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Chapter9

ScaleDeposition,Removal,
and Prevention
Causes of scale deposition
Prediction of scaling tendency
ldentification of scale
Scale removal
ScaIe-preventi o n m eth od s

of the 70O,000 oil, gas, and service wells in the U.S


have appreciably reduced productivity or injectivity
becauseof scale deposited in the wellbore, perforations. the formation matrix, or in formation fractures.
Scale causes a large number of costly pulling jobs'
fracturing of wells to bvpass scale, and other remedial
work each year in both production and iniection
wells, such as the two examples cited below. Many
oil and gas fields have probably been prematurely
abandonedbecauseof scale.

INTRODUCTION
Scale is deposited in formation matrix and fractures. wellbore, downhole pumps, tubing, casing,
flowlines, heater treaters, tanks, and salt water disposal and waterflood systems. Scale deposits usually
form as a result of crystallization and precipitation of
minerals from water.
The direct cause of scaling is frequently pressure
cirop, temperature change, mixing of two incompatible waters, or exceeding the solubility product. Scale
sometrmeslimits or blocks oii and gas production by
plugging the formation matrix or fractures, perforations, wellbore, or producing equipment.
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
(CaCOr), gypsum (CaSOo ' 2H2A), barium sulfate
(BaSOo)and sodium chloride (NaCl) (See Table 9-l).
Calcium sulfate (CaSO) or anhydrite does not usually
deposit downhole but may be deposited in boilers and
heater treaters. A less common deposit is strontium
sulfate (SrSO).
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.

l. Mobil reported gypsum (gyp) scale caused by


mixing incompatible waterflood waters plugged a 4in. flowline in four days.
2. ln l95l , Earlougher reported that 187 remedial
fracturing jobs were performed to bypass scale plugging of the formation flow channels and wellbores in
a single waterflood project in West Texas.
CAUSESOF SCALEDEPOSITION
Primary factors affecting scale precipitation, deposition, and crystal growth are: supersaturation;mingling of two unlike waters having incompatible compounds in solution; change of temperature; change of
pressureon solution; evaporation (affects concentration); agitation; contact time; and pH.
Tendency to Scale-CaCOt
In oil wells, calcium carbonate precipitation is
usually caused by pressure drop releasing COr from
bicarbonateions (HCO,-t). When CO, is released
from solution, the pH increases, the solubility of
dissolved carbonatesdecreases,and the more soluble

Loss of Profit
The greatest loss of profit each year in the U.S.
from scale deposits is probably caused by the loss of
oil and gas production. It is estimated that a rnajorit)171

PRODUCTION
o P E R A T T O N S / V2O L .
Workover,
andStimulation
WellCompletions,

172
TABLE9.i

Chemical Name

Mineral Name

Chemical Formula
Water Soluble Scale

Sodium Chloride

Halite

NaCl
Acid Soluble Scales

Calcium Carbonate
lron Carbonate
lron Sulfide
lron Oxide
lron Oxide
M a g n e s i u mH y d r o x i d e

Calcite
Siderite
Trolite
Hematite
Magnetite
Brucite

CaCO.
FeCO.
FeS
FerO.
Fe.Oo
Mg(oH),
Acid InsolubleScales

Calcium Sulfate
Calcium Sulfate
Barium Sulfate
Strontium Sulfate
Barium Strontium Sulfate

bicarbonates are converted to less soluble carbonates.


As an illustration of the severity of the problem, loss
of only 100 milligrams of bicarbonate per liter of
water can result in deposition of 28.6 lb of calcium
carbonate per 1,000 bbl of water.
Scale precipitation also varies 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:

Anhydrite
Gypsum
Barite
Celestite

CaSOo
CaSOo.2HrO
BaSOo
SrSOo
BaSr(SOo),

Tendency to Scale-Gypsum
Anhydrite (CaSOo)

(CaSOo' 2HrO) or

The most common form of calcium sulfate scale


deposited downhole is hydrous calcium sulfate or
gypsum (CaSOo ' 2H2O).
A reduction in pressure decreases solubility and
causes scaling. Pressure drop from 2,000 psi to atrrrospheric pressure may precipitate as much as 900
ppm (0.3 lb/bbl of water) calcium sulfate from a typical Permian basin saline water. Fieure 9-226 i[us-

-Scaling

will increase with increased temperature.


