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SPE 10217

SPE
Society of Petroletm Engineers of A 1M E

Evaluation and Development of Cement Systems for


Geothermal Wells

by Erik B. Nelson,* Louis H. Eilers,* and Lloyd B. Spangle, Dowell Div. of Dow
Chemical U.S.A.

'Member SPE·AIME

This paper was presented at the 56th Annual Fall Technical Conference and Exhibition of the Society of Petroleum Engineers of AIME, held in
San Antonio, Texas, October 5-7, 1981. The 'material is subject to correction by the author. Permission to copy is restricted to an abstract of
not more than 300 words. Write: 6200 N. Central Expressway, Dallas, Texas 75206.

Th is work wa s performed under the au spi ces of the environment. Phase II involved laboratory and well
U.S. Department of Energy, Contract No. DE-AC02- site evaluation of candidate geothermal cement
77ET28324, and coordi nated by Brookhaven National systems. Also involved in Phase II was a basic re-
Laboratory. By acceptance of this article, the search program havi ng to do with the chemi stry of
publisher and/or reCipient acknowledges the U.S. cements at the el evated temperatures commonly en-
Government's right to retain a nonexclusive countered in geothermal \tJell s. Results of the
royalty-free license in and to any copyright cover- bas i c research have been pr evi ousl y pr esent-
ing this paper. ed 3 ,4,5 and will not be covered here.

ABSTRACT
PHASE I
Results of a three-year study concerni ng the ce-
menting of geothermal wells are reported. The U.S. To better defi ne the geotherma 1 pr ob 1em and to de-
Department of Energy (DOE) funded research included termine the properties a geothermal well cement
some specific tasks: (1) determination of proper- must possess, several operators and engi neers frorll
ties an adequate geothermal well must possess; (2) various companies with geothermal drilling and
thorough evaluation of current high-temperature completion expertise were interviewed. For reasons
oi 1we 11 cement i ng technology ina geothermal con- of confidentiality, the operators surveyed will not
text; and (3) recommendation of specific cement be identified here nor will the exact area in which
systems suitable for use in a geothermal well. they are currently doing business be revealed. This
concession was necessary to obtain most of the
information. The information gleaned from these
I NTRODUCTI ON i ntervi ews wa s ext reme ly va 1uab 1e in that sever a 1
misconceptions concerning geothermal cementing were
At the present time, geothermal wells are completed cleared up, and a more accurate and representative
in much the same manner as co nvent i ona 1 0 i1 wells; testing program could be designed and initiated. A
however, the environment with which completion summary of the most important findings is found in
materials must contend in a geothermal well can be Table 1.
much rnore severe. For example, the bottom-hole
temperature in a geothermal well can be as high as
370°C and the format i on bri nes downhole are often The survey result s show that temper atur es encoun-
saline and corrosive. The lure of tered during cementing operations rarely surpass
wells n several geothermal fields l has been 216°C, and typically are in the vicinity of 115°e.
directly attributed to degradation of the cement, These temperatures are somewhat lower than what one
implying that the cementing materials currently would intuitively expect considering the bottom-
used to compl ete geotherma 1 well s may not ha ve been hole static temperatures encountered in most geo-
sufficiently evaluated. This paper describes a thermal wells. The reported reservoir temperatures
three-year research effort performed at Dowell to ranged from 200° to 375°C. In addition, most of
examine currently utilized cementing systems and the drilling/cementing programs of the companies
to identify the best formulations for the comple- i ntervi ewed call for sett i n9 of cas i ng above the
tion of geothermal wells. geothermal zone before the higher temperatures are
actually encountered.
The project was divided into two major phases.
Phase I was concerned with the definition of re-
quirements for geothermal cements, and the develop- Desired compressive strengths fall into the 15.8 to
ment of test procedures to s imul ate a geotherma 1 20.7 MPa range, but 6.9 MPa at extended time would

References and illustrations at end of paper.


