SPE-184853-MS

Smart Proppants With Multiple Down Hole Functionalities

Sachit Goyal, Arjun Raghuraman, Kaoru Aou, Fabio Aguirre-Vargas, Juan Carlos Medina, Runyu Tan, and Dan
Hickman, The Dow Chemical Company

Copyright 2017, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Hydraulic Fracturing Technology Conference and Exhibition held in The Woodlands, Texas, USA, 24-26 January
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
Objective/scope: Breakthrough technologies for down-hole capture of radium-226 or hydrogen sulfide
contaminants in fracking operations have been developed, and are presented here. These technologies could
enable significant reduction in topside waste concentrations, and therefore simplify waste management
operations and reduce expenses in fracking operations. These novel technologies still possess desirable
primary functions of proppants such as flow back control and conductivity.
Methods, procedures, process: Multifunctional coatings supported by a variety of urethane chemistries
were designed for down-hole capture of Ra-226 or H2S while preserving primary proppant functionality.
Polymer coatings were applied to 20/40 or 20/30-mesh Northern White sand proppants. Coated proppants
with Radium-capturing abilities were exposed to simulated brine spiked with Ra-226 in batch mode. Ra-226
was analyzed in the brine before and after treatment using liquid scintillation counting and in the solids
using Gamma-ray spectrometry.
The H2S-capturing proppants were exposed to water/tetradecane spiked with H2S, and H2S was analyzed
in the headspace of the vessel containing proppant solution via gas chromatography.
Results, observation, and conclusions: In batch experiments, multifunctional resin coated proppant with
Radium-capturing abilities (slurried at 20-33 wt% in brine) showed 2350-24000 pCi Ra-226 capture
from synthetic brine /lb proppant used (water containing 5.0 wt% NaCl, 2.6 wt% CaCl2 and/or 0.07 wt
% BaCl2.2H2O). The capture was dependent upon: concentration of salts in brine, initial concentration
of Ra-226 (2500-35000 pCi/L), brine temperature (70-90 C), and duration of exposure (1h - 1week).
Radium capture was not affected by Na+ and Ca2+ concentration in the brine, but was significantly affected
by Ba2+ concentration. Furthermore, other proppants were also designed to deliver only contaminant-
capturing abilities. In this case, and under same experimental conditions, we observed up to 22000 pCi
Radium capture/ lb proppant. This more economical approach can be used to impart only waste capturing
functionality to proppants. Experiments in water at 70C for 1 hour of exposure with multifunctional resin
coated proppants for H2S capture showed 66-100% capture (initial [H2S] in liquid at equilibrium = 100
ppm, experimental capacity demonstrated ~1.1E-03 lb S removed/lb proppant used). Analogous H2S capture
experiments in tetradecane solvent (simulated hydrocarbon) showed a slower rate of capture.
2 SPE-184853-MS

Please explain how this paper will present novel (new) or additive information to the existing body
of literatures that can be of benefit to a practicing engineer Presented multifunctional proppants can
enable simplification of topside waste water treatment, enable waste water reusability, mitigate pipeline
corrosion, and limit worker exposure by keeping key contaminants down-hole (Ra 226 or H2S) in the
fractures. This is the first demonstration of truly multifunctional resin coated proppants that successfully
capture waste from synthetic brine.

Introduction
Upon drilling of a well bore for oil and gas recovery, a commonly used technique to enhance production in
unconventional wells is to introduce fracturing fluid into the well bore in order to crack open subterranean
formations using fluid pressure.1,2 An unconventional well is one that that is drilled into an unconventional
formation, which is defined as a geologic shale formation where natural gas generally cannot be produced
except by horizontal or vertical well bores stimulated by hydraulic fracturing.3 Drilling and hydraulic
fracturing of a typical unconventional well requires 4-6 million gallons of fracturing fluid, which comprises
water (90-95%), solid proppant (5-10%) and chemical additives (< 1%) to ensure good flow during
production. Examples of chemical additives used in fracturing fluid are scale inhibitors, wax inhibitors,
biocides, oxygen scavengers and friction reducers. Generally, 10-40% of the drilling fluid is recovered
during the initial period (7-14 days) of production and is referred to as flowback water. Once the well is in
production, it will typically continue to produce some amount of water that is called produced water. As
can be expected, there is a wide variability in the composition of flowback and produced water, and this
makes wastewater management challenging.

