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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
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.
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
Anhydrite
Gypsum
Barite
Celestite
CaSOo
CaSOo.2HrO
BaSOo
SrSOo
BaSr(SOo),
Tendency to Scale-Gypsum
Anhydrite (CaSOo)
(CaSOo' 2HrO) or
-Scaling
E
6
3
E
!
Temperature,'F
o
6
3
i
N o C t{ 9 / l l
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)
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
Scales
175
TABTE9.3
Effect of Temperatureon NaCl Solubility
Temperature
oF
32
86
140
176
212
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
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.
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
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
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
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
-Degrease
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
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.
REFERENCES
J. Burcik,E. J.: "The Inhibition of Gypsum Precipitation
by Sodium Polyphosphate," Producers Monthly, 19. No' 1
(Nov. 1954)42.
2. Case,L. C.: "ChemicalTreatment of Oil Welts for the
Preventionof Corrosion and Scale," U.S' Patent No'
2,429,593,.Oct. 28, 1947.
3. Case, L. C.: "Prevention and Removal Methods for
Scafesin Oil-ProducingEquipment," Oil & Gas Journal' 45'
No. 22 (Oct. 5, 1946)68.
4. Case.L. C.: "scales in Oil-ProducingEquipment .
Their Occurrenceand Causes,"Oil & Gas Journal,45, No.
21 (Sept.28, 1946)76.
5. Crawford, P. B.: "Scale Forming Waters. Part 1," Pro'
ducers Monthly,21, No. 12 (Oct. 1957) 15.
6. Crawford, P. B.: "Scale Forming Waters, Part 2," Producers Monthly, 22, No. 1 (November 1957132,
7. Crawford. P. B.: "Scale Forming Waters, Part 4," Producers Monthlv, 22, No.4 (January 1958)6'
8. CravWord,P. B.: "How a Corrosive Water Becomes
Scale Forming Between the Wellhead and the Sandface."
ProducersMonthly,22, No.4, Part 3 (Feb. 1958)16.
9. Crawford, P. B.: "Scale Forming Waters, Part 5," Producers Monthly,22, No.5 (Mar. 1958)10.
Scale Deposition,Removal,
and Prevention
181