Pipeline Scale
Mineral salts deposits
A deposit or coating formed on the
surface of metal, rock or other material.
➢ Causes of scale deposition:
i. Supersaturation
ii. Mingling of two unlike waters
having incompatible compounds in
solution
iii. Change of temperature
iv. Change of pressure on solution
v. Evaporation (affects concentration)
vi. Agitation
vii. Long exposure time (crystal growth)
viii. Change of pH
Pipeline
The most common scale deposits in
oil and gas pipeline
Minerals Formula
Calcite CaCO3
Anhydrite CaSO4
Halite NaCl
Barite BaSO4
Pipeline
Mechanism
Auto scaling Incompatible mixing
Another mechanism is the
Scale appears as minerals starting incompatible mixing when two
to precipitate when the fluids mix together and the ion
concentration of mineral exceeds concentration rises above solubility
its saturation limit. This could be limits. Two fluids mixing usually
caused by the change of some happen in process like enhanced oil
physical properties of fluid recovery operations where the sea
(usually water) such as pressure, water is injected and this interacts
temperature, and pH. chemically with the formation
water.
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Super Saturation
Aqueous solutions can become supersaturated, which means that they
contain higher concentrations of dissolved solute than their equilibrium
concentration. Such solutions are not stable and are easily triggered into
dropping back to saturation level, forcing the dissolved compound to
precipitate. Even when a bulk solution is less than fully saturated, scale
formation can occur spontaneously due to localized super saturation, at a
surface for example.
pH Effect
The pH of the solution is directly related to its acid content (typically
carbonic acid). The higher the acid content, the lower the pH number. The
solubility of calcium carbonate is directly affected by the pH of the water. If
the pH of the water is decreased, more calcium carbonate solid can be
dissolved. Conversely, if the pH of the water rises, it will force calcium
carbonate out of solution and scale deposits will therefore form.
Pipeline
H2O + CO2 → H2CO3 (carbonic acid)→ Relatively weak naturally
occurring acid
2HCO3-2 → CO3 2- + CO2 + H2O
Ca+2 + CO32- → CaCO3
Calcium carbonate is usually caused by pressure drop releasing
CO2 from bicarbonate ions (HCO3-1). When CO2 is released from
solution, the pH increases, and the more soluble bicarbonates are
converted to less soluble carbonates.
Pipeline Temperature Effect
Gases in general - specifically carbon dioxide - are less soluble in water at
high temperatures. Therefore, as the temperature rises, the dissolved carbon
dioxide decreases. This increases the pH of the fluid, reducing the solubility
of the calcium carbonate and forcing the mineral to deposit.
Pipeline
Pressure Effect
Carbon dioxide and gases in general are more soluble under higher
pressure. Therefore, as the pressure drops, carbon dioxide gas will be
forced out of solution, lowering the carbonic acid concentration. The
rise in pH is associated with a drop in calcium carbonate solubility,
leading to the formation of mineral scale deposits.
Pipeline
Identification of scale
X-ray diffraction Chemical Analysis
This involves directing a beam of X-rays
Chemical analysis may also be used for
onto a powdered sample of scale crystals.
scale identification. Samples of scale
Each crystalline chemical compound in the
decomposed and then dissolved in
scale diffracts X-rays in a characteristic
chemical solution. Chemical elements are
manner, which permits its identification. It
then analyzed by standard techniques of
is the fastest method and require the least
titration or precipitation.
amount of sample.
Pipeline
XRD
Pipeline Laboratory or Field Test for Scale
Scale Additive for Test Results
Acid Soluble Scale
Calcium Carbonate HCl Bubbles vigorously
Iron Carbonate HCl Bubbles-Solution yellow
Iron Sulfide HCl Bubbles-H2S gas
Iron Oxide HCl Dissolves-Solution yellow
Magnesium Hydroxide HCl Dissolves-Solution clear
Acid Insoluble Scale
Calcium Sulfate 1. Soak overnight in Bubbles vigorously
Baking Soda (NaHCO3)
2. Treat with HCl
Barium Sulfate -------------------------- Not soluble
Strontium Sulfate -------------------------- Not soluble
Sodium Chloride Fresh water Dissolves
Pipeline
Scale Removal
Mechanical Chemical
Mechanical removal is done by
means of a pig or by abrasive jetting
that cuts scale but leaves the tubing (i) Water Soluble (Ex- (iii) Soluble in
(ii) Acid soluble (Ex-
untouched. Pig is a device with Sodium Chloride, Calcium carbonate, chemicals other
blades or brushes inserted in a Newly formed and Iron carbonate, Iron than water or
pipeline for cleaning purposes. The porous gypsum sulfide, Iron Oxide acid (Ex-
pressure of the oil stream behind scale) Gypsum)
pushes the pig along the pipeline to
clean out rust, wax, scale and debris.
