SCALE FORMATION AND TREATMENT

INTRODUCTION:

Scale is deposited in formation matrix and fractures, well bore, down hole pumps,
tubing, casing, flow lines, heater treaters, tanks, and salt water disposal and water
flood systems. Scale deposits usually form as a result of crystallization and
precipitation of minerals from water.

CAUSES:
The direct cause of scaling is frequently due to pressure drop, temperature change,
mixing of two incompatible waters, or exceeding the solubility product. Scales
sometimes block oil & gas production by plugging the formation matrix or fractures,
perforations, well bore or producing equipments.

COMPOSITION OF SCALES:
The most of the oil fields scales are deposited calcium carbonate (CaCO3),
gypsum (CaSO4 . 2H2O), Barium Sulphate (BaSO4) and Sodium Chloride (NaCl).

Calcium Sulphate (CaSO4) or anhydrite does not usually deposited down hole
but may be deposited in boilers and heater treaters. Less common scale deposits are
Strontium Sulphate (SrSO4) .

Insoluble scales indicate Barium Strontium Sulphate BaSr(SO4)2 .

Various iron compounds like iron carbonate (FeCO3), Iron oxide (Fe2O3) and
iron Suphide (FeS) usually result as a corrosive product due to CO 2 , H2S or Oxygen
dissolved in the water.

Scale deposited very rapidly may have gas channels, be very porous and
easy to remove with acid. Scale deposited slowly may be very hard and dense and
difficult to remove with acid or other chemicals.

Tendency to Scale CaCO3 (Acid Soluble Scale) :

i. In oil wells, Calcium Carbonate precipitation is usually caused by pressure
drop releasing CO2 from Bi-Carbonate ions (HCO3- ). When CO2is
released from solution pH increases, the solubility of dissolved carbonate
decreases and the more soluble bicarbonates are converted to the less
soluble carbonate. Loss of only 100 mg of bi-carbonate per litre of water
can result the deposition of 28.6 lb of calcium carbonate per 1000 bbl of
produced water.
ii. Scale precipitation may also vary with Calcium ion concentration
(Common ion effect – such as from (CaCl2), alkalinity of water
(concentration of bicarbonate ion), temperature, total salt concentration,
contact time and degree of agitation
iii. Scaling will increase with increase in temperature as solubility of Calcium
Carbonate will decrease with increase in temperature.
iv. Scaling increase with increase in pH.
v. Scaling increases and becomes harder with increase in contact time.
vi. Scaling decreases as total salt content (not counting Calcium ions) of
water increases to a concentration of 120g NaCl / 1000g of water. Further
increases in NaCl concentration decreases CaCO3 Solubility and scaling
increases.
vii. Scaling increases with increase in turbulence.
 viii. Mixing of two incompatible waters will cause precipitation of CaCO3 scale
like in the mixing of saline water with fresh water highly charged with bi-
carbonate.

Tendency to scale – Gypsum (CaSO4.H2o) or Anhydrite (CaSO4) (

Acid Insoluble Scale)

i. The most common form of Calcium Sulphate scale deposited down hole
is Hydrous Calcium Sulphate or Gypsum (CaSO4.H2O).
ii. A reduction on pressure decreases solubility and causes scaling.
Pressure drop from 2000 psi to atmospheric pressure may precipitate 900
ppm (0.3 lb/ bbl of water) Calcium sulphate from typical basin saline
water.
iii. Mixing of two water one containing calcium ions and the other containing
sulphate ions cause gypsum scaling particularly in water flooding job.
iv. Casing leaks or poor cement jobs are frequent causes of scaling due to
down hole mixing of water form the producing zone and water form other
porous zone.
v. An increase of Magnesium ions up to 24,000 to 36,000 mg/litre may
increase the solubility of CaSO4 in distilled water hereby decrease scaling
tendency.
vi. Agitation increases scaling tendency.
vii. With the increase pH range of 6 to 8 pH has very little effect of solubility
and scaling.
viii. Evaporation of water due to evolution of free gas near or in the well bore
may cause super saturation and Gypsum scaling.
ix. Hydrates in gas wells frequently become super saturated due to
evaporation with result scaling.
x. A change in temperature will change the solubility of Calcium Sulphate
and the tendency to precipitate.
xi. In the wells having Anhydrite (CaSO4) stringers in the producing zones,
water flowing in the reservoir in saturated with anhydrite. The same water
at disturbed flow conditions near the well bore is super saturated with
respect to the Gypsum and will precipitate gypsum scale.

