Water Formed Scales

“Main Topics”
o Why Scales Form
o Common Scales
o Predicting Scale Formation
o Compatibility
o Scale Formation Prevention
o Scale Removal Methods
 Why Scales Form

o Water contains ions which are

capable of forming compound of
limited solubility

o There is a change in the physical

conditions
Scale Formation Drawbacks
o Scale formation frequently restricts the
flow through injection , flow lines and
tubing strings

o It causes pump wear or plugging Fire

tubes in all types of heaters fail
prematurely due to overheating

o Corrosion is more severe under scale

formation
 Common Scales
Name Chemical Formula
oCalcium Carbonate CaCO3
oCalcium Sulfate:
 Gypsum CaSO4 . 2H2O
 Hemi-Hydrate CaSO4. ½ H2O
 Anhdrite CaSO4

oBarium Sulfate BaSO4

oStrontium Sulfate SrSO4

 Common Scales(cont.)
Name Chemical Formula
oFerrous Compounds:
 Ferrous Carbonate FeCO3
 Ferrous Sulfide FeS
 Ferrous Hydroxide Fe(OH)2
 Ferric Hydroxide Fe(OH)3
 Ferric Oxide
Fe2O3
 CaCO3
o Calcium carbonate scale is formed
by the combination of calcium ion
with either carbonate or
bicarbonate depending on the
solution pH:

Ca+2 + CO3 -2 = CaCO3

Ca+2 + 2HCO3-1 = CaCO3 + CO2 + H2O
 CaCO3
(Effect of CO2)
o When CO2 dissolves in water , it
forms carbonic acid , which ionizes
according to the following
equations:

CO2 + H2O = H2CO3

H2CO3 = H+ + HCO3-1
HCO3–1 = H+ + CO3-2
 CaCO3
( Effect of CO2 )
“cont.”
o CO2 partial pressure =
CO2 Mole fraction x Total Pressure
o The solubility of CaCO3 increases when the
system pressure is increased or the amount of
CO2 is increased
o Conclusion:
The probability of CaCO3 deposition increases
when the partial pressure decreases
 CaCO3
(Effect of pH)
o The amount of CO2 present in the water affects
the pH of the solution and hence the solubility of
CaCO3

o Conclusion:
The probability of CaCO3 deposition increases
when the pH increases
 CaCO3
(Effect of
o
Temperature)
Calcium carbonate becomes less soluble as
temperature increases
o The increase in temperature helps CO2 to get out
of the system, the pH increases and the CaCO3
precipitates

o Conclusion:
The probability of CaCO3 deposition increases
when the temperature increases
 CaCO3
(Effect of Dissolved Salts)
o Calcium carbonate solubility increases as the
amount of salt content increases
o Adding 200,000 ppm NaCl to distilled water
increases the solubility of from 100 to 250 ppm
o Conclusion :
The probability of CaCO3 deposition increases
with the decrease of dissolved salts
 CaCO3 Formation
(Summary)
The probability of CaCO3 deposition :

o Increases with temperature

o Increases as partial pressure of CO2 decreases
o Increases as the pH increases
o Increases as total dissolved salts decreases
 CaSO4
o The calcium sulfate precipitation occurs according to the
equation:
o Ca+2 + SO4 –2 = CaSO4
o Forms of calcium sulfate:
 Gypsum (CaSO4 . 2H2O) is most stable at
temperature of 40 C or less at atmospheric pressure
 Above this temperature , anhydrite (CaSO4) may be found
 Hemi-hydrate may be found at certain temperature
 CaSO4
(Effect of
Temperature)
o Gypsum solubility increases with temperature up to 40
C, then it decreases with temperature rise (probability
of deposition increases above 40 C)

o Anhydrite and semi-hydrate are likely to occur at high

temperatures (solubility decreases by temperature rise)
CaSO4
(Effect of Dissolved Salts)
o Up to 150,000 ppm NaCl concentration:
The increase in NaCl concentration increases the
solubility of gypsum

o Above 150,000 ppm NaCl concentration:

