SPE-173792-MS

Effective Scale Prevention Using Chemically Infused Proppant - A Uinta

Basin Case History
Joshua G. Leasure, Robert J. Duenckel, and Jeff Hebert, CARBO Ceramics, Inc.

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Symposium on Oilfield Chemistry held in The Woodlands, Texas, USA, 13–15 April 2015.

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
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Abstract
Scale deposition down hole is a well-known and common production problem throughout the industry.
Successful treatment of scale where it is first deposited near wellbore can be challenging in many cases,
and sometimes impossible in others. While production assurance and scale inhibition chemicals have
traditionally been added as a liquid in the fracturing fluid, this approach is often not very efficient or
effective as a standalone inhibition strategy. Quite often a significant fraction of the chemical immediately
returns during the initial flow back with only a small portion remaining for future inhibition. This then
typically necessitates reapplication of the inhibitor chemicals using a squeeze treatment or continuous
injection.
The chemical delivery system described here utilizes porous ceramic proppant, which has been infused
with the appropriate production chemical(s) and encapsulated. The infused ceramic proppant is added at
a designed small weight fraction to the rest of the proppant volume in the fracture treatment. It is
manufactured to perform as both a proppant and a chemical delivery system so it replaces an equivalent
volume of standard proppant in its dual function as a proppant [Duenckel, 2014]. After placement in the
fracture the chemical slowly releases from the proppant over the designed treatment period. This chemical
delivery system allows for a large amount of chemical to be placed within the fracture, releasing slowly,
without negatively impacting conductivity. The proppant is encapsulated with a semipermeable membrane
which controls the release of production chemicals during placement and production. This provides long
term scale protection and production assurance which eliminates the need for additional costly well
treatments and lowers overall lease operating expense.
In addition to describing the chemical delivery system, this paper will present a case history in which
five wells in the Uinta Basin were treated with scale inhibitor using this new delivery system. In this
application the infused porous ceramic was added in at a design fraction to natural frac sand treatments.
Inhibitor returns will be presented which illustrate the efficient, long term protection of the entire
production system from both barium sulfate and calcium carbonate scale.
This paper will be useful for all production and completions engineers and technicians who are engaged
in providing long term scale prevention and production assurance.
2 SPE-173792-MS

Introduction
Scale deposition is a widely recognized production problem within the oilfield. The deposit of scale
downhole can cause severe blockage in tubulars, and proppant packs and limit the efficiency and
effectiveness of downhole pumping equipment, restricting flow and causing reduced production. The
remediation of scale can lead to costly workovers, pump repairs, and well downtime.
To avoid scale deposition and lost production time, scale inhibitor chemicals are placed downhole and
there are a number of common methods for placement. One is delivering these chemicals directly as an
additive to fracturing fluids [Brock, 2005, Szymczak, 2007]. In this case a large portion of the chemical
will return quickly to surface during flow back resulting in a limited supply of inhibitor remaining
downhole and thus limiting the duration of effective scale inhibition due to rapid depletion of the inhibitor.
When the chemical is depleted, inhibitor is often then placed into the formation (or fracture) via a squeeze
treatment [Kan, 1999; Kan, 2004]. Scale inhibitor is injected into the well with the intent that some of the
inhibitor will adsorb onto the formation and then release over time when the well is returned to production.
Squeeze treatments typically do not contact all the true areas of interest. Effective treatment of the
squeezed chemical to multiple fractures will likely not occur as the treatment will follow the path of least
resistance, often times where the least scaling has occurred. Chemical can also be injected down the
annulus via capillary tubes when scaling is predicted to form. This process requires the operator to install
costly capillary tubes during the initial completion of the well or in subsequent remedial activity.
Chemical must be monitored and replenished. Injection of inhibitor through capillary tubes is designed to
deliver chemical inside the wellbore but will not prevent scale from forming anywhere below the injection
point, including the perfs or in the formation. Scale inhibitor can also be introduced into the fracture by
use a particulate material that carries inhibitor [Szymczak, 2006; Collins, 2006] that is incorporated with
the proppant volume. However these particulates generally are quite weak, may not perform as proppants
and can be detrimental to proppant conductivity.
Similarly, scale inhibitor can be introduced during the initial fracturing of the well by this new chemical
delivery system, by way of an infused and encapsulated porous ceramic proppant. This proppant has
engineered interconnected porosity allowing for an ideal balance of both strength and chemical storage
volume. The semipermeable membrane encapsulating the proppant serves to reduce the amount of
chemical lost during placement and maximize treatment length. The chemically infused proppant is
pumped as a small percentage blend in standard proppant. Placement in the fracture allows for treatment
of the water phase at the beginning of scaling potential. This early treatment prevents scale from forming
in the reservoir, the near wellbore region and the entire topside production system. Treatment of the
produced water in this manner prevents scale deposition and allows for maintained flow. Because this
delivery system utilizes an engineered ceramic proppant, no conductivity is lost in the proppant pack.
Typical treatments are designed to last for 24 months based on water production rates. This treatment
lifetime, however, can be altered to accommodate for longer or shorter periods of time. The delivery
system allows scale inhibiting chemicals to be released at a slow rate when the proppant comes in contact
with water.