Tendency to Scale BaSO4 and SrSO4 (Chemically Inert Scales) :

i. For a given NaCl solution, BaSO4 scaling increases with decrease in
temperature as a result of decreasing BaSO4 solubility.
ii. Both BaSO4 and SrSO4 scales are usually caused by mingling of two
unlike waters, one containing soluble salts of Barium or Strontium and the
other containing soluble sulphate.
iii. Pressure drop may affect the solubility of Barium Sulphate in a given
solution of NaCl.
iv. Barium Sulphate is often precipitated in gas wells as hydrates are
evaporated.
v. Solubility of Barium Sulphate in high salinity oil fields brine may vary from
85 – 100 mg / litre.

Tendency to Scale NaCl (Water Soluble Scales) :

i. Precipitation of NaCl is normally caused by super-saturation due to
evaporation or decrease in temperature. 4000 mg / litre of NaCl may be
precipitated from saturated salt water if temperature drops from 140 – 86
deg F.
ii. Salt precipitation may be severe near bottom in gas producing wells or
high GOR oil wells producing very small volume of water.
 iii. Precipitation may result from both drop in temperature and pressure
through perforations and in to the tubing. Dry gas will evaporate the water
leaving the salt as a precipitated scale.

PREDICTION OF SCALES

i. Analysis of water properties immediately after sampling is the best approach

to predict the scale formation tendency.
ii. Analysis of water flood water provides a reliable basis for estimating scaling in
injection lines and down hole in injection wells.
iii. Analysis of produced brine predicts the scaling in the surface facilities. It may
provide the basis to estimate the scaling in the down hole equipments in
producing wells because of possible prior deposition of scales due to release
of CO2 form Bi-carbonate ions in water as pressure declines.
iv. If bottom hole pressure is near original, bottom hole sample brought under
subsurface condition may provide reliable information on both down hole and
surface scaling tendencies under original reservoir condition.
v. To determine Calcium carbonate super saturation, take a well head sample of
water and run test on water at the time of sampling. If the calcium carbonate
super saturation is more than 10% of bi-carbonate alkalinity content, then the
water will usually have a scaling tendency.

IDENTIFICATION OF SCALES

i. X-ray diffraction is the most used method for the scale identification. This
involves directing a beam of X-ray on to a powdered sample of scale
crystal.
ii. Each chemical compound in the scale diffracts x-rays in a characteristics
manner which permits its identification. It is the fastest method and
requires least amount of sample.
iii. Chemical analysis may also be used for scale identification. Samples of
scales are decomposed and then dissolved in chemical solution. Scale
compounds are then analysed by standard techniques of titration or
precipitation.
iv. Scale compounds will usually not be identified unless the analysis is
made for each specific chemical compound, By comparison, all chemical
compound can readily be identified form an x-ray analysis.
v. After adding HCl to the scale sample, effervescence usually indicates
CaCO3, specially if the sample does not contain iron sulphate or iron
carbonate.

SCALE REMOVAL

Scale is classified by method of removal. Chemically inert scales are not

soluble in chemicals. Chemically reactive scales may be classified as water
soluble, acid soluble and soluble in chemicals other than water or acids

MECHANICAL METHOD:

For perforated casing, re-perforating is a most effective method of bypassing

perforations sealed with scale. Mechanical methods such as string shot, sonic
tools, drilling, or reaming have been used to remove both soluble & insoluble
scales from tubing, casing or open holes. Scales may be removed from surface
lines with pigging or reaming out.
CHEMICAL REMOVAL:

WATER SOLUBLE SCALES:

i. The most common water soluble scale is NaCl scale which can be readily
dissolved with relatively fresh water, Acid should not be used to remove
NaCl scales.
ii. If gypsum scale is newly formed and porous, it may be dissolved by
circulating water containing about 55,000 mg/litre NaCl past the scale. At
100 deg F, 55,000 mg/ litre NaCl will dissolve three times as much as
gypsum as fresh water.