The solubility of gypsum decreases with NaCl increase
CaSO4
(Effect of Pressure)
o The solubility of CaSO4 increases with the
pressure increase

o Conclusion:
Deposition of CaSO4 increases at low pressures
 BaSO4
o It is the least soluble scale

o It is formed as per the equation:

Ba+2 + SO4 -2 = BaSO4

o The extreme insolubility of BaSO4

makes it is more likely to occur once
Ba+2 and SO4 -2 exist
 BaSO4
(Effect of Temperature)
o The solubility of BaSO4 increases slightly with temperature
increase

o The increase is fairly substantial percentage wise

o Conclusion:

The deposition of barium sulfate is more likely at low temperatures

 BaSO4
(Effect of Dissolved Salts)

o Solubility increases with high dissolved salts

o The addition of 100,000 ppm NaCl to distilled water
increases the solubility from 2 to 3 ppm at 25 C
o At100,000 ppm salinity & 95 C, solubility will be about
65 ppm
o Conclusion:
The deposition of barium sulfate is more likely at low
salinity
 BaSO4
(Effect of Pressure)

o Solubility increases with the increase of

pressure as CaSO4 and CaCO3
 SrSO4
o The solubility of SrSO4 is very similar to BaSO4 , but it is
much more soluble than BaSO4

o SrSO4 solubility decreases with temperature and increased

dissolved salts

o SrSO4 seldom occurs as simple strontium sulfate. It usually

co-precipitates with barium sulfate
 Iron Compounds
o Iron ions present in water may be either naturally present in the water
or the result of corrosion

o Formation water normally contains only a few mg/lit of natural iron and
values as high as 100 mg/lit

o Carbon dioxide, hydrogen sulfide and oxygen are the main species
causing iron corrosion
Silica Deposits

o Silica deposits are not common in produced waters or in the

injection projects

o They can be quite serious in boilers and cooling waters

Mixing Waters

“Compatibility”
o Individual waters may be stable at all
system conditions and present no scale
problems
o Once they are mixed, reactions between
dissolved species may form insoluble
products
o For example , mixing a water which
contains a large amount of Ba++ with a
water containing a large amount of SO4 -
- , the formation of BaSO4 is highly
possible
Compatibility Problems

o Plugging problems in surface and

subsurface problems

o Plugging problems in injection wells

at the are of contact (near matrix)
 Compatibility Testing

o Fresh samples of the waters to be

mixed are taken, filtered to remove
any suspended solids and then
mixed at different ratios
o The various sample mixtures are set
aside and observed for precipitations
o This technique is not suitable for
CaCO3 as it is very sensitive to pH
changes
 Compatibility Testing

o Fresh samples of the waters to be

mixed are taken, filtered to remove
any suspended solids and then
mixed at different ratios
o The various sample mixtures are set
aside and observed for precipitations
o This technique is not suitable for
CaCO3 as it is very sensitive to pH
changes
 Preventing Scale
Formation
Avoid Mixing Incompatible Waters:

o Using separate injection system for

each water (split system)

o Sequential injection of the two

waters
Preventing Scale Formation
(cont.)
Water Dilution:

o An injection water that has a

tendency to form scale, may be
diluted with another water so as to
the new water is stable at system
conditions
Preventing Scale Formation
(cont.)
pH Control:
o Lowering the pH will prevent
carbonate scale
o It may causes corrosion
o It is common practice in
cooling systems
o It is difficult in oil field
applications
 Scale Control Chemicals

Definition

o Scale inhibitors are chemicals

which will delay , reduce or prevent
scales when added in small
amounts to normally scaling water
 Scale Control Chemicals
Mechanism

o When scales first begin to form, very

tiny crystals precipitate from the water

o Scale inhibitor adsorbs onto the

surface of the crystal while they are
still very tiny and prevents further
growth
 Organic Scale Inhibitors

o Phosphate Esters

o Phosphonates

o Polymers
 Phosphate Esters

o They are not recommended above

175 F (79 C) as there is a danger of
hydrolysis
 Phosphonates

o They are recommended at

temperatures up to 350 F (175 C)
 Polymers

o Polymers such as acrylics are

primarily used for high temperature
applications

o They can be used up to 350 F

(175 C)
Scale Inhibitor Application

o Continuous Injection

o Batch Treatment

o Formation Squeeze
 Inorganic Polyphosphates
o Non crystalline inorganic solids

o Two types: Plain polyphosphates

Controlled solubility

o Plain polyphosphates dissolve in water fairly

rapidly

o Controlled solubility dissolve slowly in water

 Inorganic Polyphosphates
(cont.)
o Disadvantages:

1. With time, they hydrolyze to orthophosphates

2. This reacts with Ca to form insoluble calcium
phosphates and cause plugging problems
2. This reversion depends on pH and T
3. The lower the pH and the hotter the water, the
higher the reversion
 Selection and Evaluation
of Scale Inhibitors
o Factors should be considered :

1. Chemical composition
2. Severity of scale
2. Temperature
3. pH
4. Compatibility with other chemicals
 Selection and Evaluation
of Scale Inhibitors (cont.)
1. Chemical Composition

Certain compounds are more

effective for specific scales
 Selection and Evaluation
of Scale Inhibitors (cont.)
2. Severity of Scaling

o The rate of scaling may vary with time and is not

constant over the life of the well

o Lab. is effective to identify the proper scale for

definite situation
 Selection and Evaluation
of Scale Inhibitors (cont.)
3. Temperature

o Phosphate esters for low temperatures

o Phosphonates and polymers for high

temperatures
 Selection and Evaluation
of Scale Inhibitors (cont.)
4. pH

o Liquid organic phosphonate and polymers are more

effective than phosphate esters for treating in low
pH water

o The phosphates at low pH tend to hydrolyze

 Selection and Evaluation
of Scale Inhibitors (cont.)
5. Compatibility

Some scale inhibitors are incompatible with chemicals

as corrosion inhibitors, biocides and oxygen
scavengers
 Scale Inhibitors
Performance Monitoring
1. Pipe Spools or Nipples
2. Coupons
3. Visual Inspection
4. Increased Pressure Drops
5. Decreased productivity
6. Decreased Injectivity
Scale Removal Methods ( Field Scale Analysis )

o Soak the sample in a solvent to dissolve any hydrocarbons.

Watch to see if the solvent gets darker in color.

o Check to see if the sample is magnetic. If it is strongly

magnetic , it probably contains a major amount of Fe3O4
(magnetic iron oxide). If it is weekly magnetic , it may contain
a small amount of Fe3O4 or it may be FeS (iron sulphide).

o Place the sample in 15 % HCl. Note whether or not violent

reaction occurs. Note any smell (H2S indicates FeS).

o Note the color of the acid. If it turns yellow, an iron

compound is indicated. Check the solubility in water. NaCl is
water soluble
Scale Removal Methods (Field Scale Analysis-cont.)
o After the sample has been identified , a scheme can formulated to
dissolve or remove the scale.

o Chemical removal of scale follows the same principals followed for

identification.

o If the sample contains a single component, such as CaCO3, then a

single solvent as HCL is sufficient.

o It the sample contains more than one sample, a series or combination of

treating chemicals may be decided.

o Also, mechanical removal methods could be used if BaSO4 or SrSO4

are existing (in conjunction with chemicals).
 Scale Removal Methods ( Hydrocarbons)
o Acids will not react efficiently with hydrocarbon coated scale.

o Hydrocarbon solvent is needed to remove any oil, paraffin or asphaltic

materials on the scale.

o If asphaltic deposit is present, an aromatic should be used as “ Carbon

tetrachloride (but it is very toxic and represents a pollution problem).

o Carbon disulfide is also a good solvent but it has a very low flash point.

o The best way is to consult the chemical supplier.

o Safety and environmental precautions should be followed.

 Scale Removal Methods ( CaCO3)

o Hydrochloric acid is recommended as the cheapest and

easiest way to dissolve CaCO3 scale under most
conditions.

o Concentrations used are 5, 10 or 15 % .

CaCO3 + 2 HCl = H2O + CO2 + CaCl2

o See figures
 Scale Removal Methods ( CaCO3-cont.)

o EDTA = Ethylenediaminetetraacetic Acid.

o This is a chemical which chelates or complexes with

calcium ion and form a soluble compound.

o It is too expensive to use for normal oilfield cleanout

operations.

o It takes 7.4 ppm EDTA to chelate 1.0 ppm Ca.