Improvements in Elution Control

The use of chemically infused porous ceramic proppants was introduced to the industry in the 1990’s and
a number of field applications of the technology have been documented. In these cases the chemicals
infused into the porous proppants were scale inhibitors and no encapsulation of the infused ceramic was
utilized. One of early applications of the technology occurred in Prudhoe Bay [Webb 1997, Webb 1998].
The objective of this application was the prevention of calcium carbonate scaling by placing a porous
proppant in the fracture which was infused with a phosphonate scale inhibitor (diethylenetriamine-
pentamethylene phosphonic acid, DTPMP). Prior to the field trial pack flood testing of the infused
SPE-173792-MS 3

proppant had been performed to evaluate the rate of elution of the inhibitor from the porous proppant
(Figure 1). In the pack flooding test water is flowed through a small pack of the infused proppant and the
concentration of the inhibitor in the eluted water is measured as a function of pore volumes of water
through the pack. Two different water chemistries were evaluated in the test and as can be observed, the
chemistry of the water used in this test can affect the elution behavior. These initial trials confirmed the
viability of the technology of infused porous proppant for the delivery of a scale inhibitor. The actual
inhibitor concentration as a function of produced water for the Prudhoe Bay application is shown in Figure
2.

Figure 1—From Webb, 1997 – pack flood test

Figure 2—From Webb, 1997, field trial inhibitor return profile

4 SPE-173792-MS

However, it was recognized in these early applications that loss of inhibitor occurred more rapidly than
desired and a significant loss of inhibitor actually occurred during placement. Attempts to address this
through modification of the inhibitor chemistry, while improving release behavior, was not entirely
satisfactory. To address this an encapsulation process has been developed which greatly improves the
control of the release of the inhibitor from the porous proppant.
The encapsulation of this product allows for a much slower release, resulting in a much longer
treatment life as shown in Figure 3 below [Duenckel, 2014]. Multiple iterations of semipermeable
membranes were evaluated to determine which would be the most efficient in extending the life of the
product while allowing for delivery of sufficient amounts of chemical to prevent scale formation.
Following optimization of the encapsulation process in the laboratory a yard test with full scale equipment
was performed to compare to the laboratory results. This full scale equipment test provided important data
with regard to the release rate of chemical during pumping and encapsulation adhesion allowing for
additional optimization of encapsulation type.