Figure 9-l shows the effect of temperature on solubility in fresh water of calcium carbonate.
-Scaling increaseswith an increase in pH.
-Scaling
increases and becomes harder with increased contact time.
-Scaling decreasesas total salt content (not counting
Ca ions) of water increases to a concentration of
l20g NaCl/1000g of water. Further increases in
NaCl concentration decreaseCaCO, solubility and
scaling increases.3r
-Scaling increaseswith increase in turbulence.
Mixing of two incompatible waters will cause precipitation of CaCO, scale. An example is the mixing
of saline water and fresh water highly charged with
bicarbonate.

E
6

3
E
!

Temperature,'F

FlG. 9-1-Effect of temperaturechange on solubility


of CaCO, (After Carlberg).

Scale Deposition, Removal,


and Prevention

o
6

3
i

N o C t{ 9 / l l

FfG,9-2-Gyp scale solubility at 95oF.26


Permission to publish by Society of Petroleum Engineers.

trates solubility ofgyp scale at zero and 1980 psig at


95T. with various concentrations of NaCl. These
curves should be particularly useful in estirnating
downhole scaling of gypsum.
Mixing of two waters, one containing calcium ions
and the other containing sulfate ions, often causes gyp
scaling, particularly in waterflooding.
Casing leaks or poor cement jobs ate frequent
causes of scaling due to do'wnhole mixing of water
from the producing zone with water from other porous zones.
An increase of magnesium ions in the range of
24,400-36,600 mg/liter may increase the solubility
of CaSOo up to several times the solubility of CaSOo
in distilled water and thereby decrease scaling.
Agitation increases scaling tendency.
Within ihe pH range of 6 to 8, pH has very little
effect on solubility and scaling.
Evaporation of water due to evolution of free gas
Dear or in the wellbore may cause supersaturation and
gyp scaling. Hydrates in gas wells frequently become
supersaturated due to evaporation, with resultant scalingThe effect of temperature on solubility of gyp scale
and anhydrite is illustrated in Figure 94. A change
in temperature will change the solubility of calcium

t7:l
sulfate or gyp and the tendency to precipitate.
In wells having anhydrite (CaSOo) stringers in the
producing zone, water flowing in the reservoir is saturated with (and in equilibrium with) anhydrite. The
same water, at disturbed flow conditions near the
wellbore, is supersaturated with respect to gyp and
u'ill precipitate gyp scale (CaSO 4 ' 2H2O) near or in
the wellbore.2a
Figure 9-3 Gypsum Solubility Curves by Case2s
shows the etfect of Ca and SO. ions in waters with
varying chloride ions. These curves-should be particularly useful in predicting gyp scale when mixing
waters in water injection systems. Since this figure
was originally charted by Case only for relative values of SOoas NarSOa, Ca as CaCO3, and Cl as NaCl,
values for these ions, which are obtained from a water
sample from the well or water system, must be multiplied by a conversion factor (see Fig. 9-3) in order
to obtain values for NaSoo, CaCOr, and NaCl. Once
values for these compounds are obtained, plot them
on Figure 9-3. If the relative values cf Ca and SOo
intersect above and to the right of the relative value
for Cl, gypsum scale will form. If relative values for
Ca and SOo intersect below and to the left of the Cl
Iine, CaSOo will not precipitate.
This system can be illustrated by assuming 2,000
ppm of calcium, 4,000 ppm of sulphate, and 18,000
ppm of chlorine. After conversion, the value of
CaCO, is 5,000, NaSOo is 5,920, and NaCl is
29,700. These values, when plotted on the chart, indicate that the intersettions of the values for NaSO"
and CaCO, are well above and to the right of the
NaCl line and that gypsum scale will form.

Tendency to Scal*BaSOo

and SrSOo

For a given NaCl concentration, BaSO, scaling increases with decreases in temperature as a result of
decreasingBaSOo solubility.
Both BaSO, and SrSOo scales are usually caused
by mingling of two unlike waters, one containing soluble salts of barium or strontium and the other containing sulfate ions.
Pressuredrop may decrease the solubility of BaSOo
in a given NaCl solution and cause scaling.
Barium sulfate is often precipitated in gas wells as
hydrates are evaporated.
Solubility of BaSOo is noted in Table 9-2 with
changesin percent NaCl and temperature." Solubility
of BaSO. in many of the high salinity oil-field brines
may average 85 to 100 mg/liter.