2 EVALUATION AND DEVELOPMENT OF CEMENT SYSTEMS FOR GEOTHERMAL WELLS

be acceptable to most operators. Chemistry of the normal density (greater than or equal to 1.8
reservoir fluids varies widely from essentially g/cm 3 ) and low density (less than 1.8 g/cm 3 ).
fresh-water levels up to 44,000 mg/L total dis- The maximum allowable permeabilities for the light
solved solids, with both carbonate and sulfate ions and normal weight systems were 0.25 and 0.10 md,
present. Many of the hot, dry steam wells produce respect ively.
up to two per cent noncondensible gases, 0.3 per
cent of which is hydrogen sulfide. The next test for survivi ng cement systems was a
shear bonding test. This evaluation was designed to
determine how well the cement would bond to sol-
Virtually all of those surveyed expressed interest vent-c 1eaned smooth surface pi pe. Two-i nch pi eces
in lighter density cements due to the highly frac- of lathe-surfaced pipe were placed in the center of
tured and permeable nature of most geothermal for- standard two-inch cube molds and cement slurry was
mations. Densities of 1.44 to 1.68 cm 3 are in pour ed into and around the pi pe. After 28 days of
current use, but densities in the 1.11 to 1.20 curing under water at 204°C and 17.5 MPa, the molds
g/cm 3 range are desired. Additional points men- were removed from the curing chamber or autoclave.
t i oned but not shown in the table i ndi cated that
downho 1e pressures are rarely above hydrostat i c,
and that thermal shock effects on the cement sheath The fi rst bond strength measurement determi ned the
are considered to be significant. force necessary to break the cement/steel bond in
the interior of the pipe. A compressive strength
testing press was used to punch the cement "core ll
Information from the survey was very helpful in the out of the pi pe. Next, the cement/steel bond to
design of a testing program to effectively evaluate the outer surface of the pipe was measured. Bond
existing geothermal cementing technology as well as strength was calculated by dividing the total force
new and untried systems. The testing program for necessary to break the bond by the surface area of
possible geothermal cement systems was designed to the cement/steel interface. The minimum acceptable
be comprehensive and discriminating; as a result, strength was 0.7 MPa.
literally hundreds of compositions were involved.
For each of these compositions, several tests were Following the bond tests, the surviving cement sys-
required for a complete evaluation. To minimize tems, which by now had shown considerable promise,
the total number of tests and to avoid unnecessary were tested for degree of expansion upon curing. A
and redundant evaluations, a screening program was limited amount of cement expansion can be very
devised to quickly identify unsuitable systems and beneficial in that it facilitates intimate bonding
save more complicated and time-consuming tests for of the cement to both the pipe and formation. Usu-
systems whi ch showed promi se. A flow di agr am of ally, 0.2 to 0.4 per cent expansion is considered
the screening procedure is found in Figure 1. optimum. For this screening program, however, the
Testing generally conformed to procedures s pecifi d candidate cement systems were expected at the very
by the American Petroleum Institute (API); 5 least to be dimensionally stable (Le., zero per
however, some changes were occas i ona 11y made to cent expansion). On the other hand, expansion
more accurately simulate conditions peculiar to greater than one per cent was cons i dered exces-
geothermal wells. sive.
For any cement system to be seriously considered The final step in the screening program was an ero-
for suitability in a downhole environment, one must sion test to determine the effects of dynamic steam
first be certain that the material can be success- and brine contact. Any system that exhibited ten-
fully placed in the well. Thus, a thickening time dencies of sloughing was considered unstable and
test was the fi rst step in the screeni ng proces s. rejected. To accomplish such testing, a geothermal
For this program, the tests were run at 150°C and simulator was designed and constructed. The appa-
36.0 MPa pressure. Systems that could not be ratus was named the Dynamic Brine Exposure Testing
pumped for at least three hours under these condi- Apparatus (D-BETA). A schematic diagram of the
tions were immediately dropped from consideration. D-BETA appears in Figure 2.
Systems that survived the thickening time evalua- The D-BETA is a recirculating system in which a
tion were next subjected to compressive strength synthetic geothermal brine flows past up to 32 one-
tests. Candidate cement slurries were cured at inch diameter cylindrical cement specimens. The
227° a nd 316°C. The mi nimum acceptable standa rds rate of flow is adjustable and the brine may be
for strength development were 3.5 MPa within 24 hr heated to 350°C with pressure up to 21.4 MPa. The
and 7.0 MPa within seven days of curing. composition of the brine, given in Table 2, is
typical of those found in moderately saline geo-
Cement compositions that exhibited satisfactory thermal wells at East Mesa, California 7 • After
compress i ve strength development were next eva 1ua- exposure to the brine for specified periods of
ted as to water permeability. In many cases, perm- time, ranging from 28 days to 15 months, the cement
eability is more critical than compressive strength cores were removed and exami ned.
because a highly permeable cement cannot effec-
tively isolate producing zones, and is more suscep- Cement systems that survived the screening program
tible to corrosion by geothermal brines. Maximum were next sl ated for dynami c testing under actua 1
acceptable permeabilities varied depending upon the geothermal conditions at wells located at East Mesa
density of the cement system in question. Realis- and Niland, California. The brines to which the
tically, a low-density slurry cannot be expected to cement were exposed ranged from moderate ly sal i ne
be as impermeable as a higher density composition. at East Mesa to extremely saline at Niland. Brine
Thus, the systems were divided into two groups: compositions are listed in Table 2.
SPE 10217 E. B. NELSON, L. H. EILERS AND L. B. SPANGLE 3

The testing apparatus at East Mesa was very similar slurry density. Due to some rather complex chem-
to the D-BETA in basic design. The temperature of ical interactions that occur in cements at elevated
the brine was about 150°C, and the brine did not temperatures, one must be careful when choosing an
reci rcul ate but made one pass through the appa- extender for a geothermal well cement ll . In this
ratus. At Niland, the test procedure was much investigation, the following extenders were inves-
simpler. Due to the extreme salinity of the brine, tigated: bentonite (gel), perlite, fly ash, diato-
scaling was a canmon problem and the well was shut maceous earth, coal, gilsonite and sodium silicate.
down periodically to restore circulation. Thus, In addition to these a special material, hollow
the circulating design used at East Mesa was deemed glass microspheres, was investigated as a method
unsuitable for fear of plugging. The cement sam- for produci ng geothermal cements of extremely low
ples were instead placed in a wire basket that was dens ity.
bolted inside one of the well IS flashers. Exposure
of cement to a flashing brine as corrosive as that The only nonsiliceous cement system that was thor-
found at Niland was a particularly rigorous test. oughly investigated in this study was based upon
mixtures of furfuryl alcohol and ground coal. A
50:50 mixture of furfuryl alcohol and partially
PHASE II polymerized furfuryl alcohol was blended with coal
of a particle size that would pass through a No. 20
Dur i ng Phase I I, hundreds of tests were performed sieve. ZnC12 is a catalyst "for the solidifica-
on over a hundred candidate cement systems. Due to t ion 0 f the s y stem, and the t hie ken i n9 time i s
space limitations, it would be impossible to de- controlled by varying its concentration.
scribe the performance of each of the systems;
therefore, only the mas t sign i fi ca nt result s that
serve to characterize the behavior of each cement SCREENING PROGRAM RESULTS
category are reported here. In general, this inves-
tigation was limited to materials that are current- The initial screening program, described earlier,
ly readily available in the oilfield. With few was the most comprehensive and time-consuming task
exceptions our efforts were concentrated on cemen- in this project. Table 3 lists the systems that.
titious materials based upon calcium silicate collectively. indicate the general behavior of each
hydrates. category of cand i dates. Table 4 is a compil at ion
of screening program results.

