Académique Documents
Professionnel Documents
Culture Documents
This paper was prepared for presentation at the SPE Thermal Well Integrity and Design Symposium held in Banff, Alberta, Canada, 28-30 November 2017.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.
Abstract
Often, gas travels through microfractures and channels and requires the use of a solids-free chemical to
adequately fill and block gas pathways. Recent years have shown sodium silicate as an effective and
environmentally friendly treatment option. With lower oil prices and increasing regulatory requirements
there is a greater need to improve treatment performance and reduce costs in the treatment of surface casing
vent flows and gas migration. Recognizing these needs, the chemistry of conventional sodium silicate was
modified to allow for a broader range of application and provide improved physical properties upon setting.
Conventional manufacturing methods produce aqueous sodium silicate with a defined range of molecular
size, shape and charge. An alternative production method was developed that reduces the alkalinity and
increases the silica ratio and is described as a high-ratio sodium silicate. The form and distribution of silica
in solution is quite different than commercially available sodium silicate. The silicate molecules in solution
are significantly larger and with a lower charge density. The change in silica structure positively impacts
the setting of sodium silicate by polymerization and precipitation. Several of the commonly used setting
agents used with sodium silicate and/or colloidal silica were investigated with the high-ratio sodium silicate.
Compared to conventional silicates, the high-ratio silicate could achieve longer set times and was less prone
to variations in setting agent concentration. Upon setting, the high-ratio sodium silicate showed excellent
dimensional stability with significantly less setting agent requirement vs. conventional silicates.
Initial field trials took place in Western Canada using two distinct placement techniques. The first
approach was to squeeze the high-ratio silicate into microchannels as a standalone product. The second
approach was as a compliment to a cement squeeze. Field results ranged from complete zonal isolation to
reduced levels of gas migration. Where gas migration was not completely eliminated, data suggested that
not all pathways were squeezed and/or there were secondary sources of gas. On-going field trials will allow
for improvements and comparisons of placement techniques.
Introduction
Over the last few years, the use of sodium silicate has undergone resurgence for cement repair and as a
conformance material (Olgesby), (Omekeh), and (Skrettingland). This increase in popularity has also been
2 SPE-188166-MS
seen in Western Canada, with the focus on the use of sodium silicate for treatment of surface casing vent
flow and gas migration (Hogstead) and (Samuelson). Reviewing the literature, the growth in popularity is
being driven by increased regulatory pressure in combination with the performance properties commonly
associated with sodium silicate:
• easy to pump and place (low viscosity solution consisting of small molecules)
• upon setting the final product is thermally stable, has excellent chemical resistance and good
compressive strength
• cost effective
Over the last five years, best practices have developed with placement of sodium silicate and better
matching of formulations to specific SCVF challenges. The result has been greater success rates and
reduction in cost.
As with any product, there has been feedback on how sodium silicate could perform better. The top three
desired performance enhancements are:
Past research has focused on the use of additives such as polymers, novel setting agents or filler material
to improve performance properties. These approaches have been successful, but can create a different set
of limitations such as: increased viscosity, shorter set times, and the addition of solids. A constant in the
development effort has been the choice of sodium silicate. The vast majority of conformance treatments
have used a ~3.2 ratio sodium silicate. (The ratio refers to the proportion of sand to alkali that is used
to produce a particular grade of sodium silicate, and is expressed as the weight ratio SiO2:Na2O, in this
instance 3.2 lb SiO2 for every one lb of Na2O.) Compared to lower ratio sodium silicates, a 3.2 ratio sodium
silicates system is easier to polymerize and set. Upon setting and forming a silica gel, the system has higher
compressive strength values and improved durability with a reduced level of syneresis.
A logical question is if a 3.2 ratio is better than a 2.2 ratio, why not use a 4.2 ratio or higher? The answer is
partially answered by manufacturing limits. In a furnace, once the ratio of sand and soda begins to exceed a
SiO2:Na2O ratio of ~3.2 there is a rapid increase in temperature requirements to make molten sodium silicate
as well as a corresponding increase in molten glass viscosity. Assuming a high ratio glass was produced
in a furnace using ordinary means, the material would have limited solubility and stability in water. Upon
aging, it would be prone to separation and formation of a gel.
