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Scale deposition

Scale problems in production


Wells producing water are likely to develop deposits of inorganic scales. Scales can
and do coat perforations, casing, production tubulars, valves, pumps, and downhole
completion equipment, such as safety equipment and gas lift mandrels. If allowed to
proceed, this scaling will limit production, eventually requiring abandonment of the
well.
Scale deposits usually form as a result of crystallization and precipitation of minerals
from water.

Scales: crystallisation of salts from fluids


Occurrence: Scale is deposited in formation matrix and fractures, wellbore,
downhole pumps, tubing, casing, flowlines, heater treaters, tanks, and salt water
disposal and water flood systems.
Causes: Primary factors affecting scale precipitation, deposition, and crystal growth
are:

Mingling of two unlike waters having incompatible compounds in


solution; change of temperature

Supersaturation- Supersaturation is the most important reason behind mineral


precipitation. A supersaturated is the primary cause of scale formation and
occurs when a solution contains dissolved materials which are at higher
concentrations than their equilibrium concentration. The degree of
supersaturation, also known as the scaling index, is the driving force for the
precipitation reaction and a high supersaturation, therefore, implies high
possibilities for salt precipitation.

Effect of temperature
calcium sulfate is less soluble
at higher temperatures.

Change of pressure on
solution- The sulfates of calcium, barium and strontium are more soluble at
higher pressures. Consequently, formation water will often precipitate a
sulfate scale when pressure is reduced during production. The scale may

deposit round the wellbore, at the perforations, or in the downhole pump (if
used).

Evaporation (affects concentration)

Agitation

Long exposure time (crystal growth)

Change of pH-The amount of CO 2 present in the water affects the pH of the


water and the solubility of calcium carbonate. However it really does not matter
what causes the acidity or alkalinity of the water. The lower the pH, the less likely
is CaCO 3 precipitation. Conversely, the higher pH, the more likely that
precipitation will occur

Source of Oil Field Scale: The chief source of oilfield scale is mixing of
incompatible waters. Two waters are called incompatible if they interact chemically
and precipitate minerals when mixed. A typical example of incompatible waters are
-2

+2

+2

+2

sea water with high concentration of SO4 and low concentrations of Ca , Ba /Sr ,
-2

and formation waters with very low concentrations of SO4 but high concentrations of
+2

+2

+2

Ca , Ba and Sr . Mixing of these waters, therefore, causes precipitation of


CaSO4, BaSO4, and/or SrSO4. Field produced water (disposal water) can also be
incompatible with seawater. In cases where disposal water is mixed with seawater
for re-injection, scale deposition is possible. During the production, the water is
drained to the surface and suffers from significant pressure drop and temperature
variations. The successive pressure drops lead to release of the carbon dioxide with an
increase in pH value of the produced water and precipitation of calcium carbonate.
Zinc sulfide scale is more likely when zinc ion source mixes with the hydrogen sulfiderich source within the near wellbore or the production tubing during fluid extraction. Lead
and zinc sulfide scales have recently become a concern in a number oil and gas fields.
These deposits have occurred within the production tubing and topside process facilities

Composition: The composition of scales is as variable as the nature of the waters


that produce them. The most common oil field scale deposits are calcium carbonate
(CaC03), gypsum (CaS04 2HP), barium sulfate (BaS04) and sodium chloride
(NaCl). Calcium sulfate (CaS04) or anhydrite does not usually deposit downhole but
may be deposited in boilers and heater treaters. A less common deposit is strontium
sulfate ( SrSO 4) .
Nature: Scale deposited very rapidly may have gas channels, by very porous, and
be easy to remove with acid. Scale deposited slowly may be very hard and dense,

and may be difficult to remove with acid or other chemicals.

Mechanism of scaling
1. Supersaturation: Behind every chemical process, there must be a
thermodynamic driving force. For precipitation, this is given by the difference
between the chemical potential of a given substance in the stable and
metastable/labile region. To represent this driving force, the term
supersaturation is often used. At
point A, the solution is not
supersaturated, there is no
thermodynamic driving force and
therefore no precipitation. By
changing either the temperature
or the concentration e.g. by
evaporation some solute) one
can exceed the solubility
concentration (point B and D)
and cross into the
supersaturated regime. Now, a
thermodynamic driving force for
precipitation is established and
formation of solids may take place.
2. Nucleation sites: Although a driving force is established, a solution can be
supersaturated without solid formation occurring. The short explanation to this is
that the supersaturation has tobe sufficiently high; we have to be in the labile
regime of figure 1. In the metastable region of figure 1, the driving force is not

large enough to overcome the energy amount required to form a surface; a solid
particle. Spontaneous precipitation will therefore not take place. However, when
a surface is present, already existing defects at the surface can act as
nucleation sites. By this, the surface free energy required is lowered, allowing
solid particles to form and grow even in the metastable regime.
3. Precipitation nucleation is followed by precipitation and adherence.

Oilfield Scale Types


The most common scales encountered in oilfield operations are sulfates such as
calcium sulfate (anhydrite, gypsum), barium sulfate (barite), and Strontium sulfate
(celestite) and calcium carbonate. Other less common scales have also been
reported such as iron oxides, iron sulfides and iron carbonate. Lead and zinc sulfide
scale has recently become a concern in a number of North Sea oil and gas fields
(Collins and Jordan, 2001). There follows a brief description of each scale.
1. Carbonates -Calcium carbonate or calcite scale has the greatest stability in
oilfield circumstances, so it is the most common form of calcium carbonate
encountered in oilfield production operation.
Carbonate scales frequently appear in the wellbore, especially near the
wellhead where, because of pressure drop, dissolved CO2 escaped from
produced water and caused water pH as well as the saturation index of
carbonate minerals to increase.
Carbonate scale formation occurs when connate water or aquifer water passes
through the bubble point and carbon dioxide is evolved.
First, carbon dioxide reacts with water to produce carbonic acid as seen by
reaction
CO2 (g) + H2O(l ) H2CO3 (aq)
(3)
This carbonic acid will continue to dissociate hydrogen, creating new deprotonated
species of carbonic acid, as seen in reaction 4 and 5.
H2CO3 (aq) + H2O(l) H3O+ (aq) + HCO3 (aq)
(4)
HCO3 (aq) + H2O(l) H3O+ (aq) + CO2 3 (aq)
(5)
In the water mixture there will be a mixture of the species H2CO3, HCO3 and CO2 3 .
Finally, in the presence of calcium and carbonic acid, calcium carbonate will
precipitate out as seen by reaction 6.
CO2 3 (aq) + Ca2+ (aq) CaCO3 (s)
(6)
Since produced water usually contains a carbonic acid and calcium ions, a
recombination of these reactions will give a better representation of the situation, as
seen by reaction 7.
Ca (HCO3)2 (aq) CO2 (g) + H2O(l) + CaCO3 (s)
(7)
Calcium and carbonic acid together in liquid form will be in equilibrium with water,
solid calcium carbonate and CO2 gas.

Most behaviour of the calcium carbonate equilibrium can be predicted from Le


Chteliers equilibrium principle. This principle states that a chemical system at
equilibrium will always try to counteract any imposed change in pressure,
temperature, volume and composition.
Pressure dependence: When pressure is decreased in a chemical system, the
equilibrium will try compensate by increasing the pressure. Because CO2 is the only
gaseous specie, the only way to increase pressure is by shifting the equilibrium
towards producing more CO2. A decrease in pressure will then result in more
precipitation of calcium carbonate.
Concentration dependence: If the concentration of calcium or carbonic acid is
increased or the partial pressure of CO2 is decreased, then there would be an
equilibrium shift towards the right and more precipitation of calcium carbonate.
Temperature dependence: The
solubility of calcium carbonate will
decrease as the temperature
increases. This is an interesting
phenomena because most
solubilities increase with increasing
temperature and therefor one gets
less precipitation. One of the
reasons for this behaviour is the fact
that the precipitation of calcium
carbonate require energy
(endothermic). This can be written
into the equilibrium equation as
follows:
energy + Ca (HCO3)2 (aq) CO2 (g) + H2O(l) + CaCO3 (s)

(8)

When the temperature increases, the energy also increases, and the equilibrium will
try to counteract this by consuming energy. The equilibrium is then shifted towards
right, favouring precipitation of calcium carbonate.

