the solubility of carbonate scales. Some
earlier calculations for scaling tendencies were based on
relatively low-temperature, low-salinity systems. These
procedures lack a sufficiently extensive database to yield
Composition Diagrams
A number of ways to express water analysis data graphi-
cally 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 PC’s 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 ana-
lytical data produced by a laboratory. An excellent dis-
cussion 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 correct-
ness or reliability of analysis. A complete geochemical
analysis — including the major anions and cations, mea-
sured total dissolved solids, conductivity, density, and
pH — is required to check for correctness of analysis.
The anion/cation balance
Anion/Cation Balance is the primary method of
Determining the anion/cation balance is the primary checking the
method of checking an analysis. This procedure is based completeness of an
on the fact that aqueous solutions are electrically neutral
and therefore the sum of the concentrations of anions analysis.
% difference = 100∗
[(cations) − ∑ (anions)]
[∑ (cations) + ∑ (anions)]
with a criteria of acceptance taken from Ref. 13:
Calc. TDS, mg / L = Na + + K + + Ca + + Mg + +K
2 2
The calculated TDS
2− − − 2−
+ CO 3 + HCO 3 + Cl + SO 4 + C 2 H 3 O 2 +K , mg / L
-
should be equal to the
measured TDS. Alkalinity and hardness, if expressed as mg/L as CaCO3,
must be broken down into the individual responsible
ions, with concentrations expressed in mg/L, before
being included in the above equation. Thus, total alkalin-
ity in mg/L as CaCO3 should be divided into mg/L of
measured TDS
1.0 < < 1.2
calculated TDS
Equation Reference
−6
Sp.Gr. = 1 + TDS(mg / L)∗0.695 × 10 Ostroff, Ref. 12, p. 34
−6
Sp.Gr. = 1 + TDS(mg / L)∗0.725 × 10 Jones, Ref. 14, p. 109
Abbreviations:
Sp. Gr. = Specific Gravity TDS = Total Dissolved Solids
Calculated Conductivity = ∑ (c + f+ ) + ∑ (c − f− )
Conductivity (25ºC)
µmhos/cm
Ion Per meq/L Per mg/L
Sodium 48.9 2.13
Potassium 72.0 1.84
Calcium 52.0 2.60
Magnesium 46.6 3.82
Carbonate 84.6 2.82
Bicarbonate 43.6 0.715
Chloride 75.9 2.14
Sulfate 73.9 1.54
G = λ C − (k 1λ + k 2 )C 2
3
where
G = conductivity of solution,
C = concentration of solution,
λ = equivalent conductivity at infinite dilution,
and
k1,k2 = constants for relaxation of ion cloud electro-
phoretic 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 µmhos/cm.
and
and
Calculated TDS( mg L )
= 0.55 − 0.7
Conductivity(µmhos cm)
OH − , CO 2− −
3 , or HCO 3 is possibly present, and
If 4.5 ≤ pH ≤ 8.5
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 pur-
poses, (2) to determine the amount of dispersed or free
oil in injection water for water-quality studies, or (3) to
Dissolved Oil
The individual components of crude oil vary widely in
their solubilities in water. Table 14 lists water solubili- The solubilities of crude
ties15 of some typical hydrocarbons. General trends in oil components vary
solubility behavior are evident. For any given class of
hydrocarbon compounds (a homologous series), the widely.
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
alkyenes > alkadienes > alkenes > alkanes.
Dodecanoate Dodecanoic
(Laurate), (Lauric) Acid,
C11H 23COO - C11H 23COOH Dodecane C 12H26
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.
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 unfil- The distinction between
tered sample is said to contain “total oil” (free + dis- free oil and dissolved oil
solved); the filtrate is said to contain “dissolved oil.”
is not always possible in
This method of separation is not reliable or complete
because significant amounts of free oil may bleed an analytical procedure.
through the filter media and appear in the filtrate, espe-
cially when the samples contain large amounts of free oil.
Multiple filtrations may be necessary to remove all the
Quality Control
Five issues are involved in quality control for an oil-in-
water 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 dis-
cussed specify the extraction conditions and do not
permit variations. The designated fluorocarbon
solvent was chosen because of its relatively low
SUSPENDED SOLIDS
Sampling and Analytical Procedures
A variety of analytical procedures can be used, depend-
ing on the type and sophistication of the information
desired. The sampling procedures for all analytical
methods for suspended material have one common goal:
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 analy-
sis, 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 im-
prove precision.
Some suspended solids are unstable when dried or ex-
posed to air. For example, iron sulfide may be pyro-
phoric 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 rea-
sonable assurance that we are analyzing what was origi-
nally present in the system. When identifying the com-
position 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.
Oil/Water Separation
Injection Requirements
The effect of residual oil in injection water on the perme-
ability 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
Disposal Requirements
When defining disposal of oily waters, we generally talk
about subsurface disposal into a specific zone or reser-
voir. Surface disposal of oily waters is considered dis-
charge.