To move to a lower alkali, i.e. more silicious product, the end-user needs to jump from sodium silicate
to colloidal silica. This takes the user from using a solution of silicate molecules to an aqueous suspension
of discrete, nonporous particles of amorphous silicon dioxide. Colloidal silica, under the banner of "nano
particles", is used in conformance applications. This form of silica has several desirable performance
properties for conformance applications (Jurinak). Colloidal silica can have longer, more controlled gelation
times vs. sodium silicate. The produced silica gel tends to be less prone to syneresis (i.e. shrinkage). The
trade-offs are the produced silica gel has less strength, and a higher starting concentration than for sodium
silicate is required. Further, colloidal silica is a considerably more expensive chemical.
SPE-188166-MS 3
It is not a new idea to develop a sodium silicate that would have a ratio between conventional sodium
silicate and colloidal silica. The challenge has been producing a high-solids, stable product at a reasonable
cost. Iler (1970) was able to make to a 6:1 ratio sodium silicate that was stable against premature gelation.
This composition was demonstrated to have superior water resistance and binding ability compared to
conventional sodium silicate. NASA (Schutt, 1979) developed a high-ratio potassium silicate that had
improved stability via the incorporation of a silicone. The high ratio potassium silicate was used to make
zinc-rich paints for gantries and other steel launch structures. A stable, high solids material was later
achieved by Bass (1997) using a strong cation exchange resin to condense the lower molecular weight
silicate anions. Target applications for this product were once again adhesives and binders that required
greater water resistance.
A novel, cost-effective procedure has been developed to produce polysilicates for subterranean
applications (McDonald, 2012). A 4.5 ratio for both sodium and potassium silicate was selected as the focus
ratio for comparative study with conventional sodium silicate. Table 1 provides a comparison of the 4.5
ratio vs. 3.2 ratio vs. colloidal silica referenced in Jurnack.
Table 1—Physical properties of colloidal silica vs. 3.2 ratio vs. 4.5 ratio
Figure 1—the trend towards high molecular weight, more complex polysilicate anions with increasing ratio of SiO2:Me2O
A recent paper by Nordstrom (2012) has helped to advance the understanding within the SiO2:Na2O
range of 3.3 to 8.9. Several analytical techniques were used to determine size, internal structure, shape,
distribution of molecular structures, and degree of silica condensation. Figure 2 is taken from Nordstrom
and provides a schematic summarizing the components. The paper proposes that, as the ratio moves above
3.3, there is a decrease in low molecular weight species and extensive changes in the structure of the silica
species. It is proposed that silica begins to form clusters.
The polymerization or gelation of sodium silicate to silica gel in oilfield applications is summarized in
Krumrine (1985). Polymerization occurs as three simultaneous processes;
1. Small silicate species form higher order oligomers.
2. The intramolecular condensation of silanol groups within the silicate leading to ring closure and
eventual particle formation.
SPE-188166-MS 5
Gelation Time
Gelation times were measured as a function of ratio, concentration of setting agent, and temperature. The 4.5
ratio material was compared against the 3.2 ratio using visible observations as to the time to form a firm gel.
Table 3a shows the gelation time on an SiO2 equivalent basis using citric acid, sodium acid pyrophosphate
(SAPP), and triacetin as the setting agent. The 4.5 ratio silicate is seen as requiring roughly half the volume
of setting agent as the larger polysilicate anions would have a lower buffering capacity.
A thermally responsive gelation activator in the form of lactose was used to measure set time as a function
of temperature and concentration of lactose. Table 3b shows the gelation time can be extended using higher
temperatures, allowing for deeper and more controlled placement for thermal cement remediation. The
extended gelation time is thought to be a function of the lower alkalinity of the 4.5 ratio silicate.
6 SPE-188166-MS
Table 3a—Setting 3.2 and 4.5 ratio sodium silicate with SAPP, citric acid and triacetin at room temp
3.2 ratio 25ml 25ml Citric 25ml 25ml 2.5% 10% ~20min
4.5 ratio 40ml 10ml Citric 16ml 34ml 1.6% 10% ~2min
Table 3b—Setting 3.2 and 4.5 ratio sodium silicate with lactose at 50, 65 and 80C
Table 4—Durability of consolidated sand after curing 14 days with 4.5 ratio silicate using citric acid and triacetin
Setting agent
Test cycle Remaining weight, g Cumulative weight loss Remaining weight, g Cumulative weight loss
Figure 3—Sand consolidated with 4.5 ratio-citric acid, cracked at the 6th cycle (dry vs. wet
Permeability Reduction
To assess reduction in permeability, a similar formulation of 4.5 ratio silicate/citric acid/Barco sand was
tested using ASTM D5084−16a, "Standard Test Methods for Measurement of Hydraulic Conductivity of
Saturated Porous Materials Using a Flexible Wall Permeameter. Applying Darcy’s law, the permeability of
the sand is reduced by 4 orders of magnitude to the permeability of wet silt.
