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SPE

sc3LJfJfPetmf?mmmeere3

SPE 22782
Analysis of and Solutions to the CaC03 and CaS04 Scaling
Problems Encountered in Wells Offshore Indonesia
J,E, Oddo, .Rice U.; J.P. Smith, MAXUS Southeast Sumatra Inc.; and M.B. Tomson, Rice U.
SPE Membere

Copyright

1991, society

This paper was prepared

of Petroleum

Engineers

for presemation

Inc.

at the 661h Annual Technical

Conference

and Exhibition

of the Society of Petroleum

Engineera

held in Dallas,

TX, October

6-9,

1991.

This paper was selected for presentation by an SPE Program Committee following rewew of reformation contained in an abstract submdted by the author(s). Contents of the paper,
aa presented, have not been reviewed by the Society of Petroleum Engineers and are suuecl to correction by the author(s). The material. as presented, does nfil necessarily raflect
any position of the society of Petroleum Engineers, ifs officers, or members. Papers presented al SPE meetings are subject to publication review by Ednorial Committees of Ihe Society
of Petroleum Engineers. Permission to COPY is restricted to an abstract of not more Ihan 200 words. Illustrations may not ba copied. The abstract should contain conspicuous acknowledgment
of where and by whom the psper is presented. Write Publicalione Mansger. SPE, P.(.I Box S33836, Richardson, TX 75063-3636
U.S.A. Telex, 730989 SPEDAL.

Pertamina/MAXUS Southeast Sumatra Petroleum, Inc. is


the largest offshore oil producer in Indonesia. CSC03 and CSS04
scaling in and around the submersible
pumps of
peltamin~!$
Farida/Zelda mSelVOirWdk kd to ~-riliitUIE
pump failures and costly workovers to bring the wells back into
production. Twenty-four well brines were analyzed on-site to
accurately determine brine chemistries and scale samples were
analyzed to determine exact composition. Well histories were
studied to find correlations of procedures which led to scaling
problems. Saturation Indices, developed at Rice University and
presented in the paper, were applii to the probkms to give insight
into the causes of the intermittent, but costly scale formation.
Discussions were held with a submersible pump consultant and
pumps were examined to provide additional data for the analysis.
Thiieen scale inhibitors were cvaluattxi at 225 F (107 C) and 300
psia (2.07 IMPa)in a 1.1% Q atmosphere using a flow simulator
developed at Rtce University to firtd the most effective scale
inhibhor to use in the wells to mitigate scale fomnation.
The CaS04 sealing problem was determined to be a rwult
of I-WI-ICIacid treatments performed on the wells to increase
productions rates. These acid treatments were followed by KC1
seawater ovefflush solutions. The problem can be eliminated
through the limited use of strong acid stimulationueatments and by
putting afresh water plug between the formation and the seawater
or using scale inhibitor in the seawater overflush and kill fluids.
calcium from the dissolved CSC03 in the formationdue to the acid
environment pmxipitated with sulfate ions from seawater to form
the CaS04 wale. CaC03 scale formed due to the increased
temperature, the use of rotary gas separators and the decreased
pressure in and around the submersible pumps. Since production
rates need to be maximized and increased temperatures and
decreased pressures am necessitated bj the production scheme, it
has hen decided to use chemieal scale inhibitors in the wells. The
wells are being squeezed to protect them from CaC03 wale
formation.
Wells that had phosphonate residuals from previous
inhibitor squeezes had longer pump runs than wells without
inhibitor
proteedon. One specialty prqxietmy chemical and.generic
,.
ammotmethykne phqhonic acid (ATMP) WCEfound to& the
References and IIIusaations at end of paper.

most effective scale inhibhors in flow through testing and were


effective at 1.5 ppm. Since the specialty chemical had precipitated
in the container, ATMP was recommended.

The wells of Pertamina/MAXUS, particularly the Farida


and Zelda fields, in Indonesia have a tendency to scale in and
around the submersible pumps. The type of wale is primarily
calcium carbonate, but some calcium sulfate scale has been
identified. The latter occurs to a large extent after acid stimulation
treatments. Scale formation in the pumps can cause significant and
serious damage to the pump components and results in short pump
runs which heavily impacts field economics. Although scale has
been reported p@rtaril@orn the Farida and Zelda fields, scale was
observed on or K the pumps from the Cln% Yvonne, Rama and
Intan fields (see Table 1).
A review of carbonate chemistry reveals the basic reasons
for the formation of scale in and around the submersible ~umps.
Calcium carbonate (CaC03) volubility has an inverse relationship
with temperature or stated more simply, CaC03 scale becomes
more insoluble with increasing temperature and a solution at
equilibrium with CSC03 will precipitatethe solid as the temperature
is inemascd (F@re 1).The tendeney to form CaC03 also increases
with increasing pH (as the solution becomes less acid). The
decrease in total pressure around the pumps allows dissolved
carbon dioxide (COz) to eseape from solution as a gas causing an
increase in pH with a subsequent increase in the tendency to form
solid CaC03 scale. Fhlly, the deerease in total pressure decmuqs
the volubilityof solid CSC03 and therefo!?km?ases the probability
that CaC03 scale will form. In summary, the increase in
temperature (up to 1(X)F) around the submersible pumps and the
pump motors and the decrease in pressure, both eontribute to the
formation of CaC03 scale in and around the pumps and in the
reservoir and perforations. (For a review of the basic chemistry of
CaC03,seelZ34).
Calcium sulfate (CaS04) scale formation is somewhat
dependent on temperature, but is typically precipitated due to a
deereaw in
ssure or an increase in the relative concentrationsof
calcium s or sulfate. CaS04 solubllity is fairly independent of
pH and therefore, can readily precipitate in w acid environment
(e.g. after an acid stimulation treatment). The use of a KC1

233

x,

SPE 22782

ENCOUNTEREDIN WELI& O~SHO~ ~NESIA

seawatersolution to displacethe acid during an acid stimulationand


seawater kill fluids used in conjunction with the well workovers
was no doubt responsible for the precipitation CaS04 scale in and
sround the pumps. CaS04 scale is not predicted (see below) to
form from the produced water at bottomhole or wellhead
conditions. The addition of seawater to the system increases the
sulfateconcentration from the nominal average of about 20-40 md
to the seawater average of 2650 mg/L Calcium ions liberated in the
fluids due to the dissolution of CaC03 by the acid unite with the
sulfate ions in the seawateroverflush and kill fluids to form CaS04
scale. If the pumps do not fail due to the scale build-up, the scale
will probably redissolve m the formation water is produced past the
CaS04 scale. However, if calcium carbonate wale then begins to
form due to the production parameters, the CaS04 scale maybe
trapped under a layer of CSC03 scale and not redissolve,Anhydrite
is the predicted form of CaS04 scale to form at the temperatures
and ionic strengths of the MAXUS wells. (For a discussion of
calcium sulfate scaling tendencies, seez4 6.)

With a seawater sulfate concentration (2650 m~) and increr ng


calcium concentrationsdue to the acid stimulationtreatments, there
is an increasingtendency to form anhydrite scale.

The calcium sulfate scaling problem was a result of the a$id


stimulation treahiients performed on the wells in conjunction * hh
seawater kill fluids and overflush solutions. Acid stimulations
performed on the wells can be beneficial if it can be shown that
significant fines or scales are dissolved to increase production.
However, typically acid stimulations in shale formations can
dissolve the cements that consolidatethe rock anJ liberate sand-size
and smrdkr particles which later foul the pumps and/or perforations
or build-up in the reservoir near the wellboie causing formation
damage and skin effects,The use of ethylencdianiinetetraaceticacid
(EDTA) to dissolve scales which have formed in or near the
wellbore is preferred to acid if similar increases in production rates
can be obtained. EDTA has the potential to cause far less formation
damage than the fairly concentrated acids used in the oil field. In
The inhibitor squeezes procedures recommended are being addition, the liberation of cations such as calcium by the acid can
initiated. Preliminary results of the procedures should be available cause later scaling by forming CaS04 scale upon reaction with
for the convention in Dallas.
sulfate from the seawater used in the KC1overflush.
The Pertamina/MAXUS wells would not have formed
TION OF THE SATURATIONINDICES FOR CaSO~ CaS04 scale without the addition of seawater which increastxi the
CA~
sulfate concentration in the system. Calculations of S1 values for
~
CaS04 scale formation indicated that this scale would not have
The saturation index is a measure of the tendency of the been expected in the wells under any production scenario. S1
precipitatein question to form. Mathematicallystated the saturation values are typically of the order of -1.5 to -2.5 based on the water
index is defiied as the:
analyses. However, the ZEB-1 well CaS04 S1value for anhydrite
was up to -0.8 due to $e high sulfate concentration, This well had
Cation]{Anion
recently been worked over and illustrates how CaS04 scale was
sx=log~
~
L....................(1)
probably formed by seawater KC1solutions and kill fluids where
solutions with sulfate concentrations excdlng 2600 mg/1nxcted
where
S1 = the Saturation Index of the species in question
with calcium ions from the dissolved CaC03 scale and in the
[Cation] = the concentrationof the cation in solution (M)
reservoir fluids.
[Anion] = the concentrationof the anion in solution (M)
If it is determined in the production history that
~
= the COIIdlhOIKd
volubilityof the salt in question.
~
acid stimulation treatments are n~essary to maintain
production levels, the KC1 overflush and acid solutions will be
The conditional volubility is the volubility under the mixed using freshwater relatively low in,sulfate. It qay be possible
conditions of temperature, pressure and ionic strength of the to put a sufficiently large plug of fish water Kcl betwam the acid
solution in question. It is then possible to calculate the scaling and the seawater KCI solution to eiiminate the CaS04 scaling
tendency of the water at any place in the production system. problem if the expense of transportation of large amounts of
Algorithms have been developed at Rice University to determine freshwater to the. wells is prohibitive. The required amount of
the saturation indices for the sulfate scales including calcium freshwater plug to.separate the acid from the seawater would have
(gypsum, hemihydrate and anhyfirite), barium and strontium
to be determined for each well depending on the volumes of acid,
nate,l, 3 The *uations needed number of perfomted zones, etc. involved. It must be reiteratai that
sulfatebas well as for calcium c
for the calculation of the S1 valu
T s for the sulfates and calciufn CaSO~, unlike CaC03, will readily precipitate in the kind Gfacid
carbonate are shown in Tables 2,3 iind4.
environment expected dting this procedure. It maybe possible to
An S1 = 0.0 denotes a solution at equilibrium with respect add scale inhibitor to the solutions used in the work~ver to protect
to the solid phase and no scale is predicted. A negative S1indicates the well against scale formation when acidizing for scale deposits
a solution which is undersaturated and may will dkolve the scale built up in the well using more ddute acid solutions. This is not an
in question. Although a solution with a positive S1 will, in rdtemativefor concentratedacid solutions.
principle, precipitate the solid phase. In practice, it is observed that
The cakium carbonate scahg problem concerned a balance
scale does not form in a non-turbulent clean well system until the between pump design, exptxted temperatures in the vicinity of the
S1 exceeds a value of about 0.55 with respect to calcite Scakl
submersible pumps and the decrease in pressures assaiated with
although this value is much less cmain with respect to the sulfate the pumps. The Pertamina/MAXUS wells would probably not
scales.Ilk is the primary reason that scale forms at the level of the have formed CaC03 scale if they were free-flowing. The use of
submersible pumps, but does not form in the surface equipment, as rotary gas separators in some wells compounded the scaling
will be discussed below.
problem since the ~ gas was mnoved (raising the PI-I)as well as
A typical water analysisfor the Pertamina/MAXUSwells is the hydrocarbon gases and the temperature inmased.
shown in Table 5. Calculated S1values for calcium carbonate and
The S1values (all c 0.55) calculated in the other segments
ture-pressure of the production stream indicated that scale should not have
anhydnte are shown in Table 6 for various tern
conditions. Note that the scale problem is pz icted to be most formed in those locations and indeed no scale was found. This is
serious for calcium carbonate scale at the 240F(116 C) and 500 not to say that future changes in production parameters, such as
psi (3.45 MPa) condition which would be at cr near the lower pressures, will not kad to tk? formation of scale in the
submersible pump. No scale is predicted at other temperature- , stiace quipment. Calculated downnole S1values indicated that
pmssum conditions and none is found in the system.
the wells should have been safe from CSC03 scale formation to a
Anhydrite (CaS04) is undersaturated with respect ,to the point which can & estimatcxjto be the ambient m.semoirformaticit
well chemistry at reservoir conditions with an S1= -1.86 (Table 6).
.