PRODUCTION
2 L.
oPERATIONS/VO
and Stimulation
Workover,
WellCompletions,

\I

174

ou,rrr9

|
|
l lllll
!
lhcorcticol moximw donccnlrolio
ot
85' F
SOr (NorSOr) vr. CdCoCOl)

\
roo

Keo't

30, 0ol , - N

.l

ll
5.O(o

tr

O ppm

o
z
o

a t,l

Cl (N oCl) J
tl

rd

\
\

E
c
e

\.

--l

Convcnion fo<lorr,
SO1rl.48:No1SO1
Co x 2JO: CoCOr
Clr 1.65: NoCl

l t|lill

,l@

100

r,000
ppm Co (CoCO1)

Permissionto publish by The PetroleumPublishing


FfG. 9-3-Gy psum solubilitycurves.25
Company.
An example of BaSOo precipitation occurred in the
rnixing of two incompatible waters in a 16-in. gathering system in an Illinois waterflood. Bottomhole
well temperature was 100"F. Soluble barium in water
was 13 to 310 mg/liter and the soluble sulfate range
was from 50 to 85 mg/liter. Scale deposition was so
severe that it was necessary to run a pig twice daily
to keep lines free of scale.

Tendency to Scal+-NaCl
Precipitation of sodium chloride is normally caused
by supersaturation-usually due to evaporation or decreases in temperature. For example, from Table 93" it may be noted that 4,000 mg/l of NaCl will be

Fecipitated from saturated salt water if temperature


drops from 140'F to 86'F.
Salt precipitation may be quite severe near bottom
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 NaCl, Gypsum, CaCO, and BaSrJo in distilled
water.
Tendency to Scal*lron

Scales

Iron scales are frequently the result of corrosion


products such as various iron oxides and iron sulfide.

Scale Deposition, Removal,


and Prevention

175
TABTE9.3
Effect of Temperatureon NaCl Solubility
Temperature
oF

32
86
140
176
212

FfG, 9-4.-Effect of temperaturechangeon sotubility


of gypsum and anhydritefn fresh water (After Carlberg).
Sulfate-reducingbacteriacan be a sourceof hydrogen
sulfide, which then reactswith iron in solutionor with
steelsurfacesto form iron sulfide. If oxygenis introduced to a system, it can react with iron to form a
precipitateand with steel surfacesto form an oxide
coating.
PREDICTION
ANDIDENNFrcANON
OFSCATE
Predictionof Scallng Tendencies
Techniquesdiscussedunder "Tendency to Scale"
arc very helpful in predicting various types of scale.
The Stiff and Davis2emethodhas beenusedfor many
years to show scaling tendencies.However, the age
and methodof collecting samplesmay havea bearing
on the water analysis values obtained. For example,
an aged sampleof water may show different values
than a fresh samplefor pH, bicarbonatecontent, and
COr, The best procedure is to measurwater properties immediately after sampling.
Analysis of waterflood water will providea reliable
basis for estimating scaling in injection lines and in
injection wells.
TABI.E9.2
Solubilityof BaSO.In t{acl
Temperature
oF

203
a1

203

NaCt-mg/liter

0
0
100,000
100,000

Salt in solution
Wt. percent

Mg/liter

25.9
26.8
27.1
27.7
z u ).

259,000
268.000
2 71 , 0 0 0
277,000
285,000

310,000
323,000
3 27 , 0 0 0
335,500
346,500

Analysis of producedbrine is an aid in predicting


scaling in surface facilities, but may not provide a
reliable basis to estimate downhole scaling in producing wells. Downhole deposition of scale, frequently due to releaseof CO, from bicarbonateions
in water-aspressuredeclines tends to causean error
in predicting scalingtendenciesfrom producedbrine.
If bottomholepressureis near original, bottomhole
samplesbrought to the laboratory under subsurface
pressureand temperatureconditions may provide reliable informationon both downhole and surfacescaling tendenciesunder original reservoir conditions.
To determine calcium carbonate supersaturation,
takea wellheadsampleof water and run test on water
at the time of sampling. If the calcium carbonatesupersaturationis more than l0 percent of the bicarbonatealkalinity content, then the water will usually
have a scalingtendency.
ldentificationof Scale
X-ray diffraction is the most used methodfor scale
identification. This involves directing a beam of Xrays onto a powderedsampleof scale crystals.
Each crystalline chemical compound in the scale
diffractsX-rays in a characteristicmanner,which permits its identification. It is the fastestmethodand requiresthe least amount of sample.