The most extensive group of candidates was based API Classes G and B portland cements were tested
upon s il i ca-stabil i zed port 1and cement 8 , 9. Three extensively under geothermal conditions in the
tyses of portland cement, API Classes B, G and screening program. In general, Class G systems
HI , were evaluated in conjunction which various performed better than thei r Cl ass B counterparts.
extenders, dispersants, retarders, etc., to be dis- Both portland cements were superior to most non-
cussed later. portland cements.
Several types of non-portland cements were thor- All of the normal weight Class G systems (Nos. 1, 2
oughly tested. API Class J cement is a special and 3) performed sat i sfactori ly wi th Systems 2 and
formul at i on for use in high-temper at ure we 11 bore 3 performing best. Both exhibited excellent
environments. Due to the absence of fast hydrating strength and extremely low permeability. System 3,
tricalcium silicate, Class J slurries can often be containing fly ash, exhibited the highest outside-
placed without adding retarders. bond strength of all systems in the screening
series. Normal weight Class B systems (Nos. 12 and
Some commercially prepared lightweight cements were 13) were not as successful. System 12, stabi 1 i zed
evaluated as potential geothermal binders. These with 35 per cent silica sand, exhibited poor long-
cements are essentially portland cements that have tenn strength at 227°C. In addition, outside bond
been premixed with a low-density siliceous aggre- strength to steel pi pe was unacceptabl e. System
gate materi a1. Another. modi fied portl and cement, 13, with 35 per cent silica flour, performed much
known as "sl ag cement was evaluated. Sl ag cement
II , better.
is a normal grind combination of portland cement
and special blast furnace slag with normal voJater The low-density Class G systems (Nos. 4, 5 6, 7, 8
requi rements. and 9) showed mixed performance. Those 1.6
g/cm 3 in density were satisfactory. Lighter sys-
Because geothermal wells are at high temperature t em s we r e una c c e pta b1e, usua 11 y due to 1 ow com pre s-
and the formations are typically fractured and sive strength. The best low-density Class G system
weak, the use of retarders and extenders is almost was No.6, containing gilsonite. Only two low-
mandatory. The most commonly used retarders i n- density Class 8 systems were evaluated (Nos. 14 and
clude chemicals that fall into two categories: 15). Both were marginally acceptable as to com-
lignosulfonates and modified sugars. Such chemi- pressive strength; however, they performed well in
cals, usually added between 0.1 and 3.0 per cent by subsequent tests.
weight of cement, were used extensively in this
progr am. Candidate systems based upon Class J CelTlent (Nos.
16-20) were not as successful as the portland
Extenders comprise a much more diverse group of group, but two normal density candidates looked
materials. Generally, extenders hold additional promiSing (Nos. 16 and 17). Two lightweight
water and thus allow substantial reductions in systems (Nos. 19 and 20) perforrlled acceptably as to
4 EVALUATION AND DEVELOPMENT OF CEMENT SYSTEMS FOR GEOTHERMAL WELLS SPE 10217

strength and permeabi 1 ity but were dropped when deterioration. Also, the carbonate present in the
they exhibited little or no bonding strength to brine appeared to convert the cementitious calcium
steel. It is interesting to note that the success- silicate hydrates to calcium carbonate and silica.
ful Class J systems closely paralleled the accept- The carbonate react i on was most r api d wi th low-
able portland-based cements. Again, the addition density systems due to their higher permeabil ity
of fly ash seemed to be beneficial. allowing increased brine penetration. The carbon-
ate degradation most commonly manifested itself in
High alumina cement formulations, utilizing Ciment the formation of a scale over the surface of the
Fondu, were tested (Nos. 21 and 22). A combination cement specimen that could easily be scratched away
of retarders Rl and R2 was required to obtain an by a fi ngernail •
acceptable thickening time. Systems 21 and 22 were
acceptable as to strength but were sl ightly too The O-BETA results indicate that portland cement
permeable. Because they were borderline in perfor- compositions with a density below about 1.5 g/cm 3
mance, these systems were allowed to pass to the are unsuitable for cementi ng geothermal zones that
next stage of evaluation. contain flowing acidic carbonate brine. Class J
systems also behaved much like the portland sys-
Of the systems based upon slag cement (Nos. 23-24) tems. Although these result s appear unpr om; sing
only one failed to meet minimum standards. The with rega rd to the use of low-dens ity cements for
unacceptable system, No. 25, was the lightest in geothermal wells, it is important to remember that,
density. No. 25, containing sodium metasilicate inmost situations, only a 1 imited area of the
was dropped due to low strength. System 24, con- cement sheath would actually be exposed to flowing
taining fly ash, suffered a severe strength loss brine. The low-density systems which performed
between one and seven days; however, strength never well in static tests would thus perform adequately
dropped below minimum. Permeability and bonding in most of the annular zone.
performance was excellent.