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 equip-
ment protected. Disposal wells can be drilled into zones
identified as suitable for disposal. Or existing wells
within an existing reservoir can be recompleted to dis- Many disposal wells are
posal standards. In both cases, the water will probably
be treated to a low level of oil, <10 ppm, before reinjec- completed in high
tion. However, many disposal zones are selected because permeability zones. This
of their high permeabilities and hence may be more minimizes the treatment
tolerant of oil than injection zones in the same field. We required for the injected
cannot yet define the ideal level of oil concentration for
subsurface disposal zones. The optimum level is usually water.
defined as the maximum oil concentration that the dis-
posal zone can tolerate with no injectivity loss or con-
tamination outside the disposal zone.
For disposal, the cost of oil removal is just an overhead
with no payback (except for the value of oil recovered);
the water will not generate incremental oil production.
Therefore, the goal is to remove just enough oil to main-
tain injectivity and wellbore integrity.
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
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 me-
chanical processes occur. The mechanical process pro-
vides 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
COALESCERS
Coalescers provide a solid surface that can come in con-
tact 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 ag-
glomeration and must be used with separation equip-
ment downstream. Each type of coalescer plays an
important role in effective separation of oil from water.
Three types of coalescers are currently available: plate-
pack, loose-media, and fixed-media coalescers.10,11 In this
section, we will consider only media coalescers. Plate-
pack coalescers are covered in the next section.
Loose-Media Coalescers
Loose-media coalescers are vessels containing a medium,
Coalescers provide a such as sand, that acts as a coalescing surface for oil
droplets. These coalescers may be upflow or downflow.
surface for oil droplets to
They essentially provide a surface area and contact time
contact, agglomerate and for the oil droplets to coalesce. Upflow coalescers are
grow. typically used in oilfield applications; downflow
coalescers are used in refinery applications. These de-
vices operate quite simply. Oil droplets enter the vessel
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.
FLOTATION
Flotation has become the industry standard for de-oiling
Flotation has been the produced water because of its excellent separation capa-
bilities. Conceptually, it is a simple process. Gas bubbles
industry standard for oil
unite with oil droplets to reduce their apparent specific
removal for many years. gravity, thus accelerating their rise velocity and separa-
tion. Practically, flotation occurs in a vessel that provides
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 full-
scale unit. This procedure is recommended if flotation is
being considered for an existing field’s water production.
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 µm. For a dispersed unit, the gas bubble size is
typically >100 µm. 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 µm) 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.
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 200°F
exists. At these elevated temperatures, steam condensing
in the gas blanket of a flotation cell reduces the gas vol-
ume that can be induced by the impeller of an IGF unit.
This decreased gas volume reduces gas concentration
and thus oil droplet capture efficiency.
HYDROCYCLONES
Hydrocyclones have been used for many years to sepa-
rate solids from liquids and from air. These devices are
used as clarifiers, classifiers, and thickeners in a variety
of industries, including mining.
Static Hydrocyclones
All static hydrocyclones currently available (Conoco’s
Vortoil and Hydropack, Amoco’s 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
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 variable-
speed 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 genera-
tion.
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.
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 consis-
tently achieved oil removal efficiencies of 90% at maxi-
mum rotational speed and nominal flow rate. Reduc-
tions 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 µm in diameter. Fig. 16 com-
pares typical static and dynamic cyclone performance.
Applications to Date
Most hydrocyclones in use today are permanent installa-
tions on offshore platforms. The space and weight ad-
vantages of LLHC’s over plate-pack separators and
flotation units are most useful, and savings in platform
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. Sev-
eral 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 concentra-
tion, existing chemical treatments, and, if possible, an
inlet oil droplet size distribution. The last item is ex-
tremely valuable information for predicting cyclone
performance that is not available in most situations.
Armed with the above information, the cyclone manufac-
turers 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 manu-
facturers’ predicted performance criteria should be used
Run field evaluations of if backed up by field performance data from similar
hydrocyclones to operating conditions. If not, then the origin of the data
for performance prediction should be established. Our
establish their operating
experiences indicate that manufacturers’ predictions of
capabilities. 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 character-
ize 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.
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 separa- Nutshell filters are more
tors. Typically, these filters do not act as true separators tolerant to oil than sand
but as oil accumulators. The oil in the feed stream enter- filters.
ing the filter is retained within the filter bed and is re-
moved during backwashing. One of the three commer-
cial variants, however, has the option of using an oil
take-off valve for any free oil that floats to the top of the
filter.
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 consid-
ered during selection of oil/water separating equipment.
Several facilities templates are available in the ITS phi-
losophy for selecting oil/water separation equipment.
On-Line Methods
Currently, no on-line methods exist to measure oil-in-
water 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 en-
couraging. Technical Memorandum TM91001083 in the
Appendix includes a description of this testing.
Four basic on-line techniques are used to measure oil-in-
water concentrations: infrared light scattering,
infrared absorption, ultraviolet absorption, and ultra-
sonic.
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 unit’s 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 Ang-
stroms. 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 haloge-
nated 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, pro-
vides 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
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 com-
ponent in the total absorption spectrum can be isolated.
The operating range of ultraviolet absorption oil in water
monitors is 0 to 100 ppm.
Laboratory Methods
Laboratory methods of oil-in-water determination are the
most common form of monitoring separator perfor-
mance. 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.