Figure 3—Original product, chemically modified infused chemical, and encapsulated product elution profile

The full scale equipment yard test was designed so as to mimic a “typical” pumping operation for a
multi stage completion- in particular a previous field trial with the unencapsulated product performed in
the Bakken Field. This full scale testing took place at the University of Oklahoma Well Construction
Technology Center (OU), an advanced technology center that incorporates high pressure, high tempera-
ture fluid flow in both laboratory and field scales.
Proppant slurry placement simulation at OU uses high pressure equipment commonly employed in
hydraulic fracturing operations. The test equipment included two blending tubs which fed a triplex pump
and 2000 ft. of 1.5 inch piping. The pumping at a rate during the test averaged 70gal/min. The 1.2 inch
internal diameter (ID) of the piping and this rate of flow during the test simulated a hydraulic fracture
stimulation pumped at 60bbl/min through 4.5 inch tubing with an ID of 3.9 inches resulting in a shear rate
of 1640 seconds⫺1. Sample points were located at the blending tubs and near the end of the piping. The
fluid utilized was a linear guar based gel system mixed at a polymer loading of 30 pounds per thousand
gallons. Proppant was added to the gel at loadings of 2 and 4 PPA. The proppant was a standard 20/40
lightweight ceramic containing 5% of 20/40 porous ceramic which had been infused with scale inhibitor.
Four different encapsulation systems were evaluated to investigate the effects of shear and abrasion on
chemical loss and coating integrity. The percent loss of chemical from the infused proppant resulting for
the pump test was determined for each of the encapsulation systems and the results are shown in Table
SPE-173792-MS 5

1. In addition to the calculated loss of chemical, visual inspection of the post pumping pellets showed
limited abrasion or delamination of the System 3 and 4 coatings. Based on these results encapsulation
System 4 below was the focus of subsequent study and further optimization which limits loss of chemical
during placement in a typical job to less than 5% of the chemical initially infused into the porous proppant.
The data accumulated during the yard test has also helped in development of a predictive model for
infused proppant placement and elution.

Table 1—Effectiveness of Encapsulation Systems Subjected to Shear and Abrasion

Encapsulation System 1 2 3 4
Percent of Total Available Chemical Eluted per Minute Pumping 0.41 0.47 0.22 0.11

Field Trial
A five well field trial was conducted in the Greater Monument Butte Unit (GMBU) in the Uinta Basin of
Eastern Utah to evaluate the performance and effectiveness of the chemically infused porous ceramic
proppants for scale inhibition. The Uinta Basin of Utah is approximately 120 miles long and bounded on
the west by the Wasatch Mountains and on the east by the Douglas Creek Arch. It is nearly 100 miles wide
and bounded on the north by the Uinta Mountains and on the south by the San Rafael Uplift and the Book
Cliffs. The hydrocarbon accumulations occur primarily in stratigraphic traps in fluvial and lacustrine
sandstones in the tertiary Wasatch and Green River formations [Ramakrishna 2012]. Oil reservoirs in the
Uinta Basin are extremely complex in part due to this lacustrine depositional environment which resulted
in numerous self- sourcing reservoirs that vary greatly in wettability and mineralogy. In the Monument
Butte Field there are more than twenty separate producing sand units each with its unique properties. The
oil in the Green River and Watch formation varies in paraffin content and asphaltine content depending
on burial depth/temperature and stratigraphic unit. The oil is often simplified into “black” wax (Green
River) and “yellow” wax (Wasatch). [Merkel 2014] Typical oil parameters are shown in Table 2 below.