224

SPi 22782

J,E. ODDO, J.P.SMITH,AND M.B. TOMSON

would rquire no calcium overflush, should be cheaper to


perform,and theoretically minimize the chances of formation
damage14*15. The design of the adsorption squeeze process differs
greatly from the design of the precipitation squeeze in that lower
concentrations of inhibitor are pu8hed further back into the
formation to saturate as many sorption sites as possible on the
resemoir rock matrix. More prwise knowledge of the speciation
and volubility of inliibitora will increase the understandhg of the
squeeze process and enhance the effectiveness of squeeze design.
The mechanism for most squeezes, regardle88of how they were
designed, is suggested hereto be adsorption. It can be shown that
it is not possible to differentiate between a precipitation
phenomenon and one of adsorption by monitoring flowback
concentrations of the species in question (SCC21,
pp 122-128, for
a complete discussion). Research to determine methods to
distinguish between adsorption and precipitation retention
mechanisms is currently underway in our laboratories and
preliminary results suggest a fomnof adsoqxion as the mechanism.

temperature{=240 F (116 C)) plus 20 F (11 C) and down to S00


psi (3.45 MPa). It must be cm hasizcd that this point is an
estimation and wells operated at i cse temperatures and pmsures
may, in fact, produce scale due to the uncwtainties concerning
localiml temperatures and pressures near the pumps and in the
components.
The operation of a pump motor at a point where the skin
temperature of the pump motor is 100 F (55.5 C!)higher than the
mscmmizmaycm
ateanen
vironment where scale cannot be avoided
with the use of chemical scale inhibitors. S1 values in excess of
about 2.3 indicate a situation where scale may not be controllable
with chemicals. These very It@ temperatures should be avoided
with better pump designs. The use of rotuy gas separators also
produced high S1valJes(>1.5) depending on the true efilcicncy of
the separator, These type separatcusshould also be avoided unless
significant increasesin pump efficiency can be shown and the well
is treated fw scale.
As production rates need to be maximized to produce
maximum revenue, it may not be desirable to operate within the
bounds described above. Successful operation will be
accomplished through the use of threshold chemical scale inhibks
to control scale formation in the wells. Threshold inhibitors, such
as the phosphonates, have been used to control wale since 19367,
however, little is known about the actual mechanisms involved4*8*
9111. Tomson has recently developed a mechanism to explain
the inhibition of p&ipitation of sparingly soluble salts12and this
mechanism pruduces theoreticalcalculations which agree favorably
with quantitative experimentalresults.
Chemical inhibitors can be administered in the wells by
either of two methodq treat strings or inhibitor squeezeprocaiures.
Treat strings are tubing stigs which extend downhole to a depth
where an operat~r feels secure that no deeper scale will form.
lhese de@w are known by scaling experience or calculation using
S1 C@tihOIIS. Inhibitor, is pumped down the tubing from the
surface and injected at depth directly into the brine stream. The
design of treat strings can vary signflcantly, but most rquire a
surface pump, a measuring or metering device, filters, well head
connections, and a downhole entry into the flow stream with an
optional check valve. Although many operators and chemical
companies claim that treat strings should be made of Inconel or
equivalent alloy due to the corrosive nature of many inhibitors, in
the authors experience, 316 stainless steel can be sufficient and
this should be verified with testing.
Precipitation and adsorption are the two mechanisms
generally proposed for the retention and release of the inhibitor in
the ~ese~oir. However, the actual mechanism, whether a
~pl~on
or an adsorption phenonxmon, in most specific cases
is uncertain*3. The so-called precipitation squeeze or squeeze
whereprecipitation is assumed to be the mechanism of retention
and release and is usually administered w:A a calcium overfiush or
chelated calcium to cause the precipitation of inhibitor in the
formation. The slow release of inhibitor into the production system
is thought to be a function of a relatively low volubility of the
inhibitor. However, recent work14 indicates that the calcium
phosphonatesarctoo soluble to account for the low -ntrations
of inhibitors (generally + mg/1)measured inthe produced brine
after a *ueezc. l%esedataindkatethatfff@osphonate8 either the
mechanismof inhibitorretention in the reservoir after a squeeze is
adsorption or that other cations or possibly iigands participate in,
andareimpxtantto, thepmcipitation rcacdom
An inhibitor sqiieeze is accomplished by squeezing or
flowing kk under presurc some concentration of inhibitor into
thepmducingf Ormadonamfobtaining aneventual slowrelcascofa
fewmWgramsperliter of theinhibitorinto theproductionstream
whewproductionis mxmlmenccd from the WdW 16. This slow
inhibitor release, depending on 8ite-specifK circumstances, is
usually sufficient to eliminate scale formatwnin the production
equiprnent4* 67*1%19*. A squeeze where adsorption is
8ssumcdtobe thecon@dlingmechanismfi
xtetentionandrdea8e