TABLE9.4
Solubility of Various Scale in Distilled Water
BaSOo
solubility
mg/liter

2.3
3.9
30.0
65 . 0

Temperature

Sodium chloride
Gypsum
Calciumcarbonate
Barium sulfate

OF

Solubility
mg/liter

77
77
77
77

318 , 3 0 0 . 0
2,080.0
53.0
2.3

PRODUCTION
2 L.
oPERATIONS/VO
W"fr bo-pr"tions,Workover,and Stimulation

176

TABLE9-5
Analysesof FieldBrine and Scale
Analysesof scale'

Analysesof brines
Milligrams/ liter
Chemical
S o d i u m ,N a
C a l c i u m ,C a
M a g n e s i u m ,M g
B a r i u m ,B a
Sulfates,SOo
Chlorides,Cl
A l k a l i n i r yH
, CO3-1

Bartlesville

52,000
10,700
1,807
250
nil
104,750
44

Percent

Type scale

Arbuckle

58,400
13 , 9 0 0
2,182
nil
194
120.i50
50

CaCO.
MgCO.
'BaSOn

0 . 65
8.12
80.10

SrCO,
SrSOo

4.45
3.60
0 . 11
v.lz

sio,
FerO,
Water soluble
Salts
oii
Moisture

0.87
't.02
0.46
99.60%

Total

ffio{lUbingandonrods,withpel|ettypesofSca|einthebottomofpumpingwe||s.

idenChemical analysis may also be used for scale


then
and
decomposed
are
tification. Sarnples of scale
elements
Chemical
solution'
dissolved in chemical
titration
are then a alyzed by standard techniques of
or precipitation.
und"ale^compounds will usually not be identified
chemical
specific
each
for
less the analysis is made
comcation and anion. By comparison, all chemical
analX-ray
an
from
identified
pounds can readily be
vsis.
effervesAfter adding HCI to the scale sample'
the samif
especially
CaCO3,
cence usually indicates
carbonate'
iron
or
sulfide
ple does noi contain iron
oOot of HrS will indicate the presence of sulfide
tt
"
scale.
Analysis of field brine can show scaling tendenscale
cies. Table 9-5 shows an example of BaSOo
brines
Arbuckle
and
caused by mixing of Bartlesville
from welis in the Boston Pool, Oklahoma'
Table 9-6 shows an example of predictable CaCO,
of COt
orecipitation due to pressure drop and release
Hobbs
formation'
in the Grayburg
irom'HCO.-',
field, New Mexico.
staTable 9-7 shows water analyses from two flow
field'
a
specific
in
dons and from an individual well

from indi
As a general rule, water should be taken
probscaling
well
vidual wells for analysisrelatedto
varlocations
lems. Although water from the several
suggested
analysis
servicecompany
i"J
"onria"ta6ly,
at all temperaturesabove0"F' Most
CaCb,
of
r"ufin*
Ftow station B also showedgyp scaling'
;;ll;-'ft";
TABLE9.6
Scale,Hobbs'New Mexico
and
Brine
of
Analyses
Scaleafter extraction
of water and oil

Analyses of brine

Chemical
Chlorides.Cl
Sulfates,SO.
A l k a l i n i t yH
, CO3-'
Calcium,Ca
Magnesium,Mg
Sodium, Na
Sulfides,H rS

Milligrams
per liter

4,155
54
2.335
416
291
2 , 15 0
345

Type scale Percenl

C a S Oo

1.8

CaCO,

95.5

FeS

1.2

sio,

0.9

Total

99.4

Scale Deposition,Removal,
and Prevention

177

TABLE9.7
Water Analysis from Seven Rivers--OueenFormation,
New Mexico
Milligrams / liter at various locations
Chemical
Chlorides, Cl
Sulfates,SOo
Alkalinity.HCO3-'
Calcium,Ca
Magnesium,Mg
lron, Fe
Sodium, Na
Sulficies.H rS