Filtration
Scaling and
Water Formed Solids
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) (1)
Ca
++
( )
+ 2 HCO −3 → CaCO 3 (s) + CO 2 + H 2 O (2)
Calcium Sulfate
The precipitation of calcium sulfate is given by the reac-
tion
Table 2 Common Oil Well Scale Deposits — Causes and Removal Chemicals
Chemical Most Frequent Causes Removal
Deposit Formula Mineral Name of Scale Deposit Chemical
Calcium CaCO3 Calcite Mixing Brines, Changes in 15% HCL
Carbonate Temperature and Pressure
Calcium Sulfate CaSO 4 • 2H 2 O Gypsum Same as Above Converting
CaSO 4 Anhydrite Solutions, EDTA
Type Dissolvers
Barium Sulfate BaSO4 Barite Mixing of Brines ?
Strontium Sulfate SrSO4 Celestite Mixing Brines, Changes in ?
Temperature and Pressure
Iron Carbonate FeCO3 Siderite Same as Above Sequestered
Acid
Iron Sulfide FeS Trolite Corrosion by Sour Crude or H 2S Gas Same as Above
Iron Oxide Fe2O3 Hamatite Reaction of Oxygen with Dissolved Same as Above
Fe3O4 Magnetite Ferrous Ion
Sodium Chloride NaCl Halite Evaporation of Water Water or 1–3%
HCL
Water Treatment Handbook
Barium Sulfate
This scale is especially troublesome. It is extremely
insoluble and almost impossible to remove chemically. Barium sulfate is the most
Fig. 1 compares the solubilities for common oilfield scales difficult oil field scale to
in distilled water. Barium sulfate scaling is likely when
deal with.
both barium and sulfate are present, even in low concen-
trations.
++ =
Ba + SO4 → BaSO 4 (s) (4)
Strontium Sulfate
Strontium sulfate is similar to barium sulfate, except
fortunately its solubility is much greater.
Iron Compounds
The iron deposits are much more complicated than
The oxidation state of scales. One reason is that the iron may come from the
formation water, corrosion, or both. Another complica-
iron is important in the tion is that the dissolved iron may be present in two
form these scales take. oxidation states: Fe++ (ferrous) and Fe+++ (ferric). The two
cations form compounds with the same anions but with
very different solubilities.
CO2 will react with the ferrous ion to form iron carbonate
scale. This scale has similar solubility behavior as cal-
cium carbonate vs. pH, temperature, etc., except the
solubility of FeCO3 is approximately 100 times lower.16,17
Hydrogen sulfide readily causes iron sulfide to form as a
corrosion product. This sulfide typically is very insoluble
and forms a thin, adherent scale. Suspended iron sulfide
is the cause of “black water.” This also may occur by
mixing one stream containing dissolved H 2S with an-
other containing dissolved iron.
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 concentra- Scaling tendency is a
tion of the scaling ions in solution indicates the scaling
tendency or the likelihood of scale formation. measure of the driving
force or likelihood of
Note that these calculations only provide a guideline and
are not necessarily exact. Simplifying assumptions have scale deposition.
been made in the derivation of all predictive equations;
the solubility of inorganic compounds in naturally occur-
ring waters is a complex phenomenon.
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)
IP = C Ba ++ × C SO 4 = (7)
IP
SR = (8)
K sp
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, reac-
tions 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.
If, for example, two surface waters are to be injected, two
methods are available to handle the waters without
We recommend not to mix mixing them:
incompatible waters, if
1. Split system — inject each water into its own system.
possible.
2. Sequential injection — inject the waters alternately.
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 in-
compatibility 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.
Environmental Controls
Another approach is to control the temperature and
pressure to avoid creating scaling conditions. The pro-
cess usually dictates these parameters; the operator has
limited ability to make the required adjustments.
These chemicals are perhaps the most common method
of preventing undesired water-formed precipitates.
Scale inhibitors are the Therefore, this topic is treated in greater detail.
most common method to
prevent precipitates. SCALE INHIBITORS
Principle of Use
Scale inhibitors are chemicals that delay or prevent scale
formation when added in small concentrations in nor-
mally 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-
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 draw-
backs.
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 perfora-
tions 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
SCALE REMOVAL
If preventive steps fail to halt undesirable scale deposi-
tion, chemical and mechanical methods are available to
Scale removal is the last
remove this material.
resort for fixing a
Note that scale removal is the last resort for curing a
deposition problem.
precipitation problem. Preventing scale deposition is
much preferable.
Scale Identification
One key in scale removal is first to identify the composi-
tion of the deposit. A suggested procedure for qualita-
tively identifying scales in the field include (Table 6):
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-inhibi-
tor 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.
CaCO 3 → ++ =
← Ca + CO 3 (10)
EDTA −4 + Ca ++ →
← Ca EDTA
=
(11)
Barium Sulfate
Barium sulfate is very difficult to remove chemically and
until recently was removed only by mechanical means.
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, nitrilo-
acetic acid (NTA), and EDTA are common examples.
2. Reducing agents. These chemicals convert ferric ions
to the more soluble ferrous oxidation state. Erythor-
bic 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.
Mechanical Removal
Downhole Cleanout
In downhole cleanout, scale is removed from the tubing,
perforations, formation face, and sometimes the forma-
tion 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 — re-
move deposits from the formation face or perforations.
Corrosion Effects
GENERAL CORROSION
General corrosion occurs over a large area of an exposed
metal and results in gradual thinning. The corrosion
process occurs because refined base metals are thermody-
namically unstable in the presence of oxygen or water.