The inhibitor squeeze techniques now employed by


Pertamina/MAXUS are administered at low pH and maximize
inhibitor contact area and contact time with the reservoir material.
The contact area is maximized with relatively large overtlush
volumes in conjunction with low inhibitor concentrations and tiie
contact time with at least a 48 hour shut-in period. These variables
have preliminarily been determined to be the most important to
effective inhibhor squeeze design.=
w~~
Pertamina/MAXUS wells are being treated with scale
inhibitor to protect the wells against CaC~ scale formation. T~t
strings are not recommended for the Pertamina/MAXUS wells
since a scale forming chemical environment probably extends into
the perforations and even very shallow into the adjohing reservoir.
Treat strings will not protect the perforations or the reservoir. In
addition, the placement of the treat strings in the wells would be
problematical since for sufficient mixing to occur before the fluids
enter the pumps, the tmt stings should be placed at some distance
from the pumps. However, with multiple zones open to the hole, if
the w strings are placed at some distance from the pump, only
suffkient mixing will probably omur with the fluids coming from
the zones adjacent to the end of the treat strings.
Pertamina/MAXUS engineers have determined that wells
where the pumps are placed near the top of the perforated intervals
scale less ofien than wells where the pumps are placed adjacent to
the perfomtions or below them. Wells where the pumps are placed
below the perforations draw down fluids from sands which can be
si~lcantly higher in the hole (>1800 feet in some cases). These
fluids are at equilibrium with respect to calcium carbonate in each
reservoir sand, but upon entering the wellbore, the waters from
upper sands are drawn down to a hotter environment where
calcium carbonate may precipitate. In addition, upon entering the
wellbore, the solutions will degas loosing COZ which also
contributes to generating a scale forming environment. It wa8
recommend that the ~mps be placed near the top of the perforated
intervals if no production 10SCS
result. If thk is not desirable, scale
fbrmation shmdd be inhibitedby the ChCmicdtreatment.
Wells that showed an increase in total production and an
associated increase in water cut (e.g. FAC-1) after a clean-up and
inhibhr squeeze probabl had scale built-up in the perforations of
the water zones. After tL scale is dissolved from these zones,
water production increases. There is presently no way to isolate
these zones and this phenomenon is pmbsbly a small price for a
Scakfreeaystem.
Chemical scale inhibitor squeczs were recommended to
protect the Pertamina/MAXUS welis from scale formation. The
particttlar zOn#) in a -well to be squeezed simultaneously are
Pmm@MMUs
resenoir engineem and Sc4de
control personnd. It must be certain that the sand(s) which takes

I
235
.