Ban.A

Batt. B

36,600
800
1,950
r,000
1,530
nii
20,120
60

3,900
2,200
1.075
760
440
nil
2,255
120

Well #1

12,100
300
1,695
320
218
nil
7,820
60

SCALEREMOVAT
Scale is classified by methods of removal. Chemically inert scales are not soluble in chemicals. Chemically reactive scales may be classified as (a) water
soluble, (b) acid soluble, and (c) soluble in chemicals
other than water or acid.
Mechanical Methods
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 rearning have been used to remove
both soluble and insoiuble scales from tubing, casing,
or open hole.
Scale may be removed from surface lines with
"pigs" or by reaming out.
Chemical Removal
Water-Soluble Scale-The most common watersoluble scale is sodium chloride which can be readily
dissolved with relatively fresh water. Acid should not
be used to remove NaCl 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 100T,
55,000 mg/liter NaCl will dissolve three times as
much gypsum as fresh water.28
Acid-Soluble Scale--^fhe most prevalent of all
scale compounds, calcium carbonate (CaCOr), is
acid-soluble. Hydrochloric acid (HCl) or Acetic acid
can be used to remove calcium carbonate- Formic

acid and sulfamic acid have also been used.


Acetic acid has special application downhole in
pumping wells when it is desired to leave chromeplated or alloy pump in a well during acid treatment.
Acetic acid will not damage chrome surfaces at temperatures below 200 F; however, HCI may severely
damage chrome.
Acid-soluble scales also include iron carbonate
(FeCOr), iron sulfide (FeS), and iron oxides (FerOr).
HCI plus a sequestering agent is normally used to
remove iron scale. The sequbstering agent holds iron
in solution until it can be produced from the well. A
sequestered Fe acid, such as l5%o HCI containing
Acetic and Citric acid, may provide over 15 days of
sequestering time.
Normally l57o sequestered HCI is used, bat 20Vo
may be necessary because of slow reaction with iron
compounds.
A lOVo solution of Acetic acid may be used to remove iron scales without an additional sequestering
agent; however, Acetic acid is much slower acting
than HCl.
Calculation of required acid treatment is based on
type and amount of scale as indicated in Table 9-8.
Scales are frequently coated with hydrocarbons,
thus making it difficult for acid to contact and dissolve the scales. Surfactants can be added to all types
of acid solutions to develop a better acid-to-scale contact. Surfactant selection for this use should be tested
to determine- that the surfactant will prevent acidcrude oil emulsions and will also leave rock surfaces
water-wet.
Acid-Insoluble Scales-The only acid-insoluble
scale which is chemically reactive is calcium sulfate
or 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 CaCO, or Ca(OH)r. Table 9-9 shows
the relative solubility of gyp in some of the chemicals
normally used for gyp conversion. Test conditions
TABLE9-8
Acid Requiredfor CaCO"and lron Scales
Type of
acid-soluble scale

CaCO.
Fero,
FeS

Gallonsot 15%
HCI/cu ft of icale

95
318
180

PRODUCTION
o P E R A T I O /NVSO L . 2
and Stimulation
fr"rr bo-pt"tions,Workover,

178

TABLE9.9
Gyp SolubilityTests
TYpe
of solution
NH.HCO3
NarCO.
NarCOr-NAOH
KOH

Percent gyP dissolved


72 Hours
24 Hours

87.8
I3.8
71.2
67 . 6

91.0

/ t.c

grade
were 200 cc of solution and 20 grams of reagent

to LSD to
of 24 hours. A surfactant may be added
emulsions'
prevent
water wet scale and to
and then
3. For flowing or gas lift wells, degrease
hours'
24
of
soak with LSD for a minimum
common
Chemically Inert Scales-The most
(BaSOo)
chemically inert scales are barium sulfate
scale
and stroniium sulfate (SrSOo)' Barium sulfate
rebe
may
on the formation face or in perforations
shots'
string
moved by mechanical methcds such as
by rebypassing
or
unde-r-reaming,
or
drilling out,
deposiperforiting. The best approach is to prevent
tion.

gvp.
-'iuiott

of the chemicals shown in Table 9-9 convert


gyp to
gyp to acid-soluble CaCOr' KOI{ converts
acid;
weak
a
or
water
in
which is soluble
6uionr,
Ca(OH)t'
to
converted
is
howevei, only 68 to 72Vo
leaving an unconverted scale matrix'
After converting gyp, the residual fluid is circueither
lated out. CaCO, can then be removed with
HCl or Acetic acid'
Scale-removal procedure if waxes' iron carbonate
and gyp are Present is:
with a solvent such as kerosene, or xylene, Plus a surfactant.
-Remove iron scales with a sequestered acid'
-{onvert
gyp scales to CaCO, or Ca(OH)t'
-ftsrneve converted CaCO, scale with HCI or Acetic
acid. Dissolve Ca(OH), with water or weak acid'