To clean downhole tubulars a similar
device, called a casing scraper or
paraffin scraper, may be used.
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Pigging
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Water Soluble Scale
➢NaCl: can be readily dissolved with relatively fresh water.
Acid should not be used to remove NaCl scale.
➢Newly formed porous gypsum (CaSO4.H2O): If gypsum
scale is newly formed and porous, it may be dissolved by
circulating water containing about 55,000 mg/L NaCl past the
scale. At 100℉ 55,000 mg/L NaCl will dissolve three times as
much gypsum as fresh water.
Pipeline
Acid-Soluble Scale
➢CaCO3(Calcium Carbonate): Hydrochloric acid (HCl) or acetic
acid (CH3COOH) can be used to remove calcium carbonate.
Formic acid or sulfamic acid have also been used.
➢Iron carbonate (FeCO3), Iron sulfide (FeS), and iron oxide
(Fe2O3): HCl plus a sequestering agent is normally used to
remove iron scale. It is essential to stabilize the ferric iron to
prevent precipitation of ferric hydroxide from spent acid
solutions. Sequestering agent most commonly used include citric
acid, acetic acid, mixtures of citric and acetic acids, EDTA
(Ethylenediaminetetraacetic acid) and NTA (Nitriloacetic acid).
Pipeline
✓In addition to the commonly used sequesting agents, reducing agents
such as Dowell Schlumberger’s patented erythorbic acid can be used to
prevent precipitation of ferric hydroxide.
✓Citric acid, EDTA, NTA and erythorbic acid have been proven to be
effective Fe stabilizers for several days at temperature up to at least
400℉.
✓Normally sequestered 15% HCl is used, but 20% may be necessary
because of slow reaction with iron compounds.
✓A 10% solution of Acetic acid may be used to remove iron scales
without an additional sequestering agents, however, acetic acid is much
slower acting than HCl.
✓Scales are frequently coated with hydrocarbon, thus making it difficult
for acid to contact and dissolves the scales. Surfactants can be added to
all types of acid solutions to develop a better acid-to-scale contact.
Pipeline Acid Required for CaCO3 and Iron Scales
Types of acid-soluble scale Gallons of 15% HCl/cu ft of scale
CaCO3 95
Fe2O3 318
FeS 180
Sequestering Agent: Another term for chelating agent, a chemical added to
an acid to stabilize iron. The injected acid dissolves iron from rust, mill scale,
iron scales or iron-containing minerals in the formation. Iron can exist as
ferric iron [Fe+3] or ferrous iron [Fe+2]. If the iron is not controlled, it will
precipitate insoluble products such as ferric hydroxide and, in sour
environments ferrous sulfide [FeS], which will damage the formation.
Chelating agents associate with iron [Fe+3 or Fe+2] to form soluble
complexes. Citric acid, acetic acid and EDTA are effective chelating agents
and can be used at temperatures up to 400℉ [204℃].
Pipeline
Acid Insoluble Scales
➢ Calcium Sulfate (Gypsum): Calcium sulfate though not reactive in acid,
can be treated with chemical solutions which can convert calcium sulfate
to an acid soluble compound, such as CaCO3 or Ca(OH)2.
Gypsum Solubility Tests
Types of solution Percent gyp converted
24 Hours 72 Hours
NH4HCO3 87.8 91.0
Na2CO3 83.8 85.5
Na2CO3-NaOH 71.2 85.5
KOH 67.6 71.5
Most of the chemicals shown in table convert gypsum to acid-soluble CaCO3. KOH
converts gyp to Ca(OH)2, which is soluble in water or a weak acid; however, only
68 to 72% is converted to Ca(OH)2, leaving an unconverted scale matrix. After
converting gyp, the residual fluid is circulate d out. CaCO3 can then be removed
with either HCl or Acetic acid.
Pipeline
Scale removal procedure if waxes, iron carbonate
and gyp are present:
✓ Degrease with a solvent such as kerosene, or xylene, plus a
surfactant.
✓ Remove iron scales with a sequestered acid.
✓ Convert gyp scales to CaCO3 or Ca(OH)2
✓ Dissolve converted CaCO3 scale with HCl or acetic acid.
Dissolve Ca(OH)2 with water or weak acid.
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