ANALYSISOF AND SOLUTIONS7011-iE CaCOaand CaSO~SCALINGPROBLEMS


ENCOUNTEREDIN WELLS, OFI%$HORE-NEWA

SPE 22782

the squeeze fluids will also produce significant fluids during to simulate the downholc production parameters and maintain 3(NI
reduction. As this may not be easy to determine and if this cannot psi (2.07 M.Pa),225 F (107 C) and do the experiment with a 1.1%
determined with any certainty, then the important sands should C02 in helium atmosphere. Note, helium is used instead of air so
be squeezed individually. The inhibitor to be used in such a that the pump does not develop gas bubbles in the piston chambers.
squeeze has been determined (see below) with inhibitor evaluation The synthetic brine will not precipitate CaC03 at room temperature
tests.
and pressure in a 1.1% CQ atmosphere.
Although dilute acid procedures will dissolve calcium
The evaluation is accomplished by starting the experiment
carbonate, the dilute acids that were recommended for scale clean- with two brine containers. One has scale inhibitor at 10 mg/1and
up will probably do little to stimulate the nwxvoirs in the sense the other has no inhibitor.The ratio of inhibited brine to uninhibited
of a conventional acid treatment. Ifcmcentrated acid stimulationof brine is decreased until precipitation of CaC03 is detected in the
the reservoirs is deemed to be required by Pcrtamina/MAXUS system. Recipitation was detected in the system by in-line pH
engineers, an additional step will be added to the procedures and measurement. Since the evaluation required a 1.1% C02
will be done with filtered fresh or produced water with scale atmosphtne and 300 psi (2.07 MPa), the evaluations could not have
inhibitor. Seawater will be avoided to minimize the chances of been done in a P-Mac machine. The mixing pump is capable of
calcium sulfate scale formation. Seawater treatments will not work 4500 psia and can mix the two brines accurately to less than 1%.
with strong acids. It may be stated however, that in some cases The pump contains no metallic surfaces that contact the brine so
EDTA treatments for scale removal have brought the wells back to that no adsorption of inhibitor onto a metal surface is possible. The
expected production levels and that acid stimulation of the tubing is made of PEEK material.
reservoirs may. not be required and, for reasons discussed
The results of the evaluations can also be seen in Table 4.
pnwiously, maybe detrimental.
The minimum amount of inhibitor to successfully inhibit
The procedures were designed in three parts 1) a clean-up precipitation of CaC03 is shown in the table and the inhibitors are
phase using dilute acids or EDTA to remove scale build-up from ranked from the most effective inhibitor at the top of the table and
the last production rum 2) the inhibitor squeeze phase to place the the least effective at the bottom. The proprietary A sample had a
inhibitor pill in the mervoic and 3) an overflush phase to move the precipitate in the bottom of the bottle which failed to rcdkolve
inhibitor into the reservoir a designated distance and maximize upon stirring or heating of the sample. Should the product contain
contact area. The procedures were designed to remcwe scale and precipitates in the field squeeze,these solids can plug the formation
present an environment conducive for inhibitor retention in the face and therefore, the product would need to be filtered before
rescuvoirs and slow release during production. The inhibitor use. Aminotri-(methylene phosphoric) acid (ATMP) is a generic
squeezes are now being performed with low inhibitor
product with a proven track record with CaC03 scale.
concentrations in a low pH environment with longer contact times
(48 hours) and larger overtlush volumes.
Two general procedures were discussed with ~
Pertamina/MAXUS for the inhibitor squeeze along with their
Phosphonate residuals were measured in the laboratory
advantages and disadvantages. In addition, the general ptiedures
using the extraction technique developed specifically for brines at
were alte]ti to accommodate the use of tlesh or produced water or
seawater as the basic solvent. All solutions used in the procedures Rice University. llte results of the analyses arc shown iti Table
are filtered before use in the wells to minimize the chances of 5. The wells with EDTA clean-ups and phosphonate residuals have
plugging on the formation face. This is important because some had a factor of three longer pump runs than the average. This
Pertamina/MAXUS produced brines will precipitate calcium verifies the conclusiorrs reached by calculation and laboratory
c@onate upon standing and produced water must be filtered. All simulation. The data indicate that the wells can be treated by
seawater used as kill fluids contains 10 ppm active scale inhibitor. squeeze treatments properly applied and pump runs can be
This is extremely importantand should not be minimized since significantlyincreased.
calcium sulfate scale may form in the well as a result of not adding
inhibitor to the kill fluids if seawater is used. After the inhibitor ~
squeeze is administered, the useof further kill fluids or any other
kind of solution into the zones squeezed or the wells after the Five inhibitor squeeze applications are planned for :he
overflush solution is displaced by one well volume should be _Pertamirra/MAXUS wells in Indonesia sing the techniques
described @ this paper. Results from the inhibitor squeeze
strictly avoided since Lhiswill alter the squeezeprocedure.
Since the squeem procedures to be performed in a low pH applications and the actual prcmdures followed should he available
environment, the acid fornt of the ATMP (see evaluation section for the convention.
below) is suggested to be purchased. The acid form sh6uld also be
~NCLUS 10Ns
the cheapest and most concentm.d (50% active coni+en-tition).
..* -1. The wells should be treated with scale inhibitor to protect the
..
production quipment, the producing reservoirs and the
perforations from the formation of scale. Calcium carbonate
Thirteen scale inhibitors (Table 7) were evaluated for
probably is formed only within the fust few inches from the
Pertarnina/MAXUS. The synthetic brine composition used for the
wellbore in the fotmation. Scale inhibitors should be
evaluations consisted of 200 mg/1Ca2+,750 mg/1HC03- and 8875
administered using the inhibitor squeeze process.
Cl- and represented a Zelda or Farida brine. After laboratory
analysis of the Intan brine, it is suggested that the Mm brine is 2. Saturation Indices and scale prediction methods developed by
similar enough to the synthetic brine that no further inhibitor
the authors were used and accurately accessed the scaling
evaluations am needed for the Intan Field. pmblcms.
The schematicdiagram of the inhibitorevaluation apparatus
can be see in Figure 2. The Pertarnina/MAXUS synthetic brine 3. Treat strings are not recommendedfor the PcrtaminalMAXUS
wells. Proper mixing of the inhibitors with the produced fluids
posed the problem that the brine will precipitate CaC@ at room
will be problematical with the use of treat strings due to the
temperature and pressure with an atmospheric partial pressure of
number of production zones. Treat strings will IKUprotect the
~. The brine does not precipitate in the surface quiprnent of the
well from scale formation in the perforations or in the
wells due to the pressure in the production quiprnent and the C02
adjoining formation.
gas in the brine system. Rather than change the composition of the
brine to be stable at room temperature and pressure, it was decided

236

SPE 22782
$.

J.E. ODDO, J.P. SMITH, AND M.B. TOMSON

Although the zones to be packed off and squeezed together in


any particular well need to be detegrnined with the input of
Pertamina/MAXUS petroleum and reservoir engineers, two
basic clean-up and squeeze procedures were recommended as
guides to performing scale clean-up and inhibitor squeezes in
the PertarninalMAXUSwells.

5. Thirteen scale inhibitors have been evaluated previously at 225


F (107 C) and 300 psi (2.07 MPa) under 1.1% C02 to
simulate the Pertamina/MAXUS production. The two most
effective inhibitors were found to be Proprietary chemical A
and aminotri(methylene phosphoric) acid (Dequest 2000)
(ATMP). Since the squeeze procedures are suggested to be
performed in a low pH environment, the acid form of the
inhibitor is suggested to be purchased. The ATMP acid form
should also be the cheapest and most concentmted (50% active
concentration).
6.

CSS04 scale probably forms as a result of the overflqsh of the


seawater KC1solution after an acid stimulationtreatment. Acid
treatments were being performed with acid concentrations far
in excess of what is needed for simple scale clean-up. Calcium
concentrations are controlled and calcium sulfate scale
formation eliminated or minimized with the use of more dilute
acid solutions (0.3% - 0.5%) and inhibitor in the kill fluids
and other fluids put into the wells as described in the text.

7.

CaCQ scale forms due to the increasedtemperature and/or the


decreased pressure and gas separation in or near the
submersible pumps.

8.

As a general gui&line, the outside skin temperature of a pump


motor should not be allowed to exceed 20 F (11.1 C) above
the ambient reservoir temperature at 500 psi without the
wkiitionof scale inhibitor.

9.

Excessively hot motors or very eff:cient rotary gas separators


may cnxe an environmentwhere scalecannot be controlled by
threshold chemical scale inhibitors In addition, scale formed
on pump motors will insulate the pump and cause premature
pump failures. It is strongly recommended that rotary gas
separators not be used in the wells unless significant
production increases can be demonstrated. The scaling
environment produced by the may gas separators should be
evaluated in the laboratory to determine the amount of
supersaturationin the separator if *ey are used.