ACID SOLUBLE SCALES:

i. The most prevalent of all scale compounds, Calcium carbonate (CaCO3),

is acid soluble. HCl or Acetic acid can be used to remove calcium
carbonate. Formic acid and sulphonic acids have been used effectively to
remove such scales.
ii. Acetic acid has special application down the hole in pumping wells when it
is desired to leave chrome plated or alloy pumps in a well during acid
treatment. Acetic acid will not damage chrome plated surfaces at
temperature below 200 deg. F, However HCl may severely damage the
chrome plated surfaces.
iii. Acid soluble scales also include iron carbonate (FeCO3), iron sulphide
(FeS), and iron oxide (Fe2O3).
iv. HCl plus a sequestering agent is normally used to remove iron scale. The
sequestering agents holds iron in solution until it can be produced from
the well. A sequestered Fe acid , such as HCl + .75% Acetic acid + .55%
citric acid may provide over 15 days of sequestering time.
v. Normally 15% sequestered HCl is used but 20% may be necessary
because of slow reaction with iron compounds.
vi. A 10% solution of Acetic acid may be used to remove iron scales without
an additional sequestering agent. However Acetic acid is much slower
than HCl.
------------------------------------------------------------------------------------------------
Type of acid soluble scale Gallons of 15% HCl/Cu ft of scale
-----------------------------------------------------------------------------------------------
CaCO3 95
Fe2O3 318
FeS 180
-----------------------------------------------------------------------------------------------
ACID INSOLUBLE SCALES:
i. The only acid insoluble scale which is chemically reactive is Calcium
Sulphate or gypsum. Calcium sulphate though not reactive in acid, can be
treated with chemical solutions which can convert calcium sulphate to an
acid soluble cmpounds like Calcium carbonate or calcium Hydroxide
CaCO3 or Ca(OH)2 which can be removed with acid.

-----------------------------------------------------------------------------------
----------
Type of solution % of gypsum dissolved
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
------------------------------------------------------------------------------
-----------------

ii. most of the chemical shown above convert gypsum to CaCO3 . KOH
converts gypsum to Ca(OH)2 , which is soluble in water or a weak acid;
however only 68 – 72% is converted to gypsum leaving an undissolved
scale in matrix.
iii. After converting gypsum the residual fluid is circulated out. CaCO 3 can be
removed with either HCl or Acetic acid.

SCALE REMOVAL IF WAXES, IRON CARBONATE AND GYPSUM ARE

PRESENT:
i. Degrease with a solvent such as Kerosene or Carbon Di-sulphide plus a
surfactant.
ii. Remove iron scales with a sequestered acid.
iii. Convert gypsum scales to CaCO3 or Ca(OH)2.
iv. Remove converted CaCO3 scale with HCl or Acetic acid. Dissolve
Ca(OH)2 with water or weak acid.
v. Compounds such as EDTA (Ethylene di-amine Tetra-acetic acid) and
DTPA (Di-ethylene Tri-amine Penta-acetic acid) can dissolve gypsum
without the necessity of conversion to CaCO 3 or Ca(OH)2. But EDTA or
DTPA are not used because of high cost.

CHEMICALLY INERT SCALES:

The most common chemically inert scales are Barium Sulphate (BaSO 4) and
Strontium Sulphate SrSO4 . Barium Sulphate scales on the formation face or in the
perforation may be removed by mechanical methods such as string shots, drilling out
or under reaming or by-passing by re-perforating. The best approach is to prevent
the scale deposition.