Scaling will increase with increased temperature

Scaling increases with an increase in pH

Scaling increases and becomes harder with increased contact time.

Scaling decreases as total salt content (not counting Ca ions) of water increases
to a concentration of 1 20g N aCl/ 1 000g of water. Further increases in NaCI
concentration decrease CaC03 solubility and scaling increases

Scaling increases with increase in turbulence

Stiff Davis Method (SI) - Calcium Carbonate - Methods of Predicting Scale

SI=H-K- AK where

H=actual H of water
= - log (moles of Ca++/litre)

AK= - log (equivalents of total alkalinity/litre)


Total alkalinity= CO3-2 + HCO3-2
K=a constant which is a function of
salinity composition and water temperature
SI<0
SI=0
SI>0

Brine of Under saturated And No Tendency Of Scaling


Brine at Equilibrium
Scale Formation Is Likely

2. Sulfates
i) CaS04.2H2O or anhydrite or hemihydrate - Calcium sulfate can
crystallize from aqueous solution in three forms: gypsum (CaSO4.2H2O),
hemihydrate (CaSO4.1/2H2O) and anhydrate (CaSO4).
Gypsum, the most common scale occurs at relatively low temperature. At
higher temperature (above 100 C), the stable phase predicted is anhydrite
(CaSO4). Many parameters are affecting this problem. Temperature,
pressure, fluid concentration, ratio of brine to hydrogen, fluid dynamic and
type of porous media are among these parameters.
Causes

Mixing of two waters, one containing calcium ions and the other
containing sulfate ions, often causes gyp scaling, particularly in
water flooding.

Pressure reduction : A reduction in pressure


decreases solubility and causes scaling.
Pressure drop from 2 ,000 psi to atmospheric
pressure may precipitate as much as 900 ppm
(0. 3 Ib/bbl of water) calcium sulfate.

Casing leaks or poor cement jobs are frequent


causes of scaling due to downhole mixing of
water from the producing zone with water from
other porous zones.

Casing leaks or poor cement jobs are frequent


causes of scaling due to downhole mixing of
water from the producing zone with water
fromother porous zones.

Agitation increases scaling tendency

An increase of magnesium ions in the range of 24 ,400-36,600


mg/liter may increase the solubility of CaS04 up to several times the
solubility of CaS04 in distilled water and thereby decrease scaling.

Within the pH range of 6 to 8, p H has very little effect on solubility


and scaling.

Evaporation of water due to evolution of free gas near or in the


wellbore may cause supersaturation and gyp scaling. Hydrates in
gas wells frequently become
supersaturated due to evaporation,
with resultant scaling

The effect of temperature on


solubility of gyp scale and anhydrite
is illustrated in Figure 9-4. A
change in temperature will change
the solubility of calcium sulfate or
gyp and the tendency to
precipitate.

ii) BaS04 and SrS04 - Both BaS04 and SrS04 scales are usually caused
by mingling of two unlike waters, one containing soluble salts of barium or
strontium and the other containing sulfate ions. Barium sulfate is often
precipitated in gas wells as hydrates are evaporated.

For a given NaCl concentration, BaS04 scaling increases with


decreases in temperature as a result of decreasing BaSO4
solubility

Pressure drop may decrease the solubility of BaS04 in a given NaCl


solution and cause scaling

Solubility of BaS04 is noted in Table 92 with changes in percent NaCI and


temperature. Solubility of BaS04 in
many of the high salinity oil-field brines
may average 85 to 1 00 mg/liter.

Presence of radioactive strontium in


scales is a major safety and
environmental issue.

3. NaCl

Precipitation of sodium chloride is normally caused by supersaturationusually due to evaporation or decreases


in temperature. For example, from Table
9-3, it may be noted that 4,000 mg/ l of
NaCI will be precipitated from saturated
salt water if temperature drops from
140F to 86F.

Salt precipitation may be quite severe


near bottom of the tubing or in the well bore in gas wells or high GOR
oil wells producing very little or no water at the surface.