10. It was noted by Pertamina/MAXUS engineers that longer


pump runs were experienced by wells where the submersible
pumps were placed at or near the top of the perforations.
Pumps are now being placed in this position to minimize
degassing of C02 and heating of cooler shallower brines by
pulling them deeper into the wellbore.
11. Phosphonate residuals have been measured in the
Pem.iidna/MAXUSwells and are presented in the tex~ Wells
with phosphonate residuals measured in the laboratory have
:
had significantly longer pump runs.
o~
The authors wish to thank Pertamina and MAXUS
Southeast Sumatra, Inc. and their partners for permission to
publish these data and conclusions and the editorial support
provided. This work was additionally supported by the Gas
Research Institute under contract No.5088-212-1717, but in no
way does this constitute an encasement by GRl of any products or
views cmtained herein.

1. Tomson, M.B. and Oddo, J.E.: A New Saturation Index


Equation to Predict Calcite Formation in Gas and Oil
production: SPE Joum. of Petri. Tech. (1990) Sub. 10,1990
2. Stumm, W. and Morgan, J.J.: Aquatic Chemistry, WileyInterScience,New York, NY (1981) 780p.
3. Oddo, J.E, and Tomson, M.B,: Simplfied Calculation of
CaC03 Saturation at High Temperatures and Pressures in
Brine Solutions: J. Pet. Tech. (1982)34 pp. 1583-1590.
4. Cowan, J.C. and Weintritt, D.J.: Water Formed Scale
Deposits, Gulf Publishing Co., Houston, Tx (1976) 586p.
5. Carlberg, B.L. and Matthews, R.R,: Volubility of Calcium
Sulfate in Brine, SPE AIME 4353 (1973) pp. 69-78.
6. Oddo, J.E. and Tomson, M.B.: Why Scale Forms in the Oil
Field and Methods to Predict It, SPE Prod. Oper. Sym.,
Oklahoma City, OK, SPE 21710 (1991)
7. Rosenstein, L.: Process for Treating Water, U.S. Patent
2.038.416.
(1936)
,. -.,
8. Patton, C.&:Appl~ed Water Technology, Cambell Petroleum
Series, Norman OK, Norman, OK (1986) 364p.
9. Matty, J. and Tomson, M.B.: Effectof Multiple Pnxipitation
Inhibitors on Calcium Carbonate Nucleation: App.
. . Geochem.
(1988) 3 pp. 549-556.
10. Vetter, O.J.: An Evaluation of Scale Inhibitors, J. Petri.
Tech. (1972) 24 pp. 997-1006.
11. Walton. A.G.: The Formation and Properties of Precipitates,
Wiley-Interscience,New Yodc,NY (1967)
12. Tomson, M.B.: Effectof Precipitation Inhibitors on Calcium
Carbonate Scale Formation, J. tlstl. Growth (1983)62 pp.
lo&l 12.
13. Vetter, O.: The Chemical Squeeze Process-Some New
Information on Some Old Misconceptions, J. of Petri. Tech.
(1973) March pp. 339-353.
14. Oddo, J.E. and Tomson, M.B.: The Volubility and
Stoichiometryof Calcium- Diethylenetriaminepenta(Methylene
Phosphonale:) at70 Deg C in Brine Solutions at 4.7 and 5.0
pH, App. Geodmm. (1989)5 pp. 527-532.
15. Hong, S.A. and !Xwer, P.J.: A Mathematical Model for the
Scale Inhibitor Squeeze Process, SPE Int1Sym. on Oilfield
Chern., San Antonio, Texas, SPE 16263 (1987)
16. Tomson, M.B., et al.: Use of Inhibitors for Scale Control in
Brine-producing C3asand Oil Wells, SPE 61st Ann. Conf.,
New Orleans, La, WE 15457 (1986)
17. Rogers, L.A., et aL: Use of Inhibitors for Scale Control in
Brine-Producing Gas and 011 Wells, SPE Prod. Eng. J.
(1990) pp. 77-82.
18. Shuler, P.J., Freitas, E.A. and Bowker, K.A.: Selection and
Abdication of Barium Sulfate Scale Inhibitors for a Carbon
fi;xide
Flood, Rangely Weber Sand Unit, R ngely,
Colorado, SPE Joint. Rocky Mm./hv Perm. Re 2. Sym.,
Denver, CO, SPE-1%973(1989)
19. Street, E.H., Oddo, J.E. and Tomson, M.B.: Scale
Inhibition During Co-Production of Natural Gas, J. Petr.
Tech. (1989) 41
20. Tomson, M.B. and !l~eet, E.H.J.: Scale Inhibition During
Coproduction of Natuml Gas, SPE Gas Tech. Sym., Dallas,
TX. SPE 17721 (1988)
21. Sp&ito, G;: The Sw$ke Chemisttyof Soils, Oxford Univ.
Press, N.Y. ,N.Y. (1984) 234p.
22. Kan, A.T., Yan, L., Bedient, P. B.,Oddo, J.E. and Tomson,
M.B,: Sorption and Fate of Phosphonate Scale Inhibitors in
the Sandstone Reservo&. Studied via Laboratory Apparatus
with Core Material: SPE 1991 Prod. Oper. Sym., Oklahoma
City, OK, SPE 21714 (1~1) ~
23. Kan, A. T., Varughese, K. and Tomson, M,B.:
Determination of Low Concentrations of Phosphonates in
Brines, SPE Int1Sym. on Oil Field Chem., Anaheim, CA,
SPE21OO6(1991)

237

ZEA-1
ZEA-2
ZEA-4
ZEA-5
ZEB-1

ZEB-2
ZEB-3
ZEB-4
ZEB-8
ZEB-9
ZEC-2
ZEC-5

ZEC-6
ZEC-8
ZEC-9
ZEC-12

ZED3
ZED4
ZED-5

12/8@301
09/87/333
11/75/107
09n7t93
lon8/69
02J83129
Of-#87145
08f87122
());:&m
12/88/31
01/89/9
03187138*
0518W 12
0418W184
11/81/120
09/87/10
08/87126S*
05/88/33
03/89/170
04187157
lofliiw
03188MP
10/90
07187117*
09i83/184
03/88/68
08188198*
10/89/112
())$;1
10/88/141
03t89/192
1lj89]165
09/83/63
08/87/50
10/90
06/87/66
08187f10
11/87/103
02488/107
06188J19*
0319W9