The corrosion mechanism includes two reactions: a
Corrosion of metals is an cathodic reduction reaction and an anodic metal dissolu-
electrochemical reaction tion reaction. The cathodic reaction in an aerated system
which requires an is the reduction of oxygen to hydroxide ion, which re-
electrolyte, an anodic quires free electrons:
surface, a cathodic 1
2 O 2 + H 2 O + 2e − = 2OH
surface, and a metallic
In the absence of oxygen, the cathodic reaction is the
connection between them. reduction of hydrogen ions to hydrogen gas, which also
requires free electrons:
2H + + 2e − = H 2
The anodic metal dissolution reaction converts neutral
metal atoms to positively charged metal ions, releasing
free electrons:
Me = Me ++ + 2e −
The cathodic and anodic reactions are coupled through
the electrons, so they must occur at the same rate.
Corrosion rates of the more noble metals (e.g., nickel,
chromium, copper alloys) are generally low enough that
dissolved metal ions present no problems to water qual-
ity. Also, dissolved iron is not usually a water quality
problem in itself except in boiler feedwater. The problem
arises when the water contains oxygen or dissolved
sulfides, resulting in precipitation of iron compounds.
The most common iron compounds are iron hydroxides
and iron oxides (magnetite and hematite) and iron sul-
fides (too numerous to list).
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 reac-
tions 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, intergran-
ular corrosion, corrosion fatigue, selective dealloying) see
the Corrosion Prevention Manual, Sections 120 and 300.
Pitting
Mild steel in oilfield brines will usually show a com-
bination 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
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 im-
mersed 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 pro-
tected; 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,
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 cor-
rosion is generally 5 to 20 times greater than a measured
general corrosion rate.
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 tenden-
cies. 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 tempera-
ture. If the temperature is not uniform, hotter areas are
generally anodic to cooler areas.
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 detect-
ing 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.
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 Rohrbach-
Cosasco 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 corro-
sion rates.
Pitting corrosion cannot be distinguished with a single-
probe instrument. Various types of probes are available
that respond to pitting in different ways. Wire-loop
probes are more sensitive to pitting damage than cylin-
drical 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 ele-
ment to compensate for temperature changes. In rapidly
changing temperatures, the reference element tempera-
ture will not be able to track the test element, leading to
errors in readings.
Linear Polarization
Tretolite’s PAIR and Rohrbach-Cosasco’s Corrater mea-
sure instantaneous corrosion rates using the linear polar-
ization method. These instruments also generate a con-
tinuous 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 corre-
lated to exposure time. Again, pitting corrosion is not
well detected.
These electrochemical instruments are limited to conduc-
tive 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-conductiv-
ity 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 dis-
similar metals. The same concerns apply to these instru-
ments 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
Tretolite’s Zero Resistance Ammeter oxygen monitoring
instrument.
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 re-
quirements, 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.
Inhibitors
• Organic Inhibitors — Organic corrosion inhibitors
almost exclusively have nitrogen-containing func-
tional groups. Several classes of chemicals may be
used, including low-molecular-weight amines for
vapor-phase inhibitors, filming tertiary and quater-
nary 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 neutraliz-
ing 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 some-
what less effective than water-dispersible inhibitors.
Water-dispersible inhibitors, formulated with a hy-
drocarbon 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 main-
tained 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.
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
Coatings
Coatings provide barriers to corrosion. A large variety of
coating materials, application systems, and curing tech-
niques 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 protec-
tion 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 high-
resistivity electrolytes, coatings are necessary to reduce
current requirements sufficiently that interference is not a
problem.
Surface preparation is essential in applying a good coat-
ing. 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 manufacturer’s speci-
fications. 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.
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, Hous-
ton (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).
Microbiological Problems in
Production Operations
Environmental Concerns
Like reservoir souring, the cause of environmental prob-
lems is the production of H2S by bacteria. However,
unlike souring, environmental problems can occur wher-
ever SRB are present - in the reservoir, production string,
separating and treating system, or injection system.
Hydrogen sulfide, formed
Environmental and safety concerns are related to the
by sulfate reducing extreme toxicity of H2S. The threshold limit value (TLV)
bacteria, is extremely for H2S is 10 ppm for 8-hour time-weighed-average
toxic and flammable. 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 consum-
ing or degrading treatment chemicals. Treatment chemi-
cals may stimulate bacterial activity. Some bacteria use
treating chemicals as a carbon and/or energy source for Operating costs for
metabolism. application of treating
Polymers used for scale control, diverting agents, or chemicals increase when
fracture fluid thickeners are frequently biodegradable. bacterial activity
Phosphorus-containing scale inhibitors and nitrogen-
containing oxygen scavengers may provide the trace consumes or degrades
nutrients required for bacterial growth. Biomass formed chemicals.
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.
The metabolic products of bacterial activity may react
with or deactivate chemicals. Examples include con-
sumption of chlorine and other oxidizing biocides, deac-
tivation of aldehyde-type biocides, and the formulation
of gunking polymers by H2S. Oxygen scavengers that
rely on cobalt catalysts are nonreactive when the cobalt
reacts with sulfide. The formation of corrosive H2S or
organic acids will increase the need for more effective
(and probably more expensive) corrosion-inhibitor for-
mulations.