The commerci al 1i ghtweight cement systems di d not WELL SITE EVALUATI ONS
survive the initial screening program. All of
these systems were of lO~J density and exhibited Test i ng of cement systems under actual geotherma 1
extremely poor strength. conditions was performed at two test sites in
Southern California, East Mesa and Niland. At the
To summarize, the portland cement compositions per- East Mesa Test Site, well 8-1 was selected for this
formed vJell in the initial testing, provided a evaluation. Fluid temperature was maintained at
stabi 1 i zi ng amount of s il i ca was present. Sil i ca 150 a C and 0.66 MPa pressure. The brine analysis is
flour (45 flm particle size quartz) was the most given in Table 2.
effective source. Some pozzolanic materials which
norma lly act as sour ces of s il i ca fa il ed at 316°C.
These were certa i n fly ashes, impure di atomaceous i"lost of the cement systems evaluated at East Mesa
earths and heated shale. Such problems with pozzo- had passed initial screening evaluation and had
lans in ~ortland cement have been previously re- been subjected to the D-BETA s imul ator. As men-
ported 12 , 3,14. Increasing the v.,rater content of tioned earlier, the test apparatus at East Mesa was
the cement and using extenders reduced strength and very simi 1a r to the D-BETA in design. The br i ne
increased permeabi 1 i ty, as expected. The Cl ass J flow rate, however, was much faster, 6.0 L/mi n.
systems performed much like similar weight portland Cement specimens were exposed for periods of 1, 3,
systems. The high alumina cements had lower 7 and 17 months, and evaluated in terms of compres-
strength and higher permeability than similar sive strength, water permeability and size reduc-
weight calcium sil icate hydrate systems. Commer- tion.
cial lightweight cements performed acceptably to
about 215°C. At 316°C, strength dropped and Selected East Mesa results are found in Table 6.
permeabi 1 i ty increased well beyond acceptable The performance results at East Mesa were very
limits. Slag cements performed somewhat better, but similar to those measured with the D-BETA; however,
addition of fly ash resulted in deterioration. The due to the faster fluid movement, the rate of
chief disadvantage of slag cements is the associa- deterioration or erosion was accelerated. From a
ted release of noxious and corrosive sulfides at compressive strength and permeability standpOint,
geothermal temperatures. very few systems performed satisfactorily through-
out the entire 17 months. Systems 3, 5 and 12 were
As the initial screening program neared completion, all normal weight systems. Erosion of the cement
surviving cement systems underwent evaluation under specimens was severe for all of the systems. A flow
simulated geothermal conditions. As mentioned rate of 6.0 Llmin is probably on the high side when
earlier, the D-BETA was utilized for this part of compared to the average geothermal well situation,
the investigation. Performance of the more illus- so the deterioration may be somewhat unrealistic.
trative systems in terms of compressive strength,
water permeability and erosion is given in Table 5. The cement specimens at Nil and performed different-
Initial composition of the slurries is given in ly fran East Mesa and O-BETA counterparts. Results
Table 3. are gi ven in Table 7. The sampl es were exposed
to two 38-day cycles at 170° to 182°C and 0.8 MPa.
Two general effects of exposure of cement to a cir- As Table 2 shows, the brine indigenous to Niland is
culating geothermal brine were immediately apparent unusually high in dissolved solids. All but one of
in the D-BETA program. Most systems, especi ally the systems maintained excellent compressive
the low-dens ity ones, were subject to acce 1er ated strength. Permeability could only be measured on a
SPE 10217 E. B. NELSON, L. H. EILERS AND L. B. SPANGLE 5

few systems because most of the specimens were Because slurries of such low density are desired in
cracked. The behavior of these cements illustrates geothermal applications, an evaluation of their
thei r suscept ibi 1i ty to thermal shock. L; ke East suitability was conducted. Twenty-one candidate
Mesa, the condit ions exper i enced at Nil and woul d systems were subjected to compressive strength and
probably not be seen by most of the cement in a permeability testing following exposure to simu-
geothermal well; therefore, the data reported here 1ated geothermal condit ions. Some of the more
must be kept in perspective. illustrative bubble cements are described in Table
9 and testing results are listed in Table 10.
NONPORTLAND SYSTEMS
Although the primary intent of this research was to Two grades of commercially available glass bubbles
eval uate cements based upon commonly encountered were used in this evaluation: Grade 1 and Grade 2,
oilfield materials, some rather exotic systems were a stronger and more expensive bubble with higher
also evaluated as possible geothermal cements. collapse pressure. The sl urry densities of the
Thi s part i cul ar research was very 1imited in scope glass bubble systems varied from 1.07 to 1.57
but deserves to be mentioned. g/cm 3 . Results show that when glass bubble ce-
ments are subjected to geothermal temperatures, at
least 26 per cent silica must be added to prevent
Acid catalyzed furfuryl alcohol/filler blend sys- strength retrogression. Otherwise, the glass bub-
tems were selected for evaluation as geothermal bles themselves react with the cement resulting in
binders. Several fillers, including powdered coal, disintegration of the bubbles and a highly permea-
graphite, perlite, diatomaceous earth and silica ble cement.
flour, may be used with furfuryl alcohol 15 ,16,17.
Initial testing showed that the coal system would
develop a compressive strength of approximately 21 As a group, the glass bubble cements performed much
MPa within three days of curing at 300°C. Perme- better than similar weight conventional systems.
abil ity of the system was about 0.01 md. The 1m'J Under extremely critical conditions, where ultra
density and low cost of coal also made this system lightweight slurries are essential, the glass
appear advantageous. bubble systems may be advantageous.