Precipitation may result from both drop in temperature and drop in


pressure through perforations and into the tubing. Dry gas will
evaporate water, leaving the salt as a precipitate. Table 9-4 shows the
great difference in solubility of NaCI, Gypsum, CaC03, and BaS04 in
distilled water.

4. Iron salts- iron salts are precipitated during simulation if pyrite, siderite, iron
rich in clays are present in rocks. Scales do not consist of one salt but mixtures
of barium, strontium, calcium and iron salts along with wax if present in oil.

Iron sulfide scale is present in oil and gas producing wells, sour wells and
water injectors where the injected water has high sulfate content.

The disposal water contains dissolved H2S, whereas the aquifer water
contains dissolved iron. When these two waters are mixed together, H2S
reacts with the iron ions and precipitates iron sulfide species, as shown in
Equation (2.7).

Iron scales are frequently the result of corrosion products such as various
iron oxides and iron sulfide. Sulfate-reducing bacteria can be a source of
hydrogen sulfide , which then reacts with iron in solution or with steel
surfaces to form iron sulfide . If oxygen is introduced to a system , it can

react with iron to form a precipitate and with steel surfaces to form an
oxide coating.

5. Silica silica and silicate chemistry(SiO2) is quite complicated and highly


varied in rocks and reservoir brined. Silicates scale is rarely a problem in low
temperature reservoirs.
6. Dolomite [CaMg(CO3)2] -there is no way to precipitate dolomite in lab. It forms
in 1000 to 10^6 years in field.

Prediction of Scaling Tendencies


A. Field -rapid decline in production, formation damage, perforation choking,
tubing choking
B. Analysis of water properties immediately after sampling is the best approach to
predict the scale formation tendency.
C. Analysis of water flood water provides a reliable basis for estimating scaling in
injection lines and down hole in injection wells.
D. Analysis of produced brine predicts the scaling in the surface facilities. It may
provide the basis to estimate the scaling in the down hole equipment in producing
wells because of possible prior deposition of scales due to release of CO 2 form
Bi-carbonate ions in water as pressure declines.
E. 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.
F. 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

The first step is to determine which scales are forming and where they are forming.

The simplest method of physically detecting scale in the wellbore is to run


calipers down the wellbore and measure decreases in the tubing inner
diameter
Gamma ray log interpretation has been used to indicate barium sulfate scale
because naturally radioactive radium (Ra226) precipitates as an insoluble
sulfate with this scale.
Wells with intelligent completions and permanent monitoring systems are being
designed to contain scale sensors. The function of the scale sensor is double
duty not only to provide early warning about the initiation of production
impairment by scale generation but also to provide information about possible
impairment of the smartwell sensors and valves by films of scale.
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.
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.
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.
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.
(1) After adding HCI to the scale
sample, effervescence
usually
indicates CaC03, especially if the
sample does not contain iron
sulfide or iron carbonate. The odour
of H2S will indicate the presence of
sulphide scale. Table 9-5 is a
summary of easily run laboratory or
field tests to determine type of scale

(2) Analysis of field brine can show scaling tendencies. Table 9-6 shows an
example of BaS04 scale caused by mixing of Bartlesville and Arbuckle
brines from wells in the Boston Pool, Oklahoma .

(3) Table
9-7 shows
an
example of predictable
CaC03 precipitation due to
pressure drop and release
of CO2 from HC03 1,in
the Grayburg formation,
Hobbs field, New Mexico

SCALE REMOVAL
Scale remediation techniques must be quick and nondamaging to the wellbore,
tubing, and the reservoir. If the scale is in the wellbore, it can be removed
mechanically or dissolved chemically. Selecting the best scale removal technique for
a particular well depends on knowing the type and quantity of scale, its physical
composition, and its texture. Mechanical methods are among the most successful
methods of scale removal in tubulars. When pulling costs are low (e.g., readily
accessible and shallow land locations), the least expensive approach to scaling is
often to pull the tubing and drill out the scale deposit.
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.
1. Mechanical methods
I.

Wireline chipping- time consuming, not a cost effective method

II.