Table 5—Permeability of pure sand vs. consolidated sand with 4.5 ratio and citric acid
Corrosion Inhibition
Corrosion inhibition was included as part of the test protocol as another value of sodium silicate in SCVF
repair. Leaving excess sodium silicate in the casing offers several advantages, the principle benefit being the
sodium silicate acting as an environmentally friendly corrosion inhibitor. It was thought this feature would
be of high value in steam injections wells, given the widespread challenge of corrosion in the annular space
of the surface casing. A review of the literature shows a lack of prior art on the use of conventional silicates
(let alone high ratio silicates) for corrosion control under high temperature conditions.
Potassium silicate was chosen over sodium silicate to evaluate the efficacy of conventional and high ratio
material for high temperature corrosion protection. Potassium silicate was chosen so as to minimize the on-
site risk should the material come into contact with the ground surface (Duncan, 2004).
High temperature conditions will cause water to evaporate from aqueous sodium silicate. The low
viscosity sodium silicate will thicken and when evaporation approaches 14% a 3.2 ratio sodium silicate has
in effect set. Exposure to temperatures above 100C will cause the silicate to intumesce to a hard, hydrated
silicate foam. The foam is created as water is converted to steam and expands within the silicate. To test the
corrosion inhibition properties of intumesced potassium silicate, corrosion coupons were placed in crucibles
which were then filled with potassium silicate. The crucibles were heated to the indicated temperature: the
potassium silicate formed a foam (figures 5a, b). Corrosion testing involved a series of 8 hrs. boil cycles
in a 1% NaCl solution. The intumesced potassium silicate did not dissolve in boiling salt water. It was
speculated that hardness might help inhibit dissolution with the gradual formation of calcium silicate. (The
calcium enters the system through tap water and through food-grade sodium chloride.) Upon completion of
testing, the intumesced foam was removed with a hot solution of potassium hydroxide. Per graph 1, there
was minimal corrosion with standard ratio potassium silicate and even less with 4.5 ratio potassium silicate.
SPE-188166-MS 9
Figure 5a—corrosion coupons coated with intumesced 4.5 ratio potassium silicate
Graph 1—Corrosion rate of uncoated coupon, K45 and EcoDrill 317coated coupon after 6 cyclic salt water tests
10 SPE-188166-MS
A corrosion cell simulating the annular space was constructed out of mild steel (figures 6a,b). The annular
space underwent the same sequence of testing as the corrosion coupons. Balance limitations did not allow
for measurement of corrosion rate. Upon removal of the intumesced potassium silicate, visible observations
showed no corrosion in the area of contact, but signs of corrosion just above the area that had been covered
with potassium silicate. Testing shows that intumesced potassium silicate can provide corrosion protection.
Initial data indicates the efficacy is impacted by:
Figure 6a—mild steel coated with intumesced conventional ratio potassium silicate
Field Trials
At the time of this paper a limited number of operators and service companies have evaluated 4.5 ratio
sodium silicate, but trials have so far been restricted to conventional wells. Given that successful SCVF
repair is as much of a function of good chemistry as well as good diagnostics and good placement, more
trials will need to be run to determine the true value in the field. Summarized in generic terms are different
applications of 4.5 ratio and feedback compared to 3.2 ratio sodium silicate.
SPE-188166-MS 11
A 4.5 ratio was used to shut-off a low rate vent flow. The 4.5 ratio was diluted 1:1 vol/vol with water. The
system was used without the addition of setting agent to the 4.5 ratio material because prior to placement a
small HCl squeeze was performed to open perforations and pathways. A fresh water preflush was squeezed
to remove residual HCl and hardness leftover from perforating. Upon placing a third of the 4.5 ratio
treatment volume, pump pressure rapidly increased to the frac gradient indicating the high ratio silicate had
set hard. The gas flow rate was reduced by a factor of 10 and was trending towards 0. The trial was deemed
successful, but future work would likely involve a larger preflush of water to allow for a larger volume/
deeper placement of the silicate.
A best practice to emerge with treating SCVF in Western Canada is to pump a small volume of 3.2 ratio
sodium silicate before a remedial cement squeeze. Typically, these squeezes involve a preflush of water with
a softener followed by 500 litres to 1 m3 of diluted 3.2 ratio sodium silicate. Once the silicate is squeezed
then it is followed by a water spacer and then the cement. This approach allows sodium silicate to deeply fill
and block microchannels that would otherwise quickly bridge with cement. This technique has increased
the success rate of cement remediation for blocking SCVF. Over a dozen trials were run with the 4.5 ratio
and performance appears to be similar to cement remediation using 3.2 ratio sodium silicate. Trial work
will continue with the preflush being modified and /or made smaller so as to allow more reactivity between
the 4.5 ratio sodium silicate and hardness present in the squeezed micro annuli.
Conclusions
4.5 ratio sodium silicate was developed to enhance the performance of silicate-based technology, lower
the cost, and improve success of treatments. Lab results indicate certain performance enhancements over
conventional silicate enhancement. These enhancements include;
– higher levels of corrosion inhibition
– less syneresis
– better control over gelation times
There have been insufficient field trials to indicate if high ratio is lowering costs and/or providing a better
seal. Likely there will not be one ideal ratio of silicate. The selection of potassium or sodium silicate needs to
consider several factors: downhole conditions; placement technique; and logistics. The development of high
ratio polysilicates will increase the formulation options, including placement without the use of a setting
agent.
Compared to conventional ratio silicates there is little academic research on the properties of high ratio
silicate. It is anticipated that research in silicate speciation of polysilicates will increase as commercial usage
grows.
Acknowledgements
Thanks to Dr. Julie Shang, Dr. Yu Guo and Bingfeng Xue of University of Western Ontario Geotechnical
Research Centre for their research and insights. The authors would also like acknowledge Dr. Hatzignatiou
for his early research into the application of polysilicate material for conformance applications. Recognition
also goes to Darrell Lindstrand of Charger Pumping Solutions as well as Colin Logan of Earth Fluids for
running the first field trials.
Nomenclature
SCVF = Surface Casing Vent Flow
mpy – mils per year
12 SPE-188166-MS
References
1. Bass J.,: US Patent 5,624,651 (1997)
2. Duncan J. et al., "Exceeding Drilling Performance and Environmental Requirements with
Potassium Silicate Based Drilling Fluid", SPE 86700, International Conference on HS&E,
Calgary, Alberta, March 2004
3. Hatzignatiou D. et al., "Laboratory testing of environmentally friendly chemicals for water
management", SPE 173853 Bergen One Day Seminar, Bergen, Norway, April 2015
4. Hogstead C. et al., "Remedial Casing/Cement Repair with Sodium Silicate" Canadian
Association of Drilling Engineers, Calgary, Alberta, May 2011
5. Iler, R.K. 1979. The Chemistry of Silica. New York; John Wiley and Sons
6. Iler R.: US Patent 3,492,137 (1970)
7. Jurinak J. J et al., "Oilfield Applications of Colloidal Silica Gel", SPE 18505
8. Krumrine P. H. and S.D. Boyce, Profile Modification and Water Control with Silica Gel-Based
Systems, SPE 13578 presented at the 1985 SPE International Symposium on Oilfield and
Geothermal Chemistry, Phoenix, AZ, April 9-11, 1985
9. McDonald M. : CA2771577A1 (2012)
10. Nordstrom J. et al., "Silica/alkali ratio dependence of the microscopic structure of sodium silicate
solutions", Journal of Colloid and Interface Science 397 (2013) 9–17
11. Oglesby K. et al., "Field Test Results of a New Silicate Gel System that is Effective in Carbon
Dioxide Enhanced Recovery and Waterfloods", SPE-179615-MS, SPE Improved Oil Recovery
Conference held in Tulsa, Oklahoma, USA, 11–13 April 2016
12. Omekeh A. et al., "Silicate Gel for In-depth Placement – Gelation Kinetics and Pre-flush
Design", IOR NORWAY 2017 – 19th European Symposium on Improved Oil Recovery, 24-27
April 2017, Stavanger, Norway
13. Samuelson D., "Gas Migration Repair with Sodium Silicate100/3-22-47-8W5", CSGM/SPE
Workshop held in Banff, Alberta 2015
14. Skrettingland K., et al., "Snorre In-depth Water Diversion Using Sodium Silicate – Large Scale
Interwell Field Pilot", SPE 169767, SPE EOR Conference held in Muscate, Oman, 2 April 2014
15. Schutt J.: US Patent 4,162,169 (1979)
16. Vail, J.G., "Soluble Silicates; Their Properties and Uses", Vol. 2, Reinhold Publishing, New York