Table 2—GMBU Oil Parameters

Wasatch (Yellow wax) Lower Green River (Black Wax)

API Gravity 42 32
Pour Point 120 F 105F
BH Temperature 230 F 180 F

Scale formation is a significant problem affecting production from the GMBU oil reservoirs and is
typified by the formation of both carbonate and sulfate scales. The scaling is predominated by exchange-
able cations specifically barium, strontium, calcium carbonate and sulfate scales in various parts of the
GMBU. In addition to the scaling issues associated with primary production, the scaling is compounded
by the long history of waterflooding in the GMBU with mixtures of fresh and recycled water being
injected. The problem is further aggravated by the use of H2S scavengers (usually injected down the
annulus) which can increase pH. In some cases the rate of scale formation was quite rapid with down hole
pumps scaling up in a matter of days if not immediately and adequately addressed with inhibitor.
Phosphates have historically been the inhibitors of choice and phosphonates were selected for use with
the chemically infused porous ceramic proppants in the field trial. Note that high iron concentrations in
flow back waters indicate the preferred use of polymers over phosphonates and subsequent trials with
polymers are planned and will be discussed later. The main objective of the trial was to evaluate the
6 SPE-173792-MS

chemically infused porous ceramic proppants as a consistent, predictable inhibitor delivery system relative
to other options- both liquid and solid - that have tended to vary significantly in performance.
The five trial wells were completed in oil productive intervals of Green River and Wasatch Formations
at depths ranging from 4100= to 6400=. All of the trial wells were vertical and completed in a similar
fashion. All five wells were pumped with a blend of 20/40 northern white sand and chemically infused,
encapsulated, porous ceramic proppant. Blending took place at a transload facility utilizing a metered
hopper and a transloading conveyer system. All wells were pumped using a 17# borate cross-link gel at
a rate of 35bbl/min. Data for the five trial wells is shown in Table 3 below.

Table 3—Trial wells

Well Total 20/40 Sand and Infused Proppant, k#’s Infused Proppant, k#’s Wt. % Infused Proppant Perf Interval Stages

1 404 20 5 4100-6000 5
2 355 18 5 4100-5700 4
3 276 14 5 4800-6400 6
4 206 15 7.5 4800-5800 3
5 245 18 7.5 4600-5800 3

From the yard tests described above the predicted release rate of chemical from the encapsulated,
porous ceramic proppant during pumping and placement was established. This placement release rate was
coupled with the laboratory long term elution profile (Figure 3) and modelled to take into account the
water chemistry, production rate, reservoir temperature and pressure. The modeling provided a prediction
of the minimum phosphonate inhibitor concentration (MIC) required of 2 ppm. This predicted MIC was
further validated with field observations from offset wells. This modelled performance was then used to
establish the weight per cent of chemically infused, porous ceramic proppant required to effectively inhibit
a target volume of produced water.
As shown in Table 3, the weight per cent of the chemically infused proppant incorporated with the frac
sand was varied to observe the relationship between inhibitor returns and volumes of chemically infused
proppant used in the stimulations as well as to provide data for further optimization of treatment designs.
The initial three wells pumped, Wells 1, 2 and 3, were treated with a 5 weight per cent addition of the
chemically infused proppant. In the latter two trial wells, Wells 4 and 5, the addition level was raised to
7.5 weight per cent.
Trial Results
As the trial wells were unloaded and placed on production following the fracture stimulation, water
samples were captured and analyzed daily to determine the initial inhibitor concentration in the produced
water. Frequency of sampling decreased with time to once every two weeks. Oil and water production data
for the first three trial wells is shown in Figures 4a, 5a, and 6a and the associated concentration of inhibitor
in the produced water from these wells is shown in Figures 4b, 5b and 6b. Also shown is the percentage
of the inhibitor placed in the fracture that has been produced to date. The data represents 7 months of
production history and the inhibitor concentration in all three wells remains above the MIC of 2 ppm. This
has eliminated any need to pull pumps due to scale along with elimination of the need to pump scale
inhibiting chemical down the backside via capillary tubes. Wells 1 and 2 have demonstrated somewhat
similar inhibitor return behaviors with the inhibitor levels quite steady at ~ 8ppm. The shape of the
inhibitor return curves resemble that of the lab based elution curve (Figure 3 above). Well 3 however has
shown a significant increase in inhibitor levels to about 100 ppm some 6 months after the well was
fractured suggesting that some portion of the six frac stages pumped may just now unloading/producing.
It is also noted that a relatively small fraction of the inhibitor pumped in each well has been produced thus
SPE-173792-MS 7

far ranging from about 5% in Wells 1 and 3 to just under 2% in Well 2. The inhibitor trends for all three
wells, along with the significant fraction of chemical remaining in the propped fracture are suggesting that
the scale inhibitor will remain above the MIC for some extended time period to come.