Milling- Scales are generally brittle. One of the earliest methods


used to break off the thin brittle scale from pipes was explosives: a
strand or two of detonation cord (string shot) placed with an
electronic detonation cap at the appropriate location in the wellbore,
most effectively at the perforations. Thicker scales require more
stringent means. Impact bits and milling technologies have been
developed to run on coiled tubing inside tubulars using a variety of
chipping bits and milling configurations. Such scale removal rates
are generally in the range of 5 to 30 linear ft/hr of milling.

III.

Impact techniques-works much like a jack hammer, hammering


the scales until they break. These impact techniques work best for
brittle scales.

IV.

Jetting-Tools can be used with chemical washes to attack soluble


deposits where placement is critical. Water jetting can be effective
on soft scale, such as halite, but is less effective on some forms of

medium to hard scales such as calcite and barite. The use of


abrasive slurries greatly improves the ability of jets to cut through
scale but can damage the steel tubulars and valves.
Sterling beads is an alternative abrasive material for scale removal
by jetting. This material matches the erosive performance of sand
on hard, brittle scales, while being 20 times less erosive of steel.
Sterling beads do not damage the well if prolonged jetting occurs in
one spot. The beads are soluble in acid and have no known toxicity,
simplifying use and cleanup. Hard scales, such as barite, are
removed at rates > 100 ft/hr. This tool is capable of descaling
configurations other than wellbore tubing (e.g., removing hard barite
scale deposits on two gas lift valves in a multiplemandrel gas lift
completion).
For perforated casing, reperforating 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 and insoluble
scales from tubing, casing, or open hole.
Internally plastics coated tubulars -not a cost effective solution
old wells but feasible in new wells
2. Magnetic method- a permanent or induced magnet is placed to prevent
nucleation and precipitation. It has to be planned and installed in the mechanical
completions. It is being practiced in USSR.
3. Chemical methods -most effective, cost feasible
Chemical treatment design

Objectives-to treat the pores, perforations and downhole


equipment with scale dissolver in order to remove/prevent scale
deposition

Data check listI.

Field

II.

No. of wells

III.

Well production(production/Status)

IV.

Perforated interval

V.

Petro-physics

VI.

Tubing id and od

VII.

Wireline observation

VIII.

Types of scales

IX.
X.

Produced/injected water analysis


Previous history and treatment

Treatment procedure
Carry out production test, build up if well is not in conformity with
reservoir engineer prediction
Prepare the well for injection
Demulsifier spearhead: inject a slug containing 0.1% solution of
demusifier in deoxygenated seawater along with scale inhibitor (70100 gal/ft.) of perforation +wellbore volume below packer
Inject a spacer containing (4-6 %) EDTA/Erythorbic acid in
deoxygenated seawater with 2%KCl -(70-100 gal /ft. of perforation)
Inject a more concentrate on scale dissolver solution 20-25% w/w in
deoxygenated seawater +2%KCl
Calculate the injection volume to perforate 4ft. around wellbore and
bottom of tubing. Add foaming agent if gas lift is not available.
Scale dissolver over flush solution- depending upon reservoir
pressure inject tubing volume of diesel or liquid nitrogen or seawater
with foaming agent.
Scale dissolver shut in for 24 hr. to assist the scale dissolver, agitate
after 4 to 1 hr. 4 ft. involves flowing of 5 bbl of fluid out of well (in most
cases) so that unreacted solution is moved to the scale surface.
A three stage treatment may be planned. Each may be separated
after chemical analysis of produced fluid and well performance.
Water-Soluble Scale-The most common water-soluble scale is sodium chloride
which can be readily dissolved with relatively fresh water. Acid should not be used to
remove NaCI scale. If gyp scale is newly formed and porous, it may be dissolved by
circulating water containing about 55,000 mg/liter NaCl past the scale. At 100 deg. F,
55,000 mg/liter NaCl will dissolve three times as much gypsum as fresh water.
Acid-Soluble Scalei.

ii.

iii.
iv.

The most prevalent of all scale compounds, Calcium carbonate (CaCO 3), 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.
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.
Acid soluble scales also include iron carbonate (FeCO3), iron sulphide
(FeS), and iron oxide (Fe 2O3).
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.

iii.