ZEE-1

2333-8

ZEE-9
FAA-1
FAA-2st
FAA-3
FAA-4
FAA-5st
FIM4-6
FM-7

FAA-8
FAB-1

FAB-3
FAB-5
FAB-6

FAB-7

10/87/92
03/89/36
03/88/71*
09/87/362
08/8?/178
06/88/259
05/82/520
07186/203
07/88/40
09/88/205
03/90/19
07182164
09/89/113
c3/83/146
05/83/90
09/84/184
09/84/102
08/84/64
0918314
11/88/17
09/89/115
1lj83/54
07/84/52
09~;565
08/88/110
12/88/298
09189i298
12486*
01/83/97
08/83/48
10/83nl
01/85/207
02j861697,
0MUM253
01PNW2
071841188
0318511%
0718W
03189174
081891150
04i85147
10EW14*

Table 1 (cont)
Well Name

Date Reported
Mo/Yr/RunTu

Well Name

Date Reported
Mo/Yr/RunTim

ZED-6

Wsfl
12/87/27
10M
10/90
10/90
10/90
11/86/9
11/87167
08/88/155
0@9#4

FAB-7
FAC-1
FAC-3

04/87/195
04/89f260
07/87/38
10/89/161
09/87/128
07/89/81
03/90/125
02/90/584
10/90
10/90
04W5
03@0/318

z-;
INB-5
ED-;

FAC-4
RAF-3
n~-1
s?
CID-6
CID-8

* Scale not reported, but EDTA and/or scale inhibitorduring workover indicating scale
formation at some time in the past.
The list is probably incompletedue to scale not beiig reported in well historie$ e.g.
scale inhibitor squeezejob being done with no mention of scale indicatesother wells
probably have experienceda scale problem without mention in the well histories.

2 Recommended equations to calculate calcite Saturation Index (S I ) and to calculate pH for od and gas wells. Note:
& convenience, the units on VBrl,e and Voll are BPD and ntot is MMCF at STP per day (see note at bottom of table).
: Cr. = Ca2+ = Total Calcium

(C#+)(l-my

: log

~y

+ 5.85+ 15.19X 10JT - 1.64X 106T2 - 5.27X 10SP - 3.334(1.S.)1~ + 1.431(1.S.)

~:2
/

(-Iwo;)
log

~;02

*:02

(-H

+ 8.60+ 5.31 X 1O-3T-2.253 x1o-STZ-2.237

~c~ = ~xp P(2.84


8

[)

C02= Yml
10-4 - ~0~2~~~) and Yg
c~/

l@P -0.990(1.S.)1~ + 0.658(1.S.)

$~2(5.0VBnne + 1().OVOil)l()-Sp
(

1.0+

nLOt(T+ 460)

(Caz+)(HCO~)z

= log

log

C:oz

l)

+ 3.63+ 8.68X 10-3T+ 8.55 X 10-~ - 6.56X

(HCO~)

+ 6.39- 1.198X 1O-3T+ 7.94 X


#02

10-6T2

or -

1 I

SP - 3.42(1.S.)1~ + 1.373(1.S.)

3.53X 10-5P- 1.067(1.S.)~~ + 0.599(1. S.)

(T4

: log (Ca2+)(HCO~) + pH - 2.76+ 9.88x 103T + 0.61 x 10fT2- 3.03x 1O-SP-2.348 (1.S~)l~+ 0.770 (1.S.)
(T5
(
)
e: Ca2+=Total calcium (M= mg/1+ 40,000} (HCO~) =Bicarbonate~alinity (M = mgil + 61,000); P =Total absolutepresstue (psia);
Cw = Fugacity coefflcent of C~ gas as a minor
T= Temperature (F); 1.S.=Ionicstr@th (M = mg/1TDS + 58,400 sing/1 Cl- + 35,450} @g
speciesin CH4+ Q

c%= Mole or volumefraction of Q


g=, yg

in the gas phase at the specifiedT and ~ yrot


~ a Moie or volume fraction

of CX12consideringgas plus oil plus brine--thisis essentiallythe fraction Q in the gas at the surfae, nmt
=Total number of MMCF of gas at
STP produced per day; VB~ ~ Barrels of brine produced per day VoiI~ Barrelsof oil produced per day;
C02.
Cc02 = ncoz x 1.38x 10?l(V~ + 3.04VOitknlw
MMCF of Q per day at STP= %XYmt
10I
4

c%.

u)

-u
m

n)
v
al
N

SPE 22782

and the change


able 3. Equations to calculate the change in PH. APH,
M wells. Sea the bsrttom of the fxble for units 10 be uwd.

Plop
M.=

in saturation

with

respect

AS J.,

to calcite,

for

and

od

)I(y%
+ 15.19 x 10_3AT - 1.64X l116A@)

log

-5.27

(I-2.1

X 10%AP

P2(yp)2(@;03)2
[)

(PYyf%

,PH = log

[1

+ 5.31 X

lWAT-2.253x106A(7)

-2.237

(T2.2

x K@Ap

(PY;%;%z

$cQ=,Xp
K

c02

P(2,84

X 104-

~~)

Mld~=

L@_____J

1.0+

(5.0v&ine
+ 10.OVO,I)
1O$P

@~(5.OVB,i..
[

10.OVO,I)IOSP

%0 + 460)

Vhcrc:

AS.I. = 8.68 X l&3AT - 1.64X l&6A@) - 6.56X 1O$AP

(T2.3

APH = - 1.198X 1&3Af + 7.94 X 10~A(T2) - 3.53X 105&

(T2.4

@ * f7uga~i~y~ffiticnt
P= Total absolurc PSCSSW fpsia); T = Temperature (OS%$g

OfCo2 gi3SaS a minOr sties

w * &fok ~ Oluw -on


of @ in AISg= pIM.Wat rhc spccificd T and P, nW = Totaf nUMk of ~~
Yu
d.ly, %nc = Ba2rds of kit3e f31WhKd per dafi VrM= Bards of oil pmdtsccd psr day.

n cm

+ ~

g~

of gas aI SW produc~ ~r

4 . Recommended

%ble

catcthtiosrs
or

free

!$sluratiors

re stetkd

sulfate.