As shown in Table 8, furfuryl alcohol without a SELECTION OF RECOMMENDED GEOTHERMAL CEMENTS


catalyst will not polymerize in less than six hours
at 150°C and 35.9 MPa. Three catalysts were As thi s research effort approached termi nat ion, a
eva 1uated with var i ed results. Tartar i c ac i d and final review of test results was performed and six
malic acid caused a very rapid set accompanied by a systems were selected for recommendation as viable
violent exotherm. To alleviate the exothermic geothermal cements. The systems were al so submit-
behavior somewhat, a 50:50 mixture of furfuryl ted to the National Bureau of Standards (NBS) for
alcohol and a commercial partially polymerized testing and verification. They are listed below.
furfuryl alcohol was evaluated. A 50 per cent
solution of ZnC12 was utilized as the catalyst,
and by varying its concentration from 0.2 to 1.0 l. Class G + 35% s il ; ca flour + 54% H2O
per cent, the thickening time of the slurry
fluctuated between about two to six hours. 2. Class 3 + 35% silica flour + 54% H2O
3. Class J + 44% H2O
Two of the furfuryl al coho 1/powdered coal
were evaluated for compressive strength and permea- 4. Class G + 35% silica flour + 2°1,0 bentonite +
bility characteristics. Briefly, this system gives 8.5% perlite + 116% H2O
excellent strength and low permeabil ity at high
temperatures provided the material is in contact 5. Class G + 35% silica flour + 15% diatomaceous
with fluid. When subjected to dry heat, severe earth + 91% H2O
oxidation occurs resulting in loss of integrity.
6. Class G + 100% s 11 i ca flour + 2°,1 sodium s 11 i-
,0

cate extender + 136% H2O


GLASS BUBBLE CEMENTS
Portland cement slurries with densities in the 0.96 The first three slurries are of normal density.
to 1.20 g/cm3 range are possible with the util i- The remaining systems are low density. The three
zation of lightweight glass bubbles or micro- low-density slurries behaved rather erratically in
spheres, having a specific gravity of approximately the circulating brine tests, but performed well in
0.35. Such slurries have been shown to have ac- static tests. Because only a limited amount of
ceptable properties under normal oilfield condi- cement would actually be exposed to circulation,
tions. 18 Glass bubble cements must be prepared the 1 ightweight systems should give adequate per-
and ut i 1i zed wi th care. Depend; ng upon the gr ade formance. These systems are compatible with common
of bubbles, the lightweight slurries can retain retarders and fluid-loss additives. Table 11 shows
their designed properties only when the hydrostatic typical performance of eight systems based upon the
head does not exceed 13.8 MPa. six basic formulations.
6 EVALUATION AND DEVELOPMENT OF CEMENT SYSTEMS FOR GEOTHERMAL WELLS SPE 10217

CONCLUSION

The results of this research effort have shown that Berkeley Laboratory, Univ. of CA, DOE Contract
portland cements of normal density, similar to No. W-7405-ENG-48 (September, 1977).
those al ready in use at Inost geothermal areas ap-
pear to be the best that current available cement- 8. Menzel, C. A.: "Studies of Hi gh Pressure
ing technology can offer. This fact should be Stearn Curing of Tamped Hollow Concrete BlOCk,"
reassuring to operators who have used such formula- Concrete Inst. (1935) l, 5, 64.
tions in existing wells. For those who need
ultra-light density cements, a slurry containing 9. G. L.: liThe Reaction of Cement
91 ass rni crospheres may gi ve adequate performance; at Elevated Temperatures," Proc.
however, such systems are significantly more expen- _ _ _--"- of Cement, London,
sive than conventional cements.

10. API Specifications Oil Well Cements and Cement


CONVERSION FACTORS Additives, API Spec. lOA, Section 2, 3-9.
11. Nelson, E. B.: "Prevention of Strength Retro-
MPa 145 psi gression in High Temperature Well Cements,"
g/cm 3 = 8.35 lb/gal Proc. 27th Annual Southwestern Petroleum Short
Course, Lubbock, 11-19, 1980.
ACKNOWLEDGMENTS 12. Eilers, L. H., and Root, R. L.: paper SPE 5871
presented at the SPE-AIME 46th California
The authors \'Ii sh to thank the U.S. Department of Symp., Long Beach, 1976.
Energy and Dowell Division of Dow Chemical U.S.A.
for permission to publish this paper. 13. Diamond, S., and Thawlow, N.: "A Study of
Expansion Due to Alkali-Silica Reaction as
Conditioned by the Grain Size of the Reactive
REFERENCES Aggregate,1/ Cement Research(l974) i,
591-607. --
1. Kennerly, R. A.: New Zealand J. (1961)
1,453-468.
- - 14. Ludwig, W.: "Influence of the Alkali-Admix-
ture Reaction," ..:....:.;.......:..:..;..:;;. ____ ..:..::...:..~~_ 1974)
2. Radenti, G., and Ghiringelli, L.: Geothermics i. 591-607.
(1972) l, 3, 119-123.
15. Goldstein, 1. S., and Dreher, W. A.: liStable
3. Nelson, E. B., Eilers, L. H., and Kalousek, Furfuryl Alcohol Impregnating Solutions," Ind.
G. L.: "Formation and Behavior of Calcium Chem. (1960) 52 57-58. --
Silicate Hydrates in a Geothermal Environ-
ment, II Cement Concrete Research (1981) 11, 16. Hess, P. H., et al.: "Chemical Method for
371-381-.- - - Formation Plugging," paper SPE 3045 presented
at the 45th SPE-AIME Fall Meeting; Houston
4. Eilers, L. H., and Nelson, E. S.: "Effect of 1970. .
Silica Particle Size on Degradation of Silica
Stabil i zed Portl and Cement, II paper SPE 7875 17. Siegfried, K. J.: "Furan Polymers,"
presented at the SPE-AIME Int. Symp. on Polymer Sci. Tech., John Wiley & Sons,
Oilfield and Geothermal Chemistry, Houston, 432-445 (1967) -.-
1979.
18. Smith, R. C., Powers, C. A., and Dibkins,
5. Eilers, L. H. and Nelson, E. 8.: "High T. A.: "A New Ultra Lightweight Cement with
Temperature Cement Compositions: Pectolite, Super Strength," paper SPE 8256 presented at
Scawtite, Truscottite or Xonotlite; Which Do the 54th Annual SPE-AIME Fall Meeting, Las
You Want?", paper SPE 9286 presented at the Vegas, 1979.
55th Annual SPE-AIME Fall Meeting, Dallas,
1980.

6. American Petroleum Institute Publication RP


lOB.
7. Cosner, S. R., and Apps, J. A.: "A Compila-
tion of Data on Fluids from Geothermal
Resources of the United States," Lawrence
TABLE 1

SUMMARY OF SALIENT POINTS FROM OPERATOR SURVEY

Temperature:

Reservoir 177° to 371°C


Bottom Hole Circulating 93° to 204°C

Compressive Strength:

Desired •. 15.8 to 20.7 MPa ~l 24 hr

Acceptab 1e 6.9 MPa @ extended time

Fluid Chemistry:

Bri ne 15 to 44,000 mg/L TDS w/


and
Steam 2% noncondensible gases
(includes 0.3% H2S)

S1 ur ry Dens ity:

Current Use 1.44 to 1.68 g/cm 3


Desired . . 1.11 to 1.20 g/cm 3

TABLE 2

ANALYSES OF GEOTHERMAL SRI NES AT EAST MESA AND NILAND TEST rAC! LITIES

Concentration Concent r at i on
(mg/L) (rng/L)
Spec i es East Mesa
----- -----
Ni 1and

Na 8100 47,100
1360 22,700
1050 12,000
Fe 9 240
Mn 62~

Sa 14 140
Sr 320
Zn 160
Li 40
10
Pb 29
Mg 17 Hi:i
Clr 0.5
~JH4+ 41
Cl 15,850 131,70()
CO? 200
,n
TDS (Cal c) 2/,USO ZH,4UO
TABLE 3
CANDIDA TE GEOTHERMAL CEr~ENT SYST[MS

System ity
No.
1 Kaiser Permanente "Gil Rl 1.0 SAND 35 54 1. 91
2 Rl 1.0 SF 35 54 1. 91
3 R1 1.0 SF 35 FAIN 79 93 1.81
4 R1 1.0 SF 35 PERL 8.5 BENT 2.0 116 1.62
5 R1 1.0 SF 35 COAL 27 63 1. 75
6 R1 1.0 SF 35 GILS 27 63 1. 74
7 Rl 1.0 SF 35 SMS 2.5 122 1.44
8 R1 1.0 SF 35 MSS 2.5 130 1.43
9 R1 1.0 SF 35 DE 20 91 1. 74
10 Rl 1.8 SAND 35 FAIN 79 93 1.81
11 Rl 0.8 SF 100 72 1. 92
12 Ideal "B" Rl 1.2 SAND 35 56 1. 91
13 Rl 1.5 SF 35 56 1.91
14 R1 0.6 SF 35 f)ERL 8.5 BENT 2.0 118 1.62
15 R1 1.0 SF 35 FAIN 79 120 1. 70

16 Unadeep "J" Rl 0.4 44 1.85


17 " R1 0.4 FAIN 79 75 1.80
18 Rl 0.4 PERL 8.5 BENT 2.0 106 1.60
19 Rl 0.4 BENT 4.0 65 1. 70
20 Rl 0.4 BENT 8.0 86 1. 57
21 Ciment Fondu Rl 1.5 R2 1.5 50 1.84
22 Rl 1.5 R2 1.5 FAIN 85 81 1. 78
23 Slag Cement Rl 1.3 SF 35 56 1. 91
24 II
Rl 1.3 SF 35 FAIN 79 93 1.81
25 Rl 1.3 SF 35 SMS 1.5 122 1. 54
26 R1 1.3 SF 35 pp 10 74 1. 79

ADDITIVE CODES

Rl - retarder - proprietary blend of sugar and lignin derivatives


R2 - retarder - proprietary blend of lignin and inorganic salts
SAND - silica sand, 100)J1ll average particle size
SF - silica flour, (10)J1ll average particle size
DE - diatomaceous earth
FAIL - LaDue fly ash
FAIN - Needles fly ash
PERL - expanded perlite
BENT - bentonite (gel)
SMS - sodium metasilicate
MSS - modified sodium silicate
COAL - powdered coal
GILS - gilsonite
TABLE 4
RESULTS OF INITIAL SCREENING PROGRAM
See Table 3 for System Compositions
Thickening Percent
Time Bond Expansion
System 300°F BHCT Water Permeabiity Strength (MPa) 204°C
No. (hr:min) 227°C, 3 days (md) outside inside Test 1 Test 2
1 3:24 227 23.4 15.9 37.3 30.0 0.016 1.0 10.3 0.12
316 33.5 6.1 38.6
2 +6:00 227 24.8 34.5 49.0 19.0 <0.001 3.1 16.5 0.13 0.14
316 35.5 31.4 47.4
3 +6:00 227 17.4 36.9 41.4 34.5 <0.001 5.9 16.2 0.17 0.12
316 25.0 9.9 20.1
4 +6:00 227 11.1 6.1 9.7 5.4 0.05 1.0 4.8 0.19 0.19
316 7.2 7.4 12.4
5 +5:00 227 17.6 21.6 19.0 3.4 8.8 0.15 0.18
316 9.8 37.4
6 +5:00 227 21.0 16.4 18.1 <0.001 4.5 12.2 0.20 0.22
316 5.2 19.9
7 +6:00 227 1.2
316 1.4
8 0:38 227
316
9 +6:00 227 19.8 14.7 15.9 0.058 0.7 5.9 0.15 0.17
316 13.2 38.6
12 3:19 227 20.7 23.5 4.1 0.035 0.2 2.6 0.07 0.10
316 43.8 30.6 36.6 51.0

13 +6:00 227 36.9 40.4 9.3 <0.001 0.5 0.7 0.16 0.17
316 18.8 45.1
14 +6:00 227 3.4 10.5 15.7 0.07 1.9 7.6 0.17 0.16
316 6.1 4.8
15 4:51 227 23.5 33.0 2.6 <0.001 0.7 2.4 0.24 0.20
326 31.8 28.0 19.3
16 6:00 227 30.3 37.1 29.6 22.3 2.6 11.9 0.21 0.23
316 28.2 31.3 27.8
17 6:00 227 1.7 6.7 6.4 23.1 0.03 1.2 4.7 0.00 0.07
316 19.6 25.5 22.0
18 3:18 227 0.4 3.2 4.0 0.2 2.4 0.20 0.22
316 3.6 5.7 3.4
19 4:03 227 14.5 16.8 13.9 11.4 <0.001 0 0.5 0.27 0.19
316 5.0 6.2 3.0
20 2:02 227 5.5 14.5 15.7 11.4 <0.001 0 0.14 0.10
316 5.9 6.2 4.5
21 4:07 227 6.8 23.1 0.101 4.1 11.0 0.00 0.02
316 13.7
22 +6:00 227 9.4 8.3
316 7.5 7.6

23 +6:00 227 10.5 26.1 16.5 <0.001 2.1 >17.2 0.19 0.22
316 30.0 23.8 27.4 25.9
24 5:00 227 30.3 8.3 16.8 <0.001 13.1 0.15 0.14
316 31.6 24.7 31.7 15.8
25 +6:00 227 23.4 3.1 7.4
316 7.4 7.7 3.1 8.3
26 +5 :00 227 11. 0 19.9 18.1 0.01 3.1 12.1 0.20 0.20
316 18.1 13.6 8.2 19.0
TABLE 5
RESULTS OF SIMULATED GEOTHERMAL TESTING PROGRAM UTILIZING THE D-BETA
Conditions: 150°C Circulating Brine
System Composition Given in Table 3
Depth of
System com~ressive Strength (MPa) Water Permeability (md) Deterioration
No. 14 days 8 days 3 months 15 months 14 days 28 days 3 months 15 montns (em at 15 months}
1 27.6 36.5 29.2 16.5 0.011 0.032 0.066 0.13 0.16
2 57.9 71.6 34.1 15.5 0.002 0.009 0.012 0.011 0.13
3 33.3 29.2 25.5 15.0 0.004 0.035 0.039 0.024 0.16
4 11.0 7.6 5.9 0.1 0.072 0.098 0.15 Soft 1. 27
5 31.0 0.005
12 14.8 17 .8 17.6 35.9 0.018 0.027 0.078 0.13 0.16
13 44.1 40.7 37.2 34.8 0.008 0.012 0.011 0.016 0.13
14 12.1 10.3 6.8 0.2 0.110 0.103 0.24 Soft 0.95
16 18.6 25.9 23.3 15.5 0.049 0.041 0.085 0.35 0.31
17 24.7 20.3 16.5 8.3 0.006 0.078 0.093 0.19 0.31
20 10.3 14.8 15.2 Broken 0.149 0.042 0.098 Broken

TABLE 6
RESULTS OF FIELD TESTING AT EAST MESA TEST FACILITY
Com~ressive Strength (MPa) Water Permeability (md) Size Reduction (%~
1 mo. 3 mo. 7 mo. 17 mo. 1 mo. 3 mo. 7 mo. 17 mo. 1 mo. 3 mo.
- - -- 7 mo.
- -
I 19.5 3.4 19.2 1.9 0.03 0.002 0.03 0.02 6 12 25
2 10.3 6.2 1.1 0.01 0.001 0.08 6 12
3 15.5 9.7 10.4 7.2 0.02 0.01 0.02 0.08 6 12 19
5 11.9 12.6 11.6 6.9 0.08 0.16 0.06 0.08 6 12 25
10 24.7 6.9 0.8 0.04 0.01 0.08 1.00 6 12 12
11 4.7 16.9 6.3 0.07 0.08 0.40 3 12 27
12 17.2 5.4 9.8 9.9 0.01 0.01 0.02 0.02 0 6 37
13 14.0 8.6 12.4 2.9 0.006 0.02 0.03 6 12 37
15 10.5 5.4 8.1 1.4 0.08 0.45 0.02 0.31 6 19 25
16 18.6 25.9 28.5 7.0 0.18 0.41 0.03 0.35 6 12 37
17 12.6 5.4 12.5 1.7 0.10 0.35 0.001 0.20 12 19 37

TABLE 7
RESULTS OF FIELD TESTING AT NILAND TEST FACILITY
Water Permeability (md)

1 13.5 cracked
2 23.5 cracked
3 13.9 cr acked
5 11.3 cracked
10 24.5 0.018
11 0.060
12 19.1 cracked
13 23.9 cr acked
15 30.3 0.106
16 18.3 cracked
17 10.4 cr acked
TABLE 8
TEST RESULTS FOR FURFURYL ALCOHOL/COAL SYSTEM