 Scale Removal Methods ( CaSO4-Gypsum)
o HCl is not a good solvent for CaSO4.

o The maximum solubility of CaSO4 in HCl is 1.8 wt % at 25 C and

atmospheric pressure.

o The CaSO4 can be removed by the following:

 Converters
 Gypsum solvents
 EDTA
 Sodium Hydroxide (Caustic).
 Salt Water
Scale Removal Methods ( CaSO4-Gypsum-cont.)

Converters

o Inorganic converters are usually carbonates or hydroxides which

react with CaSO4 and convert it to acid soluble CaCO3 or Ca (OH)2.

o The conversion treatment is then followed by HCl to dissolve the

resulting CaCO3 or Ca(OH)2.

o A good example of this type is ammonium carbonate. The reaction

is:

CaSO4 + (NH4)2 CO3 = (NH4)2SO4 + CaCO3 (soluble)

CaCO3 + 2 HCl = H2O + CO2 + CaCl2

Scale Removal Methods ( CaSO4-Gypsum-cont.)

Converters (cont.)

o Organic converters such as sodium citrate, potassium glycollate

and potassium acetate are also used.

o These materials react with CaSO4 causing them to swell and

show fluffing materials and become soft so that they may be
removed easily by flushing with water.

o These chemicals are expensive and require several hours

contact time.

o These chemicals should be checked on an actual sample before

application.
Scale Removal Methods ( CaSO4-Gypsum-cont.)

Gypsum Solvents

o There are some chemicals which are used to dissolve

gypsum directly.

o Two examples are C-Dex and C-Dex plus .

o They are still used rarely and there is enough experience.

Scale Removal Methods ( CaSO4-Gypsum-cont.)

EDTA

o The same approach described for CaCO3 is applied.

o It needs pre-heating and some dynamic conditions.

Scale Removal Methods ( CaSO4-Gypsum-cont.)

Sodium Hydroxide – Na(OH)

o 10 % solution of NaOH will dissolve up to 12.5 of it weight

of gypsum scale.

o BE CARFUL- CAUSTIC BURNS SKIN!.

 Scale Removal Methods ( Iron Compounds)

o Hydrochloric acid is normally used to dissolve iron compounds.

o HCl must contain corrosion inhibitor to prevent pipe corrosion.

o Iron sequestering agent will prevent the possibility of re-precipitation

of iron (in case of the acid spent and the pH is increased enough)
o The reaction:

FeS + HCl = FeCl3 + H2S.

o H2S is very poisonous and a few ppm in the air can kill you.

o Masks should be used in these situations.

 Scale Removal Methods ( BaSO4)

o Dense BaSO4 is almost impossible to chemically

removed.

o Mechanical removal methods could be used if possible.

o The best way to remove BaSO4 is to prevent it from

forming.

o This can be done by efficient scale inhibitors.

 Scale Removal From Surface Lines.
o Scale removals from surface lines is usually accomplished by the combined
use of chemicals and line scrapers or “ pigs”.

o A typical flow line cleanout to remove oil coated CaCO3 from line might
consist of the following steps:

 Slug of solvent followed by a pig.

 Slug of HCl (with corrosion inhibitor and iron sequestering agent)

followed by a pig.

 Either a neutralizing solution (high pH water) or a thorough water wash

to remove all acid residuals.

o If the carbonate scale is laminated with different layers of scale and oil, a
solvent-acid emulsion is a good choice.
 Downhole Cleanout
o Downhole cleanout consists of removing scale from tubing, the
perforations or formation face.

o The same procedures of surface flow lines are used except pigging can not
be used.

o Clean out of downhole is usually a soaking operation.

o Recommended procedure:

 Remove hydrocarbons with 700 gallons xylene.

 Acidize with 400 gallons 15 % HCl containing corrosion inhibitor and
iron sequestering agent to remove corrosion products and other acid
soluble.
 Treat with 400 gallons ammonium carbonate to covert CaSO4 to CaCO3.
 Acidize with 400 gallons 15 % HCl (inhibited to remove CaCO3.