Silica-Lime Based Hydrothermal Cements for High-Temperature Geothermal Applications

Rafael Hernández, Lance Brothers and Robert Martin, Halliburton

Key words: non-portland, cement, Silica, Lime, hydrothermal, high temperature

Abstract
To provide a more reliable composition and help eliminate strength retrogression in Portland
cements, silica-lime cements have been developed as a solution for high-temperature geothermal
cementing applications. Portland cements have been used successfully in geothermal cementing;
however, because of variations in their chemical composition, partly due to their complex
manufacturing process, these types of cements might not be acceptable when cementing wells
with bottomhole circulating temperatures (BHCT) exceeding 230°F. At these temperatures,
Portland cements can demonstrate inadequate performance. In contrast, the chemical
composition of silica-lime cement can demonstrate far less variability.
The silica-lime cement compositions consist of a mixture of ground quartz and hydrated lime. At
temperatures greater than 190°F, lime will react with quartz and water to form calcium-silicate
hydrate. The temperature at which the reaction takes place will dictate the ratio of calcium-to-
silica and water-to-calcium silicate. These compositions have been laboratory tested for
thickening time, compressive strength, rheology, and compatibility with geothermal drilling
muds. This paper presents laboratory test results as well as a discussion on the advantages of the
cement compositions. Silica-lime based cements are simple, but flexible systems that can offer
more reliability for high-temperature cementing applications.

Definitions
Hydrothermal cement. Hydrothermal cement is referred to as a hydraulic cement that requires
exposure to high temperatures to react to form a monolithic solid.

Hydrothermal well system. A Hydrothermal well system refers to the most common
geothermal well completion that is used to harvest heat from natural convective resources.

Enhanced geothermal system. An enhanced geothermal system consists of well completions

engineered to harvest heat by creating a subsurface fracture system to which water is added
through injection wells. Water is heated by contact with the rock and returns to the surface
through production wells.

Introduction
Recent advancements in drilling technology have enabled reaching deeper and hotter targets,
providing a valuable contribution to the development of hydrothermal and enhanced geothermal
system’s developments in the geothermal industry. These hotter environments have made it
increasingly difficult to design a cost-effective and competent cementing solution to provide the
necessary zonal isolation during the well-construction phase. Silica-lime hydrothermal cement
(SLHC) has been recently adapted to provide a reliable cementing solution for high-temperature
geothermal wells. Silica sand and hydrated lime react with water under the high temperature,
rendering a simple and reliable cement system (Figure 1). Conventional additives can be used
with these systems to provide slurries applicable to high-temperature well conditions.
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Although Portland cement is the most widely used cement in geothermal well construction, it is
extremely difficult to retard its hydration to allow for adequate placement time in deep hot wells.
Typical remedies have been to add excessive concentrations of retarders and dispersants. Both
methods lead to higher costs and do not always result in a satisfactory slurry. During the normal
hydration of Portland cements, calcium-hydroxide crystals are formed. Calcium hydroxide will
react with silica in solution at high temperatures to form stable compounds, such as xonotlite and
tobermorite. One of the reasons that silica is added to Portland cement is to stabilize it at elevated
temperatures. In the SLHC system, calcium hydroxide and silica are the only mineral reactants
present, with Portland cement being eliminated. The result is cement that is easy to retard
because of the absence of the rapidly hydrating phases present in Portland, such as calcium
aluminates and calcium silicates. Variations in the composition of Portland cement is another
complicating factor because all Portland cements vary from batch to batch. Portland cement has
been placed at circulating temperatures above 400°F with the addition of hydration retarders, but
design becomes difficult (Brothers et al. 2010). With SLHC, the cement is a consistent product
as long as attention is paid to purity and particle size.
The number of deep, hot wells being drilled each year, especially in EGS development,
continues to rise. Completion in these wells has magnified many of the problems normally
encountered in shallow wells. Temperature at total depth and particularly temperature differential
from top to bottom of the wellbore are the usual complicating factors. These factors, combined
with high reservoir pressures and/or low fracture gradients, produce a situation that demands
complicated completion procedures requiring the use of reliable cementing systems (Hook et al.
1971). Cement slurry-setting time must be controlled to provide ample placement time at the
bottomhole temperature, without a risk of over-retardation at surface temperature, in a cost-
effective manner. SLHC designs can improve the reliability of high-temperature geothermal
completions. Temperatures above 190°F are sufficient to promote the reaction of lime with silica
sand (Brothers et al. 2010).

Building Silica-Lime Hydrothermal Cement

The reaction of calcium hydroxide and quartz is a through-solution process that requires quartz
to dissolve and react to form calcium silicate hydrates. For this reason, silica flour with an
average particle size of 20 microns is most suitable for use because of its high surface area. This
size silica is commonly added to Portland cement at temperatures above about 230°F to prevent
strength retrogression. High calcium content and particle size are the critical factors for selection
of lime (Hook et al. 1971). The ratio of sand to lime is important for the formation of tobermorite
and xonotlite. These phases have been shown to be two of the most important strength-producing
constituents of hydrated cement (Jing et al. 2007). An optimum ratio of silica, lime, and water
must be achieved to form a high-strength silica-lime cementing system at hydrothermal
conditions without compromising slurry flow and mixing characteristics. High temperatures are
necessary to promote the reaction of lime with silica.

Retarding Silica-Lime Hydrothermal Cement

Predictable retarder response is the key factor influencing the development of SLHC systems.
This is particularly important when contrasted with Portland cement. Portland cement is
manufactured to fall within certain minimum specifications detailed in API spec 10B. However,
it has been found that Portland cements from various manufacturers or from different batches do
not necessarily have the same response to retarders, especially when subjected to high-

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temperature testing. Variations in retarder response could affect the operator’s ability to predict
Portland-cement performance. These variations might not be noticeable at lower temperatures.
However, retarder response testing should not be neglected, even for low-temperature
environments. The temperature differential between the top and bottom of most deep
completions makes it necessary to optimize retarder concentration for each job. Optimum
retarder concentration can be easier to achieve when the cement slurry is pumped in reverse-
circulation fashion (Hernández and Bour 2010). A slurry with too much retarder will not set at
the lower temperature at surface within the desired wait-on-cement time. This can result in
additional rig time and unnecessary expense.
Table 1 shows retarder response of SLHC over the temperature range of 300 to 500°F at a slurry
density of 15 lbm/gal to 15.26 lbm/gal.
Because of the low reactivity of both silica and lime, they can be combined with water and
existing Portland-cement additives to form a slurry that can be placed at extremely high
temperatures. Lignosulfonates have been used as cement retarders in well-cementing operations
for many years. A limitation is their inability to effectively retard the hydration of Portland
cement at temperatures above about 250°F (Brothers et al. 2010). The simplicity of the reaction
between high-quality silica and lime make this a system with predictable retarder response.

Mechanical Properties of SLHC

Compressive strength, Youngs’s modulus, and Poison’s ratio are critical parameters that provide
an indication of long-term cement-sheath performance. Many factors influence the mechanical
properties of different cement types and compositions (including SLHC), such as water-cement
ratio, cementitious material content, temperature, chemical composition, and additives.
Mechanical properties of SLHC data are shown in Tables 2 and 3 for slurry densities of 14.63
lbm/gal to 15.25 lbm/gal and for various retarder concentrations and a temperature range of 400
to 550°F. As in Portland cement, temperature and slurry density have an effect on the ultimate
strength of silica-lime cement.

Compatibility of SLHC
Compatibility among cement systems, additives, and drilling fluids is a critical parameter that
affects fluid performance and, ultimately, a cementing operation. Portland cement is compatible
with most water-based drilling muds widely used in geothermal drilling. However, during a
cementing operation, the interface of mud and cement can be minimized with the use of spacers
and preflushes. SLHC, as well as Portland cement, has high lime content, so a similar influence
from standard additives and drilling muds can be expected. SLHC is compatible with Portland
cement and with most standard Portland-cement additives.

Environmental Impact of SLHC

Portland cement is prepared conventionally by grinding limestone, clay, and other materials and
burning the mixture in a rotary kiln where the temperature approaches 3,000°F. The mixture is
sintered and fused together into clinker, which is then ground to a fine powder. Substantial fuel is
required to provide the energy demand for this conventional cement material. Conversely, SLHC
production does not have a substantial fuel requirement, producing less than one third the
amount of carbon dioxide on a per-pound basis of dry material; hence, a SLHC system can
provide a significantly lower carbon footprint (Brothers et al. 2010).

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Conclusions
A cost-effective and simple alternative to Portland cement is available for cementing high-
temperature geothermal wells. Silica flour and hydrated lime react to form a reliable cementing
composition for high-temperature well cementing. Conventional retarder additives developed for
Portland cement can be used to control the setting time of silica-lime hydrothermal cements.
Silica-lime cement is compatible with most drilling muds that are compatible with Portland
cement. The current state of technology requires that the temperature be a minimum of 190°F for
the material to develop compressive strength and set to a monolithic solid, with low
permeability, comparable to Portland cement. The SLHC system can provide reduction in
retarder costs. The SLHC system can provide a significantly lower carbon footprint, producing
less than one third the amount of carbon dioxide on a per-pound basis of dry material (Brothers
et al. 2010). The simplicity of the reaction between high-quality silica and lime makes this a
system with predictable retarder response.

References
Hook F.E., E.F. Morris, and R.B. Rosene, 1971. “Silica-Lime Systems for High-Temperature
Cementing Applications.” Paper SPE 3447 presented at the Annual Meeting,
New Orleans, Louisiana, 3–6 October.

Jing Z., F. Jin, T. Hashida, N. Yamasaki and H. Ishida, 2007. “Hydrothermal Solidification of
Blast Furnace Slag by Formation of Tobermorite.” Published online: 21 June. Springer
Science+Business Media, LLC.

Maravilla S. 1974. “A Hydrothermal Setting Cement for Cementing Ultradeep, Hot Wells.”
Journal of Petroleum Technology, (26)10: 1,087–1,094.

Brothers L., B. Iverson and D. Bour, 2010. “NonPortland Cement-Based Systems for
Geothermal Well Use.” Paper presented at the 35th Workshop on Geothermal Reservoir
Engineering, Stanford University, Stanford, CA, 1–3 February.

Hernández R. and D. Bour, 2010. “Reverse-Circulation Method and Durable Cements Provide
Effective Well Construction: A Proven Technology.” Paper presented at the 35th Workshop on
Geothermal Reservoir Engineering, Stanford University, Stanford, CA, 1–3 February.

Hernández R. and H. Nguyen, 2010. “Reverse-Circulation Cementing and Foamed Latex

Cement Enable Drilling in Lost-Circulation Zones.” Paper presented at the World Geothermal
Congress, Bali, Indonesia, 25–29 April.

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Fig. 1—Cement after curing showing the unique crystal structure formed through the
reaction of lime and silica (Brothers et al. 2010).

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Table 1: Cement Thickening Time

Silica:Lime Lignosulfonate Slurry Organic Temperature, Dispersant, Thickening
Weight Ratio Retarder, % Density, Acid °F % Time,
lbm/gal Retarder, hr:min
%
5:1 0.50 15.0 0 300 0.5 2:30
5:1 0.25 15.0 0 300 0.5 1:24
10:1 0.50 15.26 0 400 0 2:02
10:1 0.60 15.26 0 400 0 5:39
10:1 1.00 15.26 0 400 0 +7:15
10:1 0.60 15.26 0 450 —0 2:30
10:1 0.70 15.26 0 450 —0 4:45
10:1 1.00 15.26 0.50 400 —0 +6:00
10:1 2.00 15.26 1.00 450 —0 +6:00
10:1 2.00 15.26 1.00 500 —0 +6:00

Table 2: Mechanical Properties after Curing 28 Days at 400°F

Silica:Lime Water/Blend Slurry Compressive Young’s Poisson’s
Weight Ratio Ratio Density, Strength, Modulus Ratio
lbm/gal psi
5:1 0.35 15.25 366 2.90E+05 0.082
*
5:1 0.35 15.25 468 5.22E+05 0.074
*
2.33:1 0.35 15.12 1,207 11.1E+05 0.068
0.81:1 0.38 14.63 898 5.11E+05 0.138
*Included 1% Lignosulfonate retarder by weight of blend.

Table 3: Mechanical Properties after Curing 28 Days at 550°F

Silica:Lime Water/Blend Slurry Compressive Young’s Poisson’s
Weight Ratio Ratio Density, Strength, Modulus Ratio
lbm/gal psi
5:1 0.35 15.25 816 3.98E+05 0.084
*
5:1 0.35 15.25 724 4.49E+05 0.087
2.33:1* 0.35 15.12 852 7.31E+05 0.114
0.81:1* 0.38 14.63 2,184 7.18E+05 0.137
*Included 1% lignosulfonate retarder by weight of blend.