Figure 4a—Well I Production history

Figure 4b—Inhibitor concentration in produced water

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Figure 5a—Well L Production history

Figure 5b—Inhibitor concentration in produced water

SPE-173792-MS 9

Figure 6a—Well Q Production history

Figure 6b—Inhibitor concentration in produced water

Oil and water production data for the other two trial wells, Well 4 and 5, is shown in Figures 7a and
8a below and the associated concentration of inhibitor in the produced water from these wells and per cent
of inhibitor produced are shown in Figures 7b and 8b. The data represents just under six months of
production history and the inhibitor concentration in both wells remains well above the MIC. Wells 4 and
5 were treated with a 50% higher weight per cent addition of the infused proppant and are exhibiting a
somewhat higher overall levels of inhibitor concentration in the produced water to this point. Again the
inhibitor level remains well above the MIC and no scaling problem have occurred with either well. As
with the other three trial wells the trends here suggest long term inhibition is likely.
10 SPE-173792-MS

Figure 7a—Well K Production history

Figure 7b—Inhibitor concentration in produced water

SPE-173792-MS 11

Figure 8a—Well T Production history

Figure 8b—Inhibitor concentration in produced water

Future Applications in the GMBU

Different areas in the GMBU and changing water chemistries bring multiple challenges when overcoming
production obstacles. High levels of iron found in certain zones that are completed in this area can result
in formation damage with the use of a phosphonate based chemistry. An iron tolerant, polymer based
inhibitor infused and encapsulated ceramic proppant has been tested and implemented in the areas with
iron levels above 50 ppm. Also, a paraffin inhibitor infused proppant specific to the black and yellow
waxes in the GMBU is being developed. This inhibitor is designed to significantly reduce the pour point
of the aforementioned crude. The presence of H2S in the production stream requires the operator to
constantly inject a scavenger in the annulus. This scavenger has an added effect of altering the pH of the
12 SPE-173792-MS

fluid, increasing the rate of scale formation. Further applications involve development of a more efficient
H2S scavenger infused in a proppant that will not alter the pH of the fluid being produced.

Extensions of the Technology to Other Chemical Applications

While the focus of this field trial was the application of scale inhibitors for long term scale inhibition, this
delivery technology has application in a number of other types of production chemical processes (as noted
also for the GBMU above) for production assurance and enhancement. This could include paraffin
inhibitors, halite inhibitors, gel breakers, and others. Development of these types of systems is actively
being pursued and field applications are expected to occur in the near future.

Conclusions
This field trial has demonstrated the applicability and effectiveness of a new chemical delivery system.
The product was easily integrated into the bulk proppant and delivered to location. Placement of the
infused and encapsulated, porous proppant into the hydraulic fracture stimulation was successful. Once
the wells were placed on production, samples of the produced water showed expected levels of scale
inhibitor. The observed levels of inhibitor returns in the produced water demonstrate the effectiveness of
the system used to encapsulate the chemically infused porous proppant. No signs of scale have been
observed in any of the trial wells and these wells are on track to be successfully inhibited for at least 24
months of production and quite possibly longer.

Nomenclature
DTPMP diethylenetriamine-pentamethylene phosphonic acid
GMBU Greater Monument Butte Unit
ID Internal diameter
MIC Minimum Inhibitor Concentration
OU University of Oklahoma Well Construction Technology Center
PPA Pounds of proppant added

Acknowledgements
The authors wish to thank CARBO Ceramics for permission to publish this paper.

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SPE-173792-MS 13

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