Thickening Time Sl ur ry
150°C BHCT Dens ity
System Composition (hr :mi n) (g/crn 1 )

Neat Furfuryl Alcohol 6:00+ Poured Out

Furfuryl Al cohol +
2.4% Tartaric Acid
Solution (50%) 0: 58 Set

48.8% Furfuryl Al cohol


48.8% Powdered Coal
2.4% Mal ic Acid Solution 0: 31 Set

50.0% Furfuryl Alcohol


50.0% Powdered Coal 6: 10 Set

31.0% Furfuryl Alcohol


31.0% Experimental Resin 4607
37.0% Coal «20 mesh)
1.0% ZnC12 Solution (5OX,) 2: 25 Set

31.25% Furfuryl Al cohol


31. 25% Exper irnenta 1 Res in 4607
37.0% Coal «20 mesh)
0.5 ZnC12 Solution (50%) 4: 15 Set 36.0 29.0 Burned 0.004 0.001 Burned 1.26

31.4% Furfuryl Alcohol


31.4% Experimental Resin 4607
37.0% Coal «20 mesh)
0.2% ZnC12 Solution (50"/') 6: 25 Set 28.6 Burned 0.003 Bur ned 1. 27

TABLE 9
COMPOSITIONS OF ULTRA LIGHTWEIGHT CEMENT SLURRIES CONTAINING GLASS BUBBLES
CLASS G CEMENT

S~stem No. % Silica Flour Gl ass Bubble Grade

GB 1 1.20

GB 2 20 1.20

GB 3 35 1. 26

GB 4 35 1.40

GB 5 35 1.28

GB 6 35 1.36

TABLE 10

RESUL TS OF TEST! NG ULTRA LI GHTWE IGHT GLASS BUBBLE CEMENTS


(SPECIMEN EXPOSED TO FRESH WATER)

3-Month Compress i ve I-Month I~ater 3-Month Water


Strength (MPa) Perrneabi 1i ty (md) Permeabi 1 i ty (md)

System
GB 1.3 0.8 0.2 1.2 0.8 0.3 0.024 0.00 Soft Soft Soft Soft

GB 9.0 2.6 2.6 5.7 5.9 3.8 0.004 0.58 0.56 0.003 0.037 0.80

GB 6.6 11.5 5.8 6.6 Crumbled 6.0 3.8 3.8 0.14 0.003 0.11 0.19 Crumbled 0.002 0.12 0.29

GB 10.2 8.1 3.8 9.7 5.1 5.3 4.5 6.6 0.12 0.031 0.17 0.10 0.68 0.010 0.15 0.049

GB 2.1 6.7 2.4 4.8 Soft 1.2 0.7 5.3 0.52 0.011 0.25 0.19 Soft 0.017 0.19 0.27

GB 4.1 6.6 3.1 5.9 0.5 2.6 2.5 5.2 0.45 0.037 0.24 0.20 Soft 0.004 0.12 0.067
TABLE 11
PERFORMANCE OF PROPOSED GEOTHERMAL CEMENT SYSTEMS
Compressive Strength 400°F
Thickening 1 day 28 days Permeability
Slurry CompoSition Time (mi n) (MPa) (MPa) (md)
l. Class G + 35% silica flour
+ lignin/sugar retarder + +360 52.4 25.0 0.01
1.5% cellulosic fluid-loss
additive + 54% H2O
2. Class G + 35% silica flour
+ 1% lignin/sugar retarder +360 41.3 24.1 0.01
+ 0.35 gal/sk liquid fluid-
loss additive + 0.8% disper-
ant + 54% H2O
3. Class B + 35% silica flour +
1% lignin/sugar retarder + 150 NS 18.5 0.01
1.5% cellulosic fluid-loss
additive + 56% H2O
4. Class J + 1.5% cellulosic
fluid-loss additive + 0.4% +360 30.2 24.1 0.01
lignin/sugar retarder + 44%
H2O
5. Class J + 0.35 gal/sk liquid
fluid-loss additive + 0.8% +360 26.3 17.7 0.01
dispersant + 0.4% lignin/sugar
retarder + 44% H2O
6. Class G + 35% silica flour +
2% bentonite + 8.5% perlite + +360 14.2 10.8 0.09
1.5% cellulosic fluid-loss addi-
tive + 1.0% lignin/sugar retarder
+ 116% H2O
7. Class G + 35% silica flour + 10%
diatomaceous earth + 1.5% cellu- +360 15.5 13.8 0.10
losic fluid-loss additive + 1.0%
lignin/sugar retarder + 91% H2O
8. Class G + 100% silica flour + 2%
silica extender + 1.0% lignin/sugar +360 17.7 6.5 0.04
retarder + 1.5% cellulosic fluid-
loss additive + 1.0% NaOH + 136%
H2 O
CANDIDATE
SYSTEM

Fig. 1 - Block diagram of screening program


for candidate geothermal cement systems

KEY TO ABBREVIATIONS:

BPR Back Pressure Regulator


PI Prenure Indicator
PR Pressure Recorder
PT Pressure Transducer
TF T"mnl"mtur(' Elp.ment
TI 1 empefdlult: 1II01l.:,:IIor
TR Temperature Recorder
TT Temperature Transduct'!'r
..f Flow to CorE's
-1+ Flow from Cores to Reservoir

Fig. 2 - Schematic diagram of dynamic brine


exposure testing apparatus (D-BETA)