-Degrease

Compounds such as EDTA (Ethylenediamine-tetraacetic acid) and DTPA (diethylenetriamine-pentaof


acetic acid) can dissolve gyp without the necessity
and
EDTA
But
conversion to CaCO, or Ca(OH)r'
high
DTPA are not used ixtensively because of the
ChemDow
by
cost. EDTA is manufactured and sold
ical under the trade name of Versene'
is
Halliburton's LSD (Liquid Scale Disintegrator)
(CaSOo)
a converter and disintegrator of anhydrite
a
and gypsum (CaSOn'HrO) scale' LSD produces
alsoluble'
acid
watei &spersible sludge which is
though u"1d *uy not be required' Normal well treatrnent is:
1. Degreaseprior to LSD treatment' In a pumping
well, place lower end of tubing near the bottom of
producing zone, and circulate degreasing solvent for
1Z to Zq hours and then pump from well'
2. Dump LSD into annulus and let it soak for several hours, then circulate with pump for a minimum

SCALEPBEVENTION
Inhibition of Scale Precipitation by Inorganic
PolyphosPhates
of
Inhibiting scale with a few parts per million
a
called
is
molecularlf dehydrated polyphosphatesis
nucleus
crystal
a
"threshold treatment"' When
anC
formed, polyphosphate is adsorbed on the surface
slows further crystal growth'
For about 25 years, sand-grain size polyphosphate
fracparticles have been injected as a-part of regular
fractured
been
have
iuring treatments' Also, wells
The pospecifically to inject the phosphate particles'
anci
water
produced
iiprtotpituL slowly dissolves in
pievents scale PreciPitation'
in soReversion to Orthophosphate-When placed
orinto
hydrolyze
to
Iutiqn all polyphosphates tend
inions'
calcium
of
thophosphatei. tn ttt" presence
formed'
be
may
sotuUte calcium precipitates
in
Polyphosphates will also revert to orthophosphates
the presenceof acid.
on
Rate of reversion to orthophosphates depends
conphosphate
content,
temperature, acidity, mineral
does
tent. and nature of polyphosphates' Reversion
solution'
into
goes
not start until polyphosphate
in
Sodium-calcium phosphates are normally used
rate'
dissolving
slow
well treatment because of their
conThis property assures a near constant phosphate
time'
of
period
long
a
centration in the water over
water
The objective is for the phosphate-containing
can
reversion
before
to be iroduced from the well
occur.
lnhihition of Scale with Polyorganic Acid
polyorganic
During the mid 1960's, a very stable
This
Halliburton'17
by
u"id, LP"-55, was field-proven
through
formation
scale
tiloiA mut"rial inhibits

Sceh &posltion, Removal,


atd h*ention
"tMld
treatment" approach. It has no temperature limit and does not precipitate solids.
placed during a
Ptscement during fracturing-If
cmventional frac treatment, the LP-55 liquid should
prece& 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
scaleinhibitor 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 irrjected in a water
solutiondown the annulus to reduce scaie 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 squeezetreatments into the formation.
Calgonz3 has reported on lab and field results of its
organic inhibitors S-31 and S-51. S-31, an aminoethylenephosphonate(AMP), is designed to inhibit
against CaSOa, BaSOo and CaCO..
Some of the most successful treatments with S-3 I
appear to be effective for six to twelve months; however, Calgon reported treatments in Lake Maracaibo,
Venezuela to have inhibited scale for 15 months in
wells producing 2,000 barrels of water per day.
Calgon's most recent development is S-51, an organic phosphate, designed to inhibit against calcium
sulfate scaling.
Exxon Inhibitors-Exxon
Chemical Company offers several organic phosphate inhibitors, two of
which, COREXIT 764O and COREXIT 7641, have
been used for several years. COREXIT 7640 is primarily designed to inhibit calcium sulfate and barium
sulfate scaline bv formation squeeze treatments. It