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.
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.
v.

Remove converted CaCO3 scale with HCl or Acetic acid. Dissolve Ca(OH)2
with water or weak acid.
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 CaCO3 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.
SCALE PREVENTION

Scale prevention
Inhibition of Scale Precipitation by Inorganic Polyphosphates

Inhibiting scale with a few parts per million of molecularly dehydrated


polyphosphates is called a " threshold treatment. " When a crystal nucleus is
formed, polyphosphate is adsorbed on the surface and slows further crystal
growth.

For about 25 years, sand-grain size polyphosphate particles have been


injected as a part of regular fracturing treatments. Also, wells have been
fractured specifically to inject the phosphate particles. The polyphosphate
slowly dissolves in produced water and prevents scale precipitation.

Reversion to Orthophosphate-When placed in solution all polyphosphates tend to


hydrolyze into orthophosphates. In the presence of calcium ions, insoluble calcium
precipitates may be formed. Polyphosphates will also revert to orthophosphates in
the presence of acid.
Rate of reversion to orthophosphates depends on temperature, acidity, mineral
content, phosphate content, and nature of polyphosphates. Reversion does not start
until polyphosphate goes into solution.
Sodium-calcium phosphates are normally used in well treatment because of their
slow dissolving rate. This property assures a near constant phosphate concentration
in the water over a long period of time. The objective is for the phosphate-containing
water to be produced from the well before reversion can occur.
Inhibition of Scale with Polyorganic Acid- During the late 1960 ' s, a very stable
polyorganic acid, LP-55 , was field-proven by Halliburton. This liquid polymer inhibits
scale formation through "threshold treatment" approach. It has no temperature limit
and does not precipitate solids.
Placement during fracturing

If placed during a conventional frac treatment, the LP-55 liquid should


precede the introduction of sand. If injected during a minifrac, carried out only
to place the chemical, the well is fraced and then LP-55 is pumped in the well

at rates of 0. 25 to 1.0 bbl/minute to permit rapid leakoff. The feedback rate is


controlled by pressure drop when the well is produced from formation
capillaries or from minute fractures.

It may be combined with a corrosion inhibitor if desired; however, lab tests of


compatibility should be made before injecting both a corrosion inhibitor and
scale inhibitor into a well.

The polyorganic acid is placed on the basis of 10 gals of chemical per 1,000
gals of water or alcohol. The polyorganic acid can also be injected in a water
solution down the annulus to reduce scale deposition in the casing, tubing,
pump, and surface equipment.

It can also be used in the power oil of hydraulic lift type of downhole pumps

Inhibition of Scale with Organic Phosphates and Phosphonates


Various organic phosphates are now offered to inhibit against calcium sulfate,
barium sulfate, and to a lesser degree, against calcium carbonate scale. Many of
these water soluble liquid organic phosphates are suitable for squeeze treatments
into the formation
Exxon Inhibitors

Exxon Chemical Company offers several organic phosphate inhibitors, two of


which are COREXIT 7605 and SURFLO H-372.

Exxon Chemical's COREXIT 7605 has replaced their COREXIT 7640 to inhibit
against calcium and barium sulfate scale deposition.

Exxon Chemical 's SURFLO H-372 replaces COREXIT 7641 to inhibit against
most scales including CaC03, CaS04, and BaS04 SURFLO H-372
wasformerly sold by NL Chemicals.

COREXIT 7640 treating procedure for downhole squeeze:

Preflush with 30 bbl of freshwater

Squeeze 165 gallons COREXIT 7640 dissolved in 30 bbl of freshwater

Overflush with 100 bbl of freshwater

Shut in well for 24 hr.

Return to production.

COREXIT 7641 is a water soluble organic phosphates, especially designed to


prevent deposition of CaCO3, CaSO4, BaSO4. It may be applied by continuous
injector or formation squeeze technique.

Exxon Production Research Compan/4 reported average effective inhibiting of nine


months against very severe gyp scaling in one West Texas field, with retreatment
being considered when the inhibitor in the produced water decreases to about 7
ppm. With this approach, some wells have been relatively scale free with
retreatments every 15 months depending on water production.