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,
MICROBIOLOGICAL ENERGETICS
Bacteria require energy to Like all living things, bacteria require energy and certain
live and grow materials to live and grow (dissimilation) and to multiply
(dissimilation) and to by the synthesis of cell material (assimilation). The energy
source is usually an organic carbon compound (het-
multiply by the synthesis
erotrophic bacteria), although some bacteria can use gas-
of cell material eous or dissolved hydrogen as an energy source
(assimilation). (lithotrophic bacteria). The carbon source required for
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
MICROORGANISMS INVOLVED IN
MICROBIAL PROBLEMS
Bacteria are scientifically classified by genus and species.
The genus refers to a group of related bacteria; the spe-
cies refers to different bacteria within a genus. The types
of bacteria and microorganisms that contribute to or
influence problems in producing operations are de-
scribed 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 con-
sortia 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.
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.
Slime-Forming Bacteria
Slime-forming bacteria do not represent any single group
or genus of organisms. They represent a general group-
ing of aerobic or facultative (can grow without oxygen)
bacteria. These bacteria are characterized by the produc-
tion of slimy bacterial cells and extracellular polymeric
substance that lead to plugging and pitting corrosion
Slime-forming bacteria
problems. They enhance pitting corrosion by shielding
produce large amounts of portions of the surface, depleting oxygen, and forming
extracellular polymeric differential oxygen concentration cells.
substances that lead to In addition to their plugging and fouling capabilities,
plugging and pitting they stimulate the growth and activity of SRB (1) by
corrosion. providing protective biofilms, (2) by reducing oxygen
concentrations and providing anaerobic regions in the
biofilms, and (3) by providing usable carbon/energy
sources.
Specific bacterial types of slime formers are Pseudomonas,
Flavobacterium, Micrococcus, Aerobacter, Aspergillus, and
Nocardia. They are usually detected by culturing meth-
ods like total plate count, plate count, or total count
(discussed later). When detected by culturing methods,
they are identified as “general bacterial count” in
API RP 38.6
Iron Bacteria
These heavy slime formers can oxidize soluble iron
[Fe(II)] to insoluble iron [Fe(III)] using dissolved oxygen Iron bacteria oxidize
as the oxidizing agent. The insoluble iron (1) contributes
soluble iron (II) to
to plugging and fouling; (2) provides anaerobic niches for
other bacteria, including SRB; and (3) enhances corrosion insoluble iron (III) and
from differential oxygen concentration cells. These produce large amounts of
bacteria are aerobic but can grow with <0.5 ppm oxygen. slime.
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 diffi-
cult to culture. Direct microscopic techniques are recom-
mended for detection.
By Habitat
Monocultures — single species
Consortia — mixed cultures
Planktonic Bacteria
Planktonic bacteria are the free floaters. They are found
Planktonic bacteria are in the bulk water stream. They move with the flowing
stream and frequently contaminate the downstream
free floating in the liquid
portion of treating and injection systems. These bacteria
phase. usually are introduced into the system through inad-
equately treated water input streams.
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.
The techniques for sampling and analyzing bacteria
Microbiological sampling differ considerably from those used for chemical analysis
(Table 6). Assistance from someone trained or experi-
and analysis require enced in microbiological procedures may be necessary to
technique, equipment, obtain reliable data. Frequently, the chemical service
and experience that is companies are better qualified and have the necessary
uniquely different from equipment to determine whether bacterial problems are
present, to prescribe treatment and control procedures,
chemical sampling and and to train operating personnel in further bacterial
analysis. monitoring. The ideal situation is to have trained and
experienced operators working with the chemical suppli-
ers.
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 sam-
pling or as soon as possible afterward by techniques
described in following sections. Maintain anaerobic
conditions when sampling for SRB.
Test Methods
Culturing Procedures
Direct Methods
Broth Bottles
Culturing with broth bottles (bug bottles) is probably the
most common method in oilfield situations. The cultur- Broth bottles are the most
ing medium is made up and enclosed in a small bottle
common culturing
sealed with a rubber septum. A sterile, disposable sy-
ringe is used to introduce the sample into the sealed method used in oilfields.
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 stan-
dard 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 API has a revised version
was published. RP 38 is currently being revised; reissue of RP 38 that has not been
is on hold, pending possible publication of a NACE released as of June 1994.
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 augment- The new NACE Test
ing this with additional nutrients and chemicals specific Method TM 0194-9416 also
to the bacteria being studied provide the most suitable contains compositions for
media. Postgate’s4 monograph is the standard for tech- standard media for SRB,
niques and media for SRB. Another useful reference is
Mittleman and Geesey’s8 book. It contains a number of APB, and GAB.
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
Pour-Plate Method
The sample, or dilutions thereof, is mixed with molten
agar containing the desired media. The temperature of
the molten agar (45°C) 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). There-
fore, it may give false positive tests for SRB from sulfite-
reducing bacteria that would not be active in a sample
that does not contain sulfite.
ATP Assay
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
ATP Assay uses the firefly
of all living bacteria. Therefore, ATP assay does not
luciferose enzyme to specify the type of bacteria present. ATP is extracted
detect all living bacteria. from the bacterial cells and detected by reacting with an
It cannot differentiate enzyme (firefly luciferase) in the presence of oxygen and
measuring the amount of emitted light with a special
between types of bacteria
photometer. ATP is quickly lost from bacterial cells when
or detect dead bacteria bacteria die, so the method detects only live bacteria.
that have lost ATP. Samples for analysis must be processed and preserved at
the sampling point to retain ATP. The method is rela-
tively 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 standard-
ization procedures performed by experienced personnel.