179
may also be used in surface water distribution systems.
Exxon Production Research Company2a reported
average effective inhibiting of nine months against
very severegyp scaling in one West Texas field, with
retreatment being considered when the inltibitor in the
produced water decreasesto about 7 ppm. With this
approach, some wells have been relatively scale free
with retreatments every 15 months depending on
water production.
COREXIT 7640 treatine procedure for downhole
squeezeis:
l. Preflush with 30 barrels fresh water.
2. Squeeze 165 gallons COREXIT 7640 dissolved
in 30 banels of fresh water.
3. Overflush with 100 barrels fresh water.
4. Shut-in well for 24 hours.
5. Return to production.
COREXIT 7641 is a water soluble organic phosphate, especially designed to prevent deposition of
CaCO' CaSOo and BaSOo. It may be applied either
by continuous injections or by the formation squeeze
technique.
Division of Nalco ChemVisco Inhibirors-Visco
ical Co. offers three organic phosphate scale inhibitors-VISCO 950,953, and 959.
VISCO 950 inhibits against deposition of BaSOo,
CaSOa, and CaCOr. VISCO 950 may be added to
surface watgf systems or may be used for continuous
feed into down the casing-tubing annulus. As an effective tbrmation squeeze treatment. scale inhibitor,
Visco 950 is best used with a l:9 ratio of produced
water, with 200-500 barrels of overflush into the formation.
Visco 953 controls CaCO3, CaSOo, and BaSOo
scalesat very low dosagesin oil and gas wells, water
injection systerns, 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 l:9 ratio with overflush into the formation. However, the most effective treatment is to
mix a l-37o solution of Visco 953 '*'ith produced
water, displacing the solution into the formation.
VISCO 959 is designed for formation squeezejobs
to inhibit CaCO, and sulphate deposits in oil and gas
wells and producing equipment. Typical treatment is
to preflush with 5 to l0 bbl of produced water, pump
in VISCO 959 mixed with formation water at a ratio

PRODUCTION
o P E R A T T O N S / V2O L .
Workover,
and Stimulation
WellCompletions,

180

of one to ten, overflush with 50 to 250 bbl of formation water, depending on daily water production.
Usual treatment is about 165 gal of VISCO 959.
Tretolite Inhibitors---Tretolite SP-223, an organic
phosphorate,has been reported as very successful in
preventing calcium carbonate and calcium sulfate
scaling. It may be used on a continuous basis to circulate into a well or squeezed into the formation.
Welis or lines are protected from scaling as long as
5 ppm of chemical can be detected in the fluid stream
in contact with the pipe or equipment.
Tretolite SP-219, a liquid scale inhibitor, which is
a combination of a phosphateand a polymer, prevents
deposition of bprium sulfate and calcium carbonate.
It may also be used to protect against CaSOo deposition. Concentrations of SP-219 for protection against
BaSOo and CaCO, are from 5 to 50 ppm, depending
on the severity of the problem.
Baroid Inhibitors-Surflo H-35 is an anionic organic phosphonatedesigned to prevent the deposition
of Calcium Carbonate, Calcium Sulfate, and Barium
Sulfate. It may be injected as a continuous treatment
in wells or used as a periodic squeeze treatment into
the formation. When squeezed, 4 to l2Vo of Surflo
H-35 is mixed with fresh water or prcduced water and
then overflushed with 25 to 100 bbl of water.
lnhibiting Scale with Polymers
ARCOHIB 3-223,27a salt of polyacrylic acid, developed by Atlantic-Richfield, is marketed by major
service companies under various trade names. Procedure for use in prevention of BaSOo, CaSOo and
CaCO, is as follows:
1. Pump in 100-500 gal HCI spearheadto insure
CaCO, scale cleanup.
2. Pump in a slug consisting of 45 bbl produced
water, 100 gal l5%o HCl, and 100 gal ARCOHIB
polymer.
3. Follow up with enough CaCL, to raise the
CaCL, content in the 45 bbl slug of water to 10,000
ppm. This raises the pH from about 1.2 to about 4.5
and causes the polymer to crosslink and precipitate
as a gel in the formation.
4. The crosslinked polymer is then pushed into the
formation and dispersed with 100 to 200 bbl of produced water. The polymer is slowly dissolved by produced water to provide inhibition against BaSOa,
CaSOo, and CaCO, scale.

Exxon Chemical's COREXIT 7647, a low molecular weight polymer, has been effectively used for
continuous injection and circulation of wells and surface systems and also for squeeze treatments into the
formation. It is a stable inhibitor up to 500'F and controls deposition of both carbonate salts of calcium and
magnesium, strontium and barium.
CaCO, 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 nleans of reducing
scaline.

Summary
Stepsto be takenin solving scaleproblemsare:
1. Identify the scaleand the reasonfor its deposition,
2. Remove deposit by chemical or mechanical
means.
3. In perforatedcompletions,it may be more satisfactory to bypassscaledperforationsby reperforating.
4. Inhibit againstfurther scaledeposition.

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