Rapid, High-Temperature, Field Test

Method for Evaluation of

Geothermal Calcium Carbonate
Scale Inhibitors
R.G. Asperger, * SPE, Phillips Petroleum Co.

Summary. A new test method is described that allows the rapid field testing of calcium carbonate scale
inhibitors at 500°F [260°C]. The method evolved from use of a full-flow test loop on a well with a mass flow
rate of about 1 x 10 6 lbm/hr [126 kg/s]. It is a simple, effective way to evaluate the effectiveness of inhibitors
under :field conditions. '
Five commercial formulations were chosen for field evaluation on the basis of nonflowing, laboratory
screening tests at 500°F [260°C]. Four of these formulations from different suppliers controlled calcium
carbonate scale, deposition as measured by the test method. Two of these could dislodge recently deposited scale
that had not age-hardened. Performance-profile diagrams, which were measured for these four effective
inhibitors, show the concentration interrelationship between brine calcium and inhibitor concentrations at which
the formulations will and will not stop scale formation in the test apparatus. With these diagrams, one
formulation was chosen for testing on the full-flow brine line. The composition was tested for 6 weeks and
showeda,cl*~mnatic decrease in the scaiiHgoccurringat the tlC)1.7V',cQ~trol,valve. 'This,s,caJing . was about to force a
shutdown of a major, long-term flow test being done for reservoir economic evaluations. The inhibiror stopped
the scaling, and the test was performed without interruption.

Introduction
Calcium carbonate scale is often a severe operational prob- scale deposition on the aboveground piping of geother-
lem in geothermal brine-handling equipment. Deposition mal wells at that temperature. Harrar et al. 9,10 also
of this scale is rapid whenever the solution loses CO 2 studied scale prevention in geothermal brines by chemi-
gas, which allows the brine to become supersaturated in cal additives, seeding, and other approaches. However,
calcium carbonate compared with its soluble precursor their work was limited to temperatures not exceeding
calcium bicarbonate. Deposition of the carbonate solid on 260°F [127°C]. Lindenmuth et al. 11 studied several
the surfaces of process equipment has been prevented at commercial antiscaling agents in the 300 to 340°F [149
low temperatures with organic polymers and phosphonic to 171 °C] temperature range. These investigators ob-
acid materials. Essentially no work on calcium carbonate served that many antiscalants that are effective at low tem-
scale inhibitors at 500°F [260°C] has been reported peratures become ineffective as the brine temperature
previously. increases.

Statement of Problem Study Methods. Because our work was carried out at
This work was designed to find a rapid procedure for brine temperatures of about 500°F [260°C], we confirmed
evaluating high-temperature anticarbonate chemicals. that many of the low-temperature antiscalants were in-
Although laboratory tests could be used successfully to deed ineffective at this high temperature, as demonstrated
screen ineffective material's from those of questionable by our laboratory bottle tests.
utility, field evaluation was necessary to make a final de- About 40 commercial antiscalant formulations were
termination of effectiveness. evaluated in the laboratory. The most effective five were
A new, rapid, useful field test method was needed to tested in a field test loop with the new, accelerated test
compare inhibitor candidates quickly in flowing brines at reported here. Four were found to be effective inhibitors
about 500°F [260 °C] . under test conditions. One was chosen for on-line testing
of its ability to stop scale in the producing well's master
Previous Studies. Vetter et al. 1-8 studied scaling and control valve. It did work, eliminating further scale depo-
scale prevention ,methods in geothermal brines. They sition and preventing an inevitable, premature shutdown
evaluated organic scale inhibitors at about 350°F [177°C] of the deliverability test then under way in 1979.
and found several commercial compounds that prevent
Methods Used. Attempts were made to evaluate the scale
·Now with Petrolite Corp, deposition rates in the aboveground equipment with a wire
Copyright 1986 Society of Petroleum Engineers mesh screen mounted inside a 12-in. [30.5-cm] -ID spool