Phospholipid Signature
This procedure identifies the distinct signature of phos-
pholipids unique to each strain of bacteria. It uses diffi-
cult procedures and expensive equipment in a controlled
laboratory environment. The method is good for qualita-
tively identifying bacterial types and strains but is not
calibrated for quantitatively measuring numbers of
bacteria. Its use is confined to research studies for identi-
fying bacteria.
Radio-Respirometry
This method measures the rate of biogenic production of
Radio-respirometry CO2 from a radioactive carbon source or H2S from a
measures bacterial radioactive sulfate source in the culture media. It is an
extremely sensitive way to detect and measure bacterial
activity rather than activity. Unlike most other methods of bacterial detec-
bacterial numbers. tion, the radio-respirometric method measures bacterial
activity (i.e., the rate at which CO2 or H2S is produced)
rather than the number of bacteria present. Bacterial
activity in the culture media may or may not match
activity in natural surroundings, especially if carbon and
energy sources and concentrations are different. The
Chemical Analysis
The presence and activity of bacteria can sometimes be
inferred by changes in water chemistry, i.e., the appear-
ance of products of bacterial metabolism or the disap-
pearance of compounds used by bacteria. Thus, the
presence and activity of SRB can be inferred by a de-
crease 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 (82°C). Sulfate levels
follow an inverse relationship, decreasing from stations
to wells.
Water Injection
Well 6F52 3E86 2D24 10D15 6A59 7B89
H2S, mg/L 2. 3. nil 5. 3.4 7.7
SO2−
4 , mg/L
14. 19.8 23. 13. 24.4 16.4
pH 7.3 7.4 7.4 7.3 7.6 7.6
Temperature, ºC 77 78 82 78 72 78
δS = 34 32
34 ( )
S 34 S 32 sample
− 1 × 1000
( )
S S standard
(1)
Types of Biocides
A variety of organic and inorganic chemicals and chemi-
cal 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, hypochlo-
Biocide Selection
We should consider four guiding principles when select-
ing 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.
Sample Number
Percent Kill = 1- × 100 (3)
Control Number
where control number and sample number are the num-
ber 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)
If the serial dilution culturing method discussed in the
Broth Bottles section is used, the log reduction is numeri-
cally equal to the number of bottle reductions defined as
Biocide Toxicity
By their very nature, biocides must be toxic to bacteria
and other microorganisms. However, their toxicity to Toxicity is the potential or
higher life forms is of prime importance in protecting the capacity of a test material
environment. This is true whenever water is discharged.
It is also important whenever there is a spill, a leak, or to cause detrimental
accidental contact with biocide-treated water. effects on living
Before discussing the toxicity of specific biocides, we organisms.
should define a few important terms. Toxicity is the
potential or capacity of a test material to cause detrimen-
tal effects on living organisms. Toxicity may be acute as
the result of a relatively short-term exposure (2 to 4 days
Chemical Injection
A nio ns C hloride C l-
C O =3
C arbonate
H C O −3
B icarbonate
H yd roxid e OH-
SO =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 -
General
Except for a few cases, commercially supplied oilfield
chemicals are not single chemical compounds. They
generally consist of the following:
1. One or more chemical compounds that are the “back-
bone” of the chemical (i.e., the active ingredient)
added to perform the designed function of the chemi-
cal. These chemicals often are produced from petro-
chemical streams or other natural organic materials.
These materials are mixtures of chemical compounds
having a range of molecular weights and different
chemical groups.
2. A solvent or mixture of solvents, required because the
main chemical compounds are viscous or solid in
their 100% active form. In some cases, the solvent
may be water; in many applications, however, refin-
ery cuts, paraffinic or aromatic hydrocarbon mixtures,
are used.
3. Other additives to enhance the activity of the main
chemical compounds, increase their solubility or
dispersibility, increase storage life, or prevent freez-
ing. Chemical suppliers consider these additives
active components of the formulation. Only the
solvent is considered inert.
The method of addition and the chemical concentrations
vary tremendously. Some surfactants to assist oil/water
separation are injected continuously at very low concen-
tration levels (a few ppm). Others, like biocides and filter
backwash chemicals, are injected in slugs of a few hun-
dred to a few thousand ppm. Scale inhibitors and similar
“well squeeze” chemicals are injected into the well at
concentrations of thousands of ppm but are produced
back over long time periods at much lower concentra-
tions. Some corrosion inhibitors are injected continu-
ously at 5 to 100 ppm; others are batch-treated at 1,000 to
5,000 ppm. The most reactive and concentrated chemi-
cals used in oilfield operations are stimulation acids,
which are used at concentrations of up to 30 wt%.
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 pro-
duction operations can be classified as:
Biocides
Two general classes of biocides are used in the oil field:
1. Strong oxidizers, including chlorine, sodium hy-
pochlorite, and chlorine dioxide.
2. Organic-based biocides, including quaternary ammo-
nium 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 reac-
tions 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 separa-
tion:
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.