Visco Inhibitors-Visco Division of Nalco Chemical Co. offers a number of


phosphate, phosphonate, and polyacrolate scale inhibitors
I.

VISCO 950 inhibits against deposition of BaSO4, CaS04, and CaC03. VISCO
950 may be added to surface water systems or may be used for continuous
feed into down the casing-tubing annulus. As an effective formation squeeze
treatment scale inhibitor, Visco 950 is best used with a 1 :9 ratio of produced
water, with 200-500 barrels of overflush into the formation.

II.

Visco 953 controls CaC03, CaS04, and BaS04 scales at very low dosages in
oil and gas wells, water injection systems, and salt water disposal systems.
For water injection systems, continuous treatment is best; for downhole usage
, batch treatment or semicontinuous treatment is most effective. Visco 953
also is used as a formation squeeze treatment scale inhibitor, mixed at a 1 :9
ratio with overflush into the formation. However, the most effective treatment
is to mix a 1-3% solution of Visco 953 with produced water, displacing the
solution into the formation.

III.

VISCO 959 is designed for formation squeeze jobs to inhibit CaC03 and
sulphate deposits in oil and gas wells and producing equipment. Typical
treatment is to preflush with 5 to 1 0 bbl of produced water, pump in VISCO
959 mixed with formation water at a ratio of one to ten, overflush with 50 to
250 bbl of formation water, depending on daily water production. Usual
treatment is about 1 65 gal of VISCO 959.

Inhibiting Scale with Polymers


ARCOHIB S-223, a salt of polyacrylic acid, developed by Atlantic Richfield is
marketed by major service companies.
Procedure for use in prevention of BaSO4, CaSO4, CaCO3 is as follows:

Pump in 100-150 gal. HCl spearhead to ensure CaCO3 scale clean up. Pump
in the slug consisting of 45 bbl of produced water, 100 gal of 15% HCl and
100 gal AACROHIB polymer.

Follow up with enough CaCl2 to raise the CaCl2 content in the 45 bbl slug of
water to 10,000 ppm. This raises the pH from 1.2 to about 4.5 and causes the
polymer to crosslink and precipitate as a gel in the formation.

The crosslink polymer is then pushed into the formation and dispersed with
100-200 bbl of produced water.

CaC03 Scale Prevention by Pressure Maintenance-If calcium carbonate scale can


be predicted as a result of drop in reservoir pressure, pressure maintenance should
be considered as a means of reducing scaling.

Case study
Details: semoga field is an oil field in the rimau block, which is located south
Sumatra Indonesia. There is also a nearby oil field in this block
These fields have experienced reservoir souring when H2S is being generated from
the reservoir and entering the system. To reduce the H2S concentration in the
facilities H2S scavenger to injected in the system.
Problem: there was a separation system problem at Free Water Knock Out (FWKO)
semoga station. FWKO outlet was dismantled for the injection purposes. It was
found that oil outlet down at the downstream valve LCV ---- 0.5 only
Reason:

X-ray diffraction and x-ray fluroscence analysis confirm that the deposit is
CaCO3 scale.

There is H2S scavenger brand X injection at the downstream of the LCV in


the FWKO with a conc of 11,030 ppm.

The scale dosage was 9-10 ppm only. Lab test shows H2S scavenger brand
X injection reduced scale inhibition % from 97.2 to 35.3% with a 9 ppm of
scale inhibitor.

No deposits found in oil outlet line at downstream of LCV at kaji station which
has same H2S scavenger point and dosage. Dosage was 17.3<22ppm. Lab
test shows 20 ppm dosage given 58% scale.

Solution: H2S scavenger injection will affect scale inhibitor performance it will
degrade the scale inhibition % compared with the system without H2S scavenger
injector. In maintaining the scale inhibitor performance to prevent scale growth,
increasing scale inhibitor dosage is not always the answer. It is important to
understand that scale inhibitor performance behaviour on a certain H2S scavenger
brand before taking preventive measures.
By applying the appropriate scale inhibitor concentration on an H2S scavenger
influenced system the production loss of 8,190 barrels of oil in semoga station could
have been prevented.