SPE Production Engineering, September 1986 359

 BRINE, FROM WELL

!
TO SEPARATOR -====:::;-;==t><I:~ TABLE 1-BRINE COMPOSITION ROOSEVELT
HOT SPRINGS 12
SCALE
WIRE SCREEN
INHIBITOR
INSIDE
mg/L
TEST SPOOLA\CALCIUM \
CHLORIDE, /
tI I 6' SPOOL
8i0 2 405

l
, 2 INCH
INE OFF
Ca 19

D ! Mg 3.3
TO ............... ~'----'I:~::::::::J><C:::;-~.:. BOnOM Na 2,080
PIT -~~7 120
K 472
ORIFICE INCHES
PLATE !... _._ HC0 3 158
80 4 65
CI 3,810
Fig. 1-Ten-inch-diameter test loop. F 7.1

inserted into a V-shaped test loop about 55 ft [17 m] long. pecially at points where CO 2 could be flashed because
The design is shown in Fig. 1. Although calcite formed of a constriction-induced drop in pressure.
on the screen, its formation was too slow to be useful as Two test sequences were used. In the first, the concen-
a rapid antiscaling field test method. So a 2-in. [5.I-cm] tration of calcium ion in the flowing brine was changed
line was taken off the bottom of the test loop, as shown incrementally by an increase in the addition rate of the
in Fig. 1. We found that the slow aqdition of a calcium calcium stock solution while the inhibitor concentration
chloride solution to the side stream would accelerate the was held constant. The changes were continued until a
I scaling rate at the test orifice plate, speeding up its detec- measurable drop in downstream pressure was observed
tion from days to minutes. The pressure drop across the within 10 minutes or less, which indicated that scaling
V2-in. [1.3-cm] orifice plate was monitored vs. time by was occurring and defined the scaling region on the per-
Heise™ gauges that allowed a change of IA psig [1.7 formance diagram (Figs. 2 through 5).
kPa] to be noted. In the second test sequence, the injected calcium ion
The calcite observed on the screen, however, was found concentration was held constant, and the inhibitor con-
to adhere and grow only on a magnesium silicate phase, centration was incrementally lowered from an initial value
whose X-ray diffraction was not found in the literature. in the no-scale region until a pressure change indicated
This gray phase was always found on top of a corrosion scaling at the orifice plate. After the lowest effective in-
product layer that appeared to be an ill-defined phase of hibitor concentration was found for a particular calcium
FexS y . Calcite was never found growing on or adhering ion concentration, it was raised back to its previously ef-
to the FexS y phase directly, but always on the silicate fective concentration, and the effectiveness was
phase. The silicate phase was never found attached to bare remeasured. ~
steel, but always on the dark FexS y phase. In two cases, the return to the higher inhibitor concen-
The brine used in these experiments was delivered at tration caused a lowering of the orifice pressure drop, sug-
about 495°F [257°C] from a well at Milford, VT, in the gesting that recently deposited scale could be broken
Roosevelt KGRA. The composition was similar to that loose. This property is a distinct advantage for commer-
shown in Table 1. With brine of this composition, the sur- cial uses because the inhibitor is able to remove scale that
face equipment was slowly scaling inside with calcium may form as a result of use of the inhibitor below its ef-
carbonate. Calcium carbonate deposition was an oper'l- fective concentration for a short time. If the scale has
tional problem for flow-testing the well and reservoir, es- hardened for several hours, however, this property is lost,

ADDED CALCIUM ION CONCENTRATION

(Ca+ 2] IN PPM ADDED CALCIUM ION CONCENTRATION
AREA OF UNCERTAINlY [Ca+ 2] IN PPM
o 0

40 NO SCALE
NO SCALE
o 0 0 0
° 0 0
30 AREA OF
UNCERTAINlY

KEY ~ 20
Scaling stops when
Scaling stops when
inhibitor concentration
Inhibitor concentration
is raised from 1 to 2 10
10 IS rOlsed from 1 to 2

0.1 0.2 0.3 0.4 0.5 0.6 0.8 10 20 30 4.0 6.0 80 100
0.1 0.2 0.3 0.4 0.5 0.6 0.8 1.0 2.0 3.0 4.0 60 8.0 10.0
SCALE INHIBITOR B
SCALE INHIBITOR A

Fig. 2-Performance-profile diagram of diethylenetriamine- Fig. 3-Performance-profile diagram of amino(methylene-

penta(methylenephosphonic acid). Scale inhibitor concen- phosphonic acid), Supplier 1. Scale inhibitor concentra-
tration is in ppm. .tion is in ppm.

360 SPE Production Engineering, September 1986

 AREA OF
ADDED CALCIUM ION CONCENTRATION
AC~:W':H
ADDED CALCIUM ION CONCENTRATION
[Ca+ 2] IN PPM
.. B:INE [Ca+ 2] IN PPM

40 40
°
SCALE ::;'''\ NO SCALE SCALE

30 30

°
20 20

FULL FLOW FOR

06 WEEKS 10
°

01 0.2 03 0.4 0.5 0.6 0.8 1.0 2.0 3.0 4.0 6.0 8.0 10.0 01 02 0.3 0.4 05 06 08 1.0 2.0 3.0 4.0 6.0 8.0 10.0
SCALE INHIBITOR C SCALE INHIBITOR D

Fig. 4-Performance-profile diagram of amino(methylene- Fig. 5-Performance-profile diagram of polyacrylamide,

phosphonic acid), Supplier 2. Scale inhibitor concentra- molecular weight unknown. Scale inhibitor concentration
tion is in ppm. is in ppm.

and freshly deposited scales become permanently bound

to the scale matrix. Fresh scale was loose and mushy. It
became dense and hard on aging at high temperature in TABLE 2-FIELD TESTED SCALE INHIBITORS
the flowing brine solution. The hard scale was calcite. Code Structure
The 'soft and mushy scale was not characterized.
A Diethylenetriaminepenta{methylenephosphonic
lf the inhibitors were diluted with geothermal brine or acid) (see Fig. 6)
potable water, it did not matter. They were effective as B Amino{methylenephosphonic acid), Supplier 1
acids or neutral solutions. We presume that they would (see Fig. 7)
be equally effective if used as their alkali metal salts. C Amino{methylenephosphonic acid), Supplier 2
. (see Fig. 7)
The testing of one inhibitor at three levels of added cal- D Polyacrylamide, molecular weight unknown
cium ions could be accomplished in about 3 hours. E Modified polyacrylamide, molecular weight
unknown
Material Tested. The compounds that have been tested
are shown in Table 2 (see Figs. 6 and 7).
The inhibitors were used as received and their concen- percentage of the starting product that had been decom-
tration specified on that basis rather than on an active posed to lower-molecular-weight fractions as shown by
weight basis because the active component concentration the NMR spectra.
was not known. The decomposition products of some of
the inhibitors have also been found to be antiscalants. This Analytical Methods. Samples of the downhole scale had
was confirmed by phosphorous nuclear magnetic been characterized as calcite by X-ray diffraction of macro
resonance (NMR) spectroscopy and laboratory testing of samples. * Scale samples taken from the test loop screen
solutions of Inhibitor A that were partly chemically and orifice plates were characterized by X-ray diffraction.
decomposed at 500°F [260°C] in the laboratory with brine
in teflon bottles. The decomposition products were fol- Results and Discussion
lowed by comparison of their NMR spectra. The anti- The results of these studies are ~hown in Figs. 2 through
scaling effectiveness of these partly decomposed samples 5. Three regions are defined in each performance-profile
was evaluated in the laboratory scaling test; the samples diagram: a scaling region, a no-scale region, and a region
showed significantly higher anticarbonate scaling prop-
erties than would have been expected on the basis of the • Personal communication with R. Petrovich.

o CH2 - - - - - - N ----.....,...- CH2

II I I I
HOPCH2 OH-P=O CH2 OH-P=O
I
I I I
OH ' OH-P=O OH
OH "'" /
N CH2 CH2 N CH2 CH2 N I
~ / I ,,~ OH
HOPCH2 CHI2 " CH2POH Fig. 7-lnhibitors Band C, amino(methylenephosphonic
I I acid).
OH HOP=O OH
I
OH

Fig. 6-Diethylenetriaminepenta(methylenephosphonic
acid).

SPE Production Engineering, September 1986 361

of scaling uncertainty. If more experiments were done, Acknowledgments
the boundaries of the last region could be better defined. Thanks are extended to the following people whose ideas
Each experimental point, however, would require longer and professional skills helped to make this project suc-
time periods for each inhibitor/calcium concentration used cessful: Dale lavine, Radomir Petrovich, John Walters,
because the scale buildup is so slow in that region. For Terry Allen, and Stuart Johnson.
commercial purposes, however, the present level of cer-
tainty can be used to ensure that these materials will con- References
trol calcite scale deposition at about 495 of [257°C].
One of these compositions, Inhibitor C (see Fig. 4), was 1. Vetter, o.f, Campbell, D.A., and Walker, M.J.: "Summary of
Geothennal Fluid Investigations at Republic's East Mesa Site," U.S.
used to prevent continued carbonate scaling of the master DOE (June 21, 1978).
flow-control valve during a long-term deliverability test. 2. Vetter, OJ., Campbell, D.A., and Walker, M.J.: "Geothermal
Scaling had been occurring at such a rate that a well shut- Fluid Investigations at RGI's East Mesa Test Site, Part I: Experi-
down was inevitable, but all scaling was stopped by in- ence with Field Test Loops," U.S. DOE (June 21, 1978).
3. Vetter, O.J., Campbell, D.A., and Walker, M.l.: "Geothermal
jection of the inhibitor at a concentration 'in the no-scale Fluid Investigations at RGI's East Mesa Test Site, Part II: pH Con-
region as defined by the calcium content of the brine. This trol of Geothermal Fluids," U.S. DOE (June 21, 1978).
demonstration was convincing proof of the usefulness of 4. Vetter, O.J. et ai.: "Geothermal Fluid Investigations at RGI's East
this method for evaluation of inhibitors and their effec- Mesa Test Site, Part III: Non-Condensable Behavior in Geother-
mal Fluids," U.S. DOE (June 21, 1978).
tive usage rates.
5. Vetter, O.J. et al.: "Sampling in Geothermal Operations-
Laboratory studies have shown that several of these in- Philosophy and Reality," Trans., Geothermal Res. Council (July
hibitors lose their anticalcite properties if heated at about 2, 1978) 693.
495°F [257°C] for 1 hour in a low-total-dissolved-solids 6. Vetter, O.J.: "Scale Prediction in Geothermal Operations-State
(TDS) brine. This will be a severe problem because these of the Art," paper SPE 6593 presented at the 1977 SPE Inti.
Symposium on Oilfield and Geothermal Chemistry, La Jolla, CA,
inhibitors must not become chemically impotent during June 27-28.
the downhole, injection, and residence times if they are 7. Vetter, O.J.: "Geothermal Sampling and Analysis," ASTM
to be useful for preventing downhole calcite wellbore Standardization News (Oct. 1979) 11.
plugging in producing wells. Thus Compound A, whose 8. Vetter, O.J. and Campbell, C.A.: "Scale Inhibition in Geother-
mal Operations-Experiments with Dequest 2060 Phosphonate in
total time to loss of chemical effectiveness is much longer
Republic's East Mesa Field," LBL 9089 GREMP-5 UC 66a,
at 500°F [260°C] than the other five compositions test- Lawrence Berkeley Nat!. Laboratory, Berkeley (May 27, 1979).
ed, is the only good candidate for downhole injection by 9. Harrar, J. E. et ai.: "Preliminary Results of Tests of Proprietary
a capillary string to prevent in-wellbore calcite plugging. Chemical Additives, Seeding, and Other Approaches for the
Reduction of Scale in Hypersaline Geothermal Systems, "
UCID-18051, Lawrence Livermore Nat!. Laboratory (Feb. 1,
1979).
10. Harrar, J.E. etai.: "Studies of Brine Chemistry, Precipitation of
Conclusions Solids and Scale Formation at the Salton Sea Geothermal Field, "
For a low-TDS brine of high temperature (495°F UC-66b MS, Lawrence Livermore Natl. Laboratory (Jan. 8,1979).
11. Lindenmuth, T .E. et ai.: "Experience in Scale Control With East
[257°C]) that deposits calcite on CO 2 flashing, four com-
Mesa Geothermal Brine," paper SPE 6605 presented at the 1977
mercial calcium carbonate inhibitors were effective at ec- SPE Inti. Symposium on Oilfield and Geothermal Chemistry, La
onomical concentrations. The test method, which used Jolla, CA, June 27-28.
added calcium ions to accelerate the rate of scale deposi- 12. Mundorff, J.C.: "Major Thermal Springs in Utah," Utah
tion, was shown to be viable. Geological and Mineral Survey, Water Resources, Bull. 13 (1970).
Performance-profile diagrams of four commercial in-
51 Metric Conversion Factors
hibitors are drawn that correlate regions of no scale and
scale for various combinations of calcium ion and inhibi- ft x 3.048* E-Ol m
tor concentrations. in. X 2.54* E+OO cm
This technique can be used to evaluate quickly and eas-
ily the performance of any proposed scale inhibitor in a 'Conversion factor is exact. SPEPE
native geothermal brine. It will also demonstrate the ability Original manuscript received in the Society of Petroleum Engineers office April 9,
1985. Paper accepted for publication Feb. 16, 1986. Revised manuscript received
of an inhibitor to remove freshly deposited scale that has April 16, 1986. Paper (SPE 13549) first presented at the 1985 SPE IntI. Symposi-
not age-hardened. um on Oilfield and Geothermal Chemistry held in Phoenix, AZ, April 9-11.

362 SPE Production Engineering, September 1986