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

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.)
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







BaSO
4
(Effect of Pressure)



o Solubility increases with the
increase of pressure as CaSO
4
and
CaCO
3









SrSO
4



o The solubility of SrSO
4
is very
similar to BaSO
4
, but it is much
more soluble than BaSO
4


o SrSO
4
solubility decreases with
temperature and increased
dissolved salts

o SrSO
4
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










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 CaCO
3
oCalcium Sulfate:
Gypsum
Hemi-Hydrate
Anhdrite

CaSO
4
. 2H
2
O
CaSO
4
. H
2
O
CaSO
4
oBarium Sulfate BaSO
4

oStrontium Sulfate SrSO
4
Common Scales(cont.)










Name Chemical Formula
oFerrous Compounds:
Ferrous Carbonate
Ferrous Sulfide
Ferrous Hydroxide
Ferric Hydroxide
Ferric Oxide

FeCO
3
FeS
Fe(OH)
2
Fe(OH)
3
Fe
2
O
3

CaCO
3

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
= CaCO
3
Ca
+2
+ 2HCO3
-1
= CaCO
3 +
CO
2
+ H
2
O






CaCO
3

(Effect of CO
2
)

o When CO
2
dissolves in water , it
forms carbonic acid , which ionizes
according to the following
equations:

CO
2
+ H
2
O = H
2
CO
3
H
2
CO
3
= H
+
+ HCO
3
-1
HCO
3
1
= H
+
+ CO
3
-2




CaCO
3

( Effect of CO
2
) cont.

o CO
2
partial pressure =
CO
2
Mole fraction x Total Pressure
o The solubility of CaCO
3
increases
when the system pressure is
increased or the amount of CO
2
is
increased
o Conclusion:
The probability of CaCO3 deposition
increases when the partial pressure
decreases





CaCO
3

(Effect of pH)

o The amount of CO
2
present in the
water affects the pH of the solution
and hence the solubility of CaCO
3

o Conclusion:
The probability of CaCO
3
deposition
increases when the pH increases







CaCO
3

(Effect of Temperature)
o Calcium carbonate becomes less
soluble as temperature increases
o The increase in temperature helps

CO
2
to get out of the system, the pH
increases and the CaCO
3

precipitates

o Conclusion:
The probability of CaCO
3
deposition
increases when the temperature
increases






CaCO
3
(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 CaCO
3
deposition
increases with the decrease of
dissolved salts






CaCO3 Formation

(Summary)

The probability of CaCO
3
deposition :

o Increases with temperature
o Increases as partial pressure of CO
2
decreases
o Increases as the pH increases
o Increases as total dissolved salts
decreases







CaSO
4

o The calcium sulfate precipitation
occurs according to the equation:
o Ca
+2
+ SO
4

2
= CaSO
4
o Forms of calcium sulfate:
Gypsum (CaSO
4
. 2H
2
O) is most
stable at temperature of 40 C or less
at atmospheric pressure
Above this temperature , anhydrite
(CaSO
4
) may be found
Hemi-hydrate may be found at
certain temperature








CaSO
4

(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)








CaSO
4
(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








CaSO
4
(Effect of Pressure)

o The solubility of CaSO4 increases
with the pressure increase

o Conclusion:
Deposition of CaSO4 increases at
low pressures








BaSO
4

o It is the least soluble scale

o It is formed as per the equation:
Ba
+2
+ SO
4

-2
= BaSO
4

o The extreme insolubility of
BaSO
4
makes it is more likely to
occur once Ba
+2
and SO
4

-2
exist







BaSO
4
(Effect of Temperature)



o The solubility of BaSO
4
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





BaSO
4
(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








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 BaSO
4
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
CaCO
3
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

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.)

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.