If

the

gypsurnj

hemihydrate
[Sofl

S1.CaS04(Gyp)

+1.86 + 4.5xl&3T
and

= [CSO, - %g

SI-CaS04(Hemi) = loglo[[QJS~lj+
SI-CaS04(An)
For

cekatite

loglo[[~a][S@)+

Sulfate

M. mcrals.

Al I terms

needed

Ttsc term,

- 1.2x KHT7

anhydrite:

= log)o([QJS@])+

for Comnrmc

[S042.] refm
to the -centration
[S042-] = CS04.
of CM* is zero, or negligible,
of the tafrte.

concentration

PK
For

I rrdcx Equations

at the WtOcn

+ 10.7x103P

- 2.38W

+ 0.581-

for

L3x10_311~)

- @K

+ [(%04

- CMg - @K

)2 + 4@K

CS041nl~

3.47 + 1.8x1133T + 2.5x1WF

- 5.9x10_5P - 1.1311n + O.~~1- 2.0xl&311~

4.04- I.9x103T + 11.9xl@m

- 6.9x@P

2.52+ 9.98xIOJT - 0.97xl&~

- 1.6611n + 0.491-

I
I
I

f166x1~31~

- 3.07x10SP - 1.09W + 0.501- 3.3x10311~

and bark
[S0:1

= [CSU - cMg - CG - I@K + [(CW - CMg - Cti . 10PK)2 + 4.1f3pKCso4]lnj/2

sI-srso4

= loglo[[CsJISO:])+

6.11 + 2.OX1O3T+ 6.4xl&~

SI-BaS04

= loglo[[CM][SO:]]+

10.03- 4.8x103T + 11.4xI0 Wz - 4.8XKJSP - 2.6211n + 0.891- 2.0x10311~

IWhsre: T= Tcrnpsnturc(l%

the

of imcomplexcd

P= T@! ?bsolute prewrc(psiak

- 4.6x105P - 1.8911~ + 0.671- 1.9x1fJ311~

I= Ionic ssrxngth (molar) =nrgJTi3S

Cw =WI suwssc
wnccnoacion

= m@

&::
rh

(Molar) = m&y7Ca + 40,0S& CS,. Totst soontiom cmumration


(Mdsr) = m~ Ba + 137.330.

~u:m

-nmarion
tsmicw

58,4C&m&l

SI$ + %,06G
CMC = TOSSIwmcsium
~en~rion (MoW

= @

(hhtar).

Cl-+

35,45Lk

W + WM
mgf7Sr + 87,62(J

Species
Calcium
?+#nedum
Bicmbon@
sulfate
m
ReseIvoir Temp.
Reservoir Press.
MM(ID gas
BOPD

BWPD ..

230 mfl
20mg/1
0.5 mg/1
976 mg/1
25 m#l
0.081 Mole Fraction
240 F(116C)
2800 psi (19.3 MPa)
0.3 (8495 m3/d)
250 (39.8 m3/d)
250 (39.8 m3/d)

e7.

lle~

Inhibitor

ChemicalAl
~&ue~2~
(ATMP)2
chemical c
De#esJ2Dw (DTPMPy
ChemicalE
ChemicalF
ChemicalG
ChemicalH
ChemicalI
chemical J
chemical K4

ldcium carbonate

Temperature
F (C)
240

:%
180
180
hlcium Sulfate
TT
240
240
2ti

Ressure
ps;8y)

SI

pH

0.00

500
500
500
300

0.68
0.11
-0.18
0.03

5.44
6.05
5.89
5.80
6.00

~ssure
p$8y)

Cakium

sulfate

2800
2800

. .
Minimum EffectiveDose
(mgll) as supplied product
1.5

:::
2.0
2.0
2.5
5.0
5.0
7.0
8.0
;::
>10.0

nhibitor sample had a precipitatein the bottom of the sample bottle which would
tissolve upon heating and stirringwithin a reasonable time. The sample may
mm supersaturatedwith respect to the inhibkor. This precipitate may cause
lngof the reservoir face during a squeeze.
IPis aminotri(methylenephosphoric) acid which was supplied by the Monsanto
any and can .bepurchased from many manufactumrs.
klP is diethylenetriaminepenta(methylenephosphoric) acid which was supplied
Monsanto Company and can be purchased from many manufacturers.
tilbition tendency was seen using this chemical at 10.0 mg/1. The evaluation was
wice to verifv the result.

mgll
::
lti

S1

mgtl
26:
26S6

-1.86
0.16
0.79

WCU Name

Iman CcqOsite
FAB-3
FAB-4
FAB.7

FAC-4
-ZEB-8
g:
ZEB-2
ZES-5
ZEW9
ZEC-2
m-s
ZEC-9
ZED-6
23Z&9
Drill Waul

Rcsd&hookMte

2.0
N.D.*
N.D.
N.D.
0.5. 0.s
1.0

N.D.
5.5, 5.4
X.D.
N.D.
0.5
0.4
N.D.
0.7
0.7, 0.6
N.D., N.D.
0.3. 0.6
N.D.

N.D. - None Dcmcwd; below the detection limit of 0.3 m&vl

Inhibited
Brine

Uninhibited
Brine

I
Oil Bath

Totally Inert

225 F

Mixing Pump

Drain

Ionic Strength M
EllEl

Figure1. The negative log of the calcite mnditionsl volubility (pKc) vs. Temperature (F)
nd Ionk Strength (M)

Figure 2. Sohematic diagram of the inhibitor evaluation apparatus configured

<

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