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 surfac-
tants 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 water-
soluble 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.
Oxygen Scavengers
To control corrosion, dissolved oxygen is generally re-
moved 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 oxy-
gen.
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.
Acids
1. Hydrochloric acid.
2. Hydrofluoric acid.
3. Formic acid.
4. Acetic acid.
5. Fluoroboric acid.
6. Citric acid.
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.
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.
Viscosifiers
1. Polymers (natural and synthetic).
A. Hydroxyalkyl celluloses.
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 chemi-
cals).
Corrosion Inhibitors
Amine Oil Cationic
Quaternary Amine Water Cationic
Amide Oil Nonionic or Cationic
Amidoamide Oil Nonionic or Cationic
Biocides
Quaternary Amine Water Cationic
Phosphonium Salt Water Cationic
Aldehyde Water Nonionic
Chlorine Water Nonionic
Thiocarbamate Water Anionic
Isothiazoline Water Cationic
Emulsion Breakers
Phenol Formaldehyde Resin Oil Nonionic
Glycol Esters Oil Nonionic
Alkyl Arylsulfonate Oil Anionic
Oxyalkylated Glycols Oil Nonionic
Reverse Breakers
Polyamine Water Cationic
Polyamine Quat. Amm. Water Cationic
Antifoamers
Esters Oil Nonionic
Silicones Oil Nonionic
Paraffin Treating
Vinyl Polymers Oil Nonionic
Sulfonate Salts Oil Anionic
Polyethers Oil Nonionic
Oxygen Scavengers
Sulfite Salts Water Cationic and Anionic
Sulfur Dioxide Water Nonionic
Sulfide Scavengers
Aldehydes Water Nonionic
Hydrate Inhibitors
Methanol Water Nonionic
Ethylene Glycol Water Nonionic
Gas Dehydration
Glycols Water Nonionic
Well Stimulation
Acids Water Cationic and Anionic
Frac Fluids Water and Oil Nonionic
Additives
Corrosion Inhibitors
Acetylenic Alcohols Water Nonionic
Surfactants Water and Oil Cationic and Anionic
Mutual Solvents Water Nonionics
Diverters Oil Nonionic and Anionic
Viscosifiers Water Nonionics
Surfactant Interactions
The most common interactions between injected oilfield
chemicals involve surfactants (surface active agents).
Many injected chemicals are classified as anionic, cat-
ionic, or nonionic surfactants. We will briefly describe
the chemistry of surfactants here because of their impor-
tance 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 seg-
ment 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 qua-
ternary nitrogen (i.e., a nitrogen atom covalently bound
to four substituents). Examples are quaternary ammo-
nium salts. As the name indicates, nonionic surfactants
do not have a charged segment. The hydrophilic seg-
ment is a polymer of ethylene oxide.
Reverse Demulsifiers
Underdosing reverse demulsifiers usually results in
inefficient operation of separation equipment. In flota-
tion 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 vol-
ume of oily water has to be skimmed to maintain oil
Water/Formation
Rock Interactions
Mica Alteration
Micaceous minerals, such as micas and illites, are nor-
mally not considered expandable, but they can undergo Injecting non-potassium
alterations that cause their structures to expand.4 Mica-
brines into a mica-rich
ceous minerals are layered, much like smectites, except
the layer charge is substantially higher and the seat of the reservoir can result in
charge is closer to the surface. Thus, the mineral is much formation damage.
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 hexago-
nal holes between the layers. This allows the structure to
remain collapsed with a 10-Angstrom basal spacing.
Even though the interlayer potassium ions are relatively
nonexchangeable, micaceous minerals in contact with a
non-potassium-salt solution will slowly lose interlayer
potassium to the solution. The interlayer sites are highly
selective for potassium ions. But when the edges of the
particles are in contact with a solution having an over-
whelming abundance of competing ions and a very low
concentration of potassium ions, some interlayer potas-
Differential Dissolution
Differential dissolution describes a permeability damage
mechanism in which permeability is decreased by less
Differential dissolution is
soluble migrating fines released by the dissolution of
a damage mechanism in more soluble rock components. 3 Most reservoir rocks,
which less soluble particularly sandstones, consist of a mixture of many
migrating fines are different minerals. Each has its own solubility and disso-
lution rate in a given brine solution.
released by the
dissolution of more Temperature, pH, and water composition affect solubility
and dissolution rates. During flow of a particular brine
soluble rock components.
solution through the rock, some minerals may readily
dissolve; others may dissolve very slowly; others may be
essentially insoluble in the solution. If the different
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 oxy-
gen in the water. The precipitated iron compounds
(mostly iron hydroxide) may plug the pore space and
damage permeability.
10
Federal
1. Resource Conservation and Recovery Act (RCRA).
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 imple-
ments CEQA.
Local
1. Various county and city ordinances regarding hazard-
ous wastes.
The federal and state agencies charged with implement-
ing 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).
REFERENCE
1. Onshore Solid Waste Management in Exploration and
Production Operations, Order No. 811-10850, Publica-
tions and Distribution Section, API, 1220 L St. NW,
Washington, DC 20005 (202/682-8375).
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
arbitrary recycling 10-9
assimilation 7-8
atomic weight 2-25
ATP assay 7-28
autotrophic bacteria 7-9, 7-17
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
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
chronic toxicity 7-54
citric acid 5-33
Class I wells 10-21
Class II wells 10-21
Class III wells 10-22
Class IV wells 10-22
Class V wells 10-22
classification of wastes 10-18
clay stabilizers 9-13, 9-14
clays 1-5, 9-3, 9-8
expanding type 9-4
cleaning 8-9
coagulant solubility 8-8
coagulants 1-18, 3-33, 8-14, 8-20
coagulants and flocculants 8-8
coagulation/coalescence 8-21
coalescence 1-14, 1-15, 3-9, 3-16, 3-32
coalescers 8-20
coalescing agents 3-24
color 2-16
combined wastes 10-11
complete oxidizers 7-12, 7-15, 7-25
compounds
polymers 1-12, 1-18
conductivity 2-16
consortium 7-15, 7-19
continuous treatment 7-53, 10-11
copper 6-4, 6-10, 6-20, 6-21
copper-nickel 6-17
core samples 9-13
coreflood procedures 3-4
corrosion 1-5, 1-7, 1-13, 10-9
microbiologically influenced 7-5, 7-11, 7-32, 7-50
pitting 7-5, 7-16
corrosion inhibitor solubility 8-7
corrosion inhibitors 1-11, 1-12, 1-17, 8-5, 8-6, 8-13, 8-14, 10-7
corrosivity 10-18
coupons 6-12, 6-13, 6-17
cracking 6-5, 6-8, 6-9, 6-13, 6-19, 6-20, 6-21
crevice corrosion 6-6, 6-19, 6-21
crude dehydration 3-10
crude oil dehydration 3-32, 3-34
cupronickel 6-10
cyanides 10-20
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
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
emulsion breaker solubility 8-8
emulsion breakers 8-7, 8-14
emulsions 3-24, 3-31, 10-12
endpoint 2-25
enhanced oil recovery 10-3
environment 10-15
environmental 1-7, 1-12
environmental problems 7-6
environmental regulations 10-3, 10-16
EOR 10-14
EPA 3-6, 10-20
epifluorescence methods 7-29
equivalence point 2-26
equivalent 2-5
equivalent weight 2-31
erosion-corrosion 6-10
extinction dilution 7-26
extracellular polymeric substance (EPS) 7-3, 7-4, 7-10, 7-16, 7-19
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
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
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
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
Index I-13
stainless steels 6-5, 6-7, 6-8, 6-9, 6-19
steam generation 3-7, 10-3
steam injection 9-7, 9-8
steam quality 3-7
stimulation 1-8, 1-9
acids 8-11
diverters 8-13
flushes 8-12
frac fluids 8-12
stimulation acids 8-5, 8-14
stimulation fluid additives 8-14
stimulation job 8-11
stimulation liquids 10-10
Stokes law 3-8
Stokes’ Law 3-26
strong oxidizers 8-24
strontium 2-7
strontium sulfate 5-8, 5-11, 8-15
subsurface disposal 3-5
sulfate 2-5, 6-10, 6-23, 9-8, 9-9
sulfate reducing bacteria (SRB) 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
sulfates 6-9, 8-18
sulfide producing bacteria (SPB) 7-13, 7-30, 7-32
sulfide scavenger solubility 8-10
sulfide scavengers 8-10, 8-14
sulfite reducing bacteria 7-27
sulfonates 8-18
sulfur dioxide 6-10, 6-23
sulfur isotope differentiation method 7-32
sulfur oxidizing bacteria 7-17, 7-18
supersaturation ratio 5-10
surface disposal 1-7
surfactant 8-8, 8-14, 8-23
solubility 8-19
surfactant cleaners 8-14
surfactant interactions 8-18, 8-23
surfactant solubility 8-9
surfactants 1-10, 1-12, 1-15, 1-17, 3-24, 3-31, 5-22, 8-5, 8-9,
8-23, 10-7
suspended solids 1-5, 1-7, 1-16, 2-4
system accumulation 10-7
system chemistry 8-23
system design 10-10
system upsets 10-10
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
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
water sensitivity 3-4
water softeners 10-9
water sources
open water 1-4, 1-6
produced waters 1-4, 1-5
source wells 1-4, 1-6
water treating
challenges 1-3
enhanced oil recovery 1-3, 1-4, 1-12, 1-14
new waterfloods 1-4
old waterfloods 1-3
systems 1-3, 1-8
water treatment
general objectives 1-10, 1-13
injection requirements 1-9, 1-10
methods - chemical 1-10, 1-15, 1-17
methods and equipment 1-10, 1-15
requirements 1-10, 1-13
special objectives 1-7
surface disposal requirements 1-10, 1-12
water treatment chemicals 3-33
water treatment plan design 10-7
waterflood 10-14
waterflooding 10-3
waxes 8-23
weight percent (% or wt %) 2-37
weighted brines 8-13
well backflowed 8-13
well completion 10-21
well injectivity 10-15
well squeeze 8-6
well stimulation chemicals 8-11
well workovers 10-7
wetting agent 1-12
wetting agents 8-23
Wilmington Field 7-5
workover fluids 8-13, 8-23, 10-10
X
x-ray diffraction (XRD) 2-66
x-ray fluorescence (XRF) 2-66
Z
zero discharge 10-14
zinc chlorides 8-8