Wastewater management with respect to naturally occurring Radium

Wastewater management is crucial to successfully and sustainably operate wells, and is essential to prevent
contamination of surface and ground water. Wastewater disposal by underground injection is the leading
management approach that accounts for more than 95% of oil and gas-associated wastewater in the US.4
Underground injection is regulated by the Underground Injection Control (UIC) program, which requires
that wastewater from oil and gas production be disposed in Class II injection wells.5 Prior to 2010, majority
of the wastewater was sent to municipal or industrial plants for treatment and discharge. These plants were
not equipped to handle the waste from oil and gas wells, which resulted in a high Total Dissolved Solids
(TDS) load, especially in Pennsylvania.4,6 The Pennsylvania Department of Environmental Protection (PA
DEP) effectively banned discharge of wastewater in 2011 which meant that underground injection for
hydraulic fracturing became the main wastewater management option. Since Pennsylvania's geology does
not lend itself to underground injection, only six injection wells exist in the state on contrast to 177 in Ohio
and approximately 50,000 in Texas.7 Therefore, most of the PA wastewater needs to be transported to Ohio
for disposal in Class II injection wells, which increases the disposal costs substantially.
The Marcellus Shale is the largest shale gas resource in the United States.4 The Marcellus formation
consists of a considerable portion of black shale, which contains high uranium and thorium levels when
compared to other sedimentary formations.8 This results in significant 226Ra and 228Ra levels (decay products
from uranium and thorium isotopes) in the flowback water.8 Radium is particularly problematic because,
unlike uranium, Ra2+ is soluble in water and is usually present as RaCl2 in flowback water. The half-life
of 226Ra and 228Ra are 1600 and 5.75 years, respectively, and 226Ra is the dominant naturally occurring
radioactive material (NORM). While 226Ra decays via alpha decay to Radon gas, 228Ra decays via beta decay
to Actinium-228.9 In addition to the problem of ground and surface water contamination, radium exposure
to workers in the oil and gas industry can occur by inhalation of radon gas.10,11
SPE-184853-MS 3

Figure 1 depicts a general overview of the wastewater management process in Pennsylvania, especially
with respect to radium. The wastewater, which has high total dissolved solids content (TDS > 100,000 ppm),
is transported to treatment facilities for reduction in TDS levels via precipitation technologies. The sludge
is separated and disposed in specialized landfills. Distillation of the treated water results in a concentrate
with up to 25% of TDS and a distilled water product. The concentrate is transported is typically West
Virginia or Ohio for disposal in underground wells because, as mentioned before, Pennsylvania as very
view underground injection wells.

Figure 1Schematic description of frack wastewater treatment process.

A second important management strategy for wastewater disposal is reuse of flowback water for
subsequent hydraulic fracturing jobs. Flowback water is stored in centralized impoundments or storage
tanks in order to be reused in a flexible manner. Reusing wastewater is associated with several challenges
1) high ion concentrations can result in sulfate, carbonate and iron-based scales which impede oil and
gas flow, 2) anaerobic bacteria can cause biological fouling, and 3) variations in salinity can compromise
formation structure by clay shrinking or swelling.4 In addition, there are logistical issues relating to the
timing and transport of water generated at one well to another. Finally, recycling tends to be feasible only
when the number of new wells being constructed exceeds those in production.
A recent report investigated the fate of 226Ra in three storage impoundments over a 2.5 year period in
southwestern Pennsylvania.11 The study revealed that 226Ra increased over this period by 44% when the
wastewater in the impoundment was not treated for radium. Furthermore, 226Ra tended to accumulate in
the bottom sludge in sufficient levels that required the sludge to be classified as radioactive waste. Radium
that is concentrated in this way is referred to as Technologically Enhanced Naturally Occurring Materials
(TENORM).12
4 SPE-184853-MS

In 2015, the Pennsylvania Department of Environmental Protection (PA DEP) published a report on
TENORM associated with oil and gas operation in Pennsylvania.13 Thirty eight well sites were sampled
during the period June 2013 to July 2014, including thirty four unconventional wells. The median 226Ra
level in the flowback water generated from these wells was found to be 4550 pCi/L. In general, majority
of the radiation is from 226Ra with the exception of produced water from conventional wells. About 12 and
9% of the radiation is from 228Ra in flowback water and fracturing fluid, respectively.
The oil and gas industry is therefore being challenged to develop cost-effective radium removal
technologies in order to continue fracturing operations in unconventional wells. To date, all technologies
for radium removal take place topside and produce radioactive waste that need to be disposed according
the regulatory requirement outlines in Table 1. These technologies are summarized in Table 2 and were
compiled from data between 1982 and 1995.14 Based on the ranges of waste concentration, underground
injection or reuse may be the only options for the liquid waste.
226 228
Table 1Regulatory limits for radium based on the combined levels of Ra and Ra as outlined by the EPA, USNRC and USDOT.

nature of waste 226

Ra + 228Ra (pCi/L) 226
Ra + 228Ra (pCi/g)

EPA drinking water standard liquid <5 -

USNRC direct discharge liquid < 60 -
USNRC discharge to sanitary sewer liquid < 600 -
RCRA-D landfill solid - < 25
RCRA-C disposal landfill solid < 2000
Low-level radioactive waste landfill solid > 2000
USDOT limit for transportation solid - < 270

14
Table 2Topside technologies for radium disposal

topside treatment waste concentrations

wastes produced
technology (pCi/L)

rinse and backwash water 8-94

cation exchange
regenerated brine 50-3500
sludge at clarifier 76-4577

lime softening a
sludge (dry) 1-22 pCi/g
filter backwash 6-22
reverse osmosis reject water 7-43
electrodialysis reject water no data
solids and supernatant
iron removalb (oxidation 12-1980
from filtration backwash
or Greensand)
green sand media 28-250
selective sorbents selective sorbent 3.6 pCi/g

sulfate precipitation hot sludge spent filter media No datac

a
Radium capture efficiency can be improved by carbonate precipitation using MgCO3.
b
Addition of KMnO4 prior to filtration improves radium capture efficiency.
c
This method produces waste containing sufficiently high radium levels that necessitate disposal in Low Level Radioactive Waste landfills.

Currently, technologies that enable treatment of radium downhole thereby either eliminating radium
concentration topside or minimizing radium topside are unheard of. A breakthrough technology enabling
SPE-184853-MS 5

capture of radium contaminants downhole can enable significant reduction in topside waste concentrations
and therefore simplify waste management operations and reduce expenses in fracking operations. In
addition, the technology can enable waste water reusability, as well as limit worker exposure by keeping
key contaminants down-hole (Ra 226) in the fractures.

H2S opportunity
Another problem encountered during production is souring, which refers to an increasing mass of hydrogen
sulfide (H2S) per unit mass of total production fluid. Generally speaking, upto less than 3 ppmv of H2S in
the liquid phase is considered benign. Well operations and associated processing equipment needs to be
maintained within NACE standards to ensure that the partial H2S pressure does not exceed 0.05 psia.15 If
H2S levels cannot be maintained within the NACE limit, the well and process equipment may have to be
closed out for tubing and wellhead replacement or upgrades. In addition to production loss, these operations
can be very expensive. Failure to remove H2S from flowback water and oil can lead to corrosion of casings
(sulfide-stress corrosion cracking), mechanical failure, fluid leakage and environmental contamination.
Other corrosion mechanisms such as, hydrogen embrittlement (HE), hydrogen-induced cracking (HIC) and
stress corrosion cracking (SCC) are also known.15,16 Other than corrosion, H2S in oil and flowback water
presents an occupational safety problem, and can react with soluble iron to form iron sulfide scales.17
Hydrogen sulfide in oil wells can result from biogenic or non-biogenic sources. Biogenic H2S results from
microbial contamination by sulfate-reducing bacteria (SRB) which convert sulfate to H2S in the absence of
O2. There are four important non-biogenic pathways that produce H2S in oilfield15 (1) thermochemical
sulfate reduction, (2) decomposition of organic sulfur compounds, (3) dissolution of pyritic material and (4)
redox reactions involving bisulfite oxygen scavengers. Factors that affect the rate of H2S generation include
the nature of the formation (pyrite/siderite balance), well temperatures and pressure.
One solution to controlling H2S levels is to use biocides to kill bacteria. This approach will only affect
H2S produced by biogenic pathways. The hydrolytic and thermal stability of biocides and their ability to be
placed and kept downhole are important to the effectiveness of this approach. Most biocides are severe eye
and skin irritants and thus pose an occupational safety hazard.18 A second way to mitigate H2S corrosion is
the use of engineering controls such as protective coatings and H2S removal equipment. Chemical treatment
of oil and gas topside is another approach to H2S removal although this approach will not protect well
casings. A breakthrough technology enabling capture of H2S downhole can mitigate pipeline corrosion and
limit worker exposure by keeping key contaminants down-hole (H2S) in the fractures thereby simplifying
waste management operations and reducing expenses in fracking operations.

Concept of multifunctional proppants

Currently resin coated proppants are desirable in hydraulic fracturing of low permeability reservoirs because
they can impart a degree of adhesion between particles under proppant which in turn prevents the proppant
from being flushed out of the well, a process commonly referred to as flowback. Flowback is undesirable
because they lead to closure of the crack and damage to equipment used in the fracturing process. Hence
resin coated proppants are typically used in the tail end of the fracture to allow for flowback control
(FC). Resin coated proppants can also improve the ability of proppants to withstand closure stresses and
can contain/mitigate fines (fines mitigation or FM) generated from cracking of the proppant substrate
thereby resulting in enhancement of conductivity of oil and gas. Known resins used to coat proppants
include phenolic resins, furan-based resins, epoxies and polyurethane thermosets. Polyurethane (PU)-based
chemistries have a number of advantages over other chemistries such as fast reaction rates, ability to cure at
lower temperatures and the lack of need of specialized equipment. The level of resin in polyurethane-coated
proppants is typically between 0.5-4.0 wt % of the substrate depending on the substrate or the application.
6 SPE-184853-MS

In this paper we introduce the concept of adding new functionalities to the resin coated proppants while
preserving the primary functionality of the proppants (flowback control, FC or fines mