Produced Water Treating

Systems
DR. FATMA ASHOUR
INTRODUCTION
When hydrocarbons (crude oil, condensate, and natural gas) are produced, the
well stream typically contains water produced in association with these
hydrocarbons. The produced water is usually brine, brackish, or salty in quality
but in rare situations may be nearly “fresh” in quality.
Water must be separated from the hydrocarbons and disposed of in a manner
that does not violate established environmental regulations.
Typically, the produced water is separated from the hydrocarbons by passing the
well stream through process equipment such as three-phase separators, heater-
treaters, and/or a free-water knockout vessel.
These gravity separation devices do not achieve a full 100% separation of the
hydrocarbons from the produced water.
The produced water separated from the hydrocarbons in these gravity
separation devices will contain 0.1 to 10 volume percent of dispersed and
dissolved hydrocarbons. Produced water treating facilities are used to further
reduce the hydrocarbon content in the produced water prior to final disposal.
Regulatory standards for overboard disposal of produced water into offshore
surface waters vary from country to country. Failure to comply with such
regulations results in civil penalties, large fines, and lost or deferred production.
Intentional violation of these regulations can result in criminal prosecution of
officers and other individuals acting on behalf of the company who intentionally
neglected compliance.
Currently, regulations require the “total oil and grease” content of the effluent
water to be reduced to levels ranging between 15 mg/l to 50 mg/l depending
upon the host country. For U.S. offshore operations, the current standard is 29
mg/l.
Disposal of produced water into onshore surface waters is prohibited by
environmental regulations. Onshore disposal requires the produced water
effluent to be injected into a saltwater disposal well.
Onshore produced water treating for hydrocarbon removal prior to injection
into a saltwater disposal well is not commonly regulated; however, a regulatory
permit is typically required before initiating any substrata water disposal
injection project.
The permitting procedure helps to safeguard subsurface drinking water supplies
by assuring that disposal wells are drilled and completed in a manner so the
fresh drinking water supply zones are isolated from communication with any
brackish or salty water zones.
Dispersed hydrocarbon removal to very low levels, comparable to those
required for offshore discharge may still be required to prepare the water for
downstream solids filtering equipment.
Disposal Standards
Offshore Operations
Standards for the disposal or produced water to surface waters both onshore
and offshore are developed by governmental regulatory authorities.
In addition to placing limits on the oil content, regulatory agencies generally
specify an analytical method for determining the oil content.
Produced water toxicity is regulated only in the United States, where a
government permit is necessary to limit the toxicity of produced water
discharged into the waters.
Disposal Standards
Worldwide Produced Water Effluent Oil Concentration Limitations
Ecuador, Colombia, Brazil 30 mg/l All facilities
Argentina and Venezuela 15 mg/l New facilities
Indonesia 25 mg/l Grandfathered facilities
Malaysia, Middle East 30 mg/l All facilities
Nigeria, Angola, Cameroon, Ivory Coast 50 mg/l All facilities
North Sea, Australia 30 mg/l All facilities
Thailand 50 mg/l All facilities
USA 29 mg/l OCS water
Zero discharge inland water
Onshore Operations
Disposal of produced water into freshwater streams and rivers is generally
prohibited except for the very limited cases where the effluent is low in salinity.
Some oil-field brines might kill freshwater fish and vegetation due to high salt
content.
Regulatory agencies generally require that produced water from onshore
operations be disposed of by subsurface injection, although there are limited
exceptions.
In addition to requiring subsurface disposal, regulatory agencies regulate the
completion and operation of the disposal wells.
Characteristics of Produced Water
Produced water contains a number of substances, in addition to hydrocarbons,
that affect the manner in which the water is handled.
The composition and concentration of substances may vary between fields and
even between different production zones within a single field.
The terminology used for concentration is milligrams per liter (mg/l), which is
mass per volume ratio and is approximately equal to parts per million (ppm).
Dissolved Solids
Produced waters contain dissolved solids, but the amount varies from less than
100 mg/l to over 300,000 mg/l, depending on the geographical location as well
as the age and type of reservoir.
In general, water produced with gas is condensed water vapor with few
dissolved solids and will be Fresh with a very low salinity.
Aquifer water produced with gas or oil will be much higher in dissolved solids.
Produced water from hot reservoirs tends to have higher TDS concentrations
while cooler reservoirs tend to have lower levels of TDS.
Dissolved solids are inorganic constituents that are predominantly sodium (Na+)
cations and chloride (Cl−) anions. Other common cations are calcium (Ca2+),
magnesium (Mg2+), and iron (Fe2+), while barium (Ba2+), potassium (K+),
strontium (Sr+), aluminum (Al3+), and lithium (Li+) are encountered less
frequently. Other anions present are bicarbonate (HCO−3 ), carbonate (CO2−3 ),
and sulfate (SO−4 ).
All produced water treating facilities should have water analysis data for each
major reservoir and for the combined produced water stream. Especially
important are constituents that could precipitate to form scales.
Precipitated Solids (Scales)
The more troublesome ions are those that react to form precipitates when
pressure, temperature, or composition changes occur. The wellknown deposits
that form in tubing, flowlines, vessels, and produced water treating equipment.
Mixing of oxygenated deck drain water with produced water should be avoided
because this may result in the formation of calcium carbonate (CaCO3), calcium
sulfate (CaSO4), and iron sulfide (FeS2) scale, along with oil-coated solids.
Calcium Carbonate (CaCO3 )

Calcium carbonate (CaCO3) precipitate can be formed by mixing two dissimilar

waters, but the usual cause is the reduction in pressure and release of dissolved
carbon dioxide from produced water. This increases the produced water’s pH,
which reduces the solubility of CaCO3 and leads to scale precipitate.
Temperature effects are equally important since CaCO3 is less soluble at higher
temperatures and will form a deposit in heat exchangers, heaters, and treaters.
Its solubility in fresh water is approximately 1,000 mg/l at 60F 15C and
diminishes to 230 mg/l asTemperature is increased to 200F 93C. Fortunately,
higher salinity increases CaCO3 solubility in produced water to a value greater
than that given above for pure water.
Calcium Sulfate (CaSO4)

Calcium sulfate (CaSO4) is one of several sulfate scales and is also called gypsum.
It forms either as a result of mixing dissimilar waters or naturally as a result of
changes in temperature and pressure as the water travels from the subsurface
to the surface treating facility.
CaSO4 solubility is at its maximum level of 2,150 mg/l at approximately 100F
38C and diminishes to 2,000 mg/l as it cools to 60F 15C.
The solubility of CaSO4 also declines with increasing temperature above 100F
with its solubility reducing to 1,600 mg/l at 200F 93C. CaSO4 also increases in
solubility as the salinity of the produced water increases.
Barium and Strontium Sulfate ( BaSO4
and SrSO4)
Barium and strontium sulfate (BaSO4 and SrSO4) are much less soluble than
calcium sulfate, but they are not as common in produced waters.
BaSO4 solubility is quite low, having a value of approximately 3 mg/l over the
range from 100F 15C to 200F 93C. SrSO4 solubility is 129 mg/l at 77F 25C and
diminishes to 68 mg/l as the solution temperature increases to 257F 125C. If a
produced water stream containing appreciable quantities of barium or
strontium ions is mixed with sulfate-rich water, barium and/or strontium scaling
can be expected.
These waters are incompatible due to this scaling characteristic and should not
be mixed.
Iron Sulfide (FeS2 )

Iron sulfide (FeS2) is a product of corrosion caused by waters containing

dissolved hydrogen sulfide coming into contact with equipment fabricated from
carbon steel or iron materials. Mixing water containing iron cations (Fe2+) with
another water containing hydrogen sulfide will also result in an FeS2 precipitate.
Scale Removal
Hydrochloric acid can be used to dissolve calcium carbonate and iron sulfide scales. However,
iron sulfide chemically reacts with hydrochloric acid and produces hydrogen sulfide, a highly
toxic gas having the odor of rotten eggs.
Due to the high toxicity of hydrogen sulfide, safety provisions need to be implemented. Calcium
sulfate is not soluble in hydrochloric acid, but chemicals are available that will convert it to an
acid-soluble form that can then be removed by the acid. This process is slow; however, because
a two-step process must be repeated to strip the scale layer by layer.
Thus, the removal of calcium sulfate is more difficult than the removal of calcium carbonate.
Practical means of dissolving barium or strontium sulfate are not available. These hard scales
can be removed by mechanical means, which is a time-consuming process. Mechanical removal
of scale can create a disposal problem for the resulting waste material and possibly could result
in contamination by naturally occurring radioactive materials (NORM).
Controlling Scale Using Chemical
Inhibitors
Scale-inhibiting chemicals are available to retard or prevent all types of scale.
They mostly function by enveloping a newly precipitated crystal, thereby
retarding growth. Common scale inhibitors include:
Inorganic phosphates (inexpensive but only applicable at low temperature)
Organic phosphate esters (easy to monitor but limited to temperatures below
100F
Phosphates (easy to monitor and have a higher thermal stability to 150F
Polymers (best thermal stability and effectiveness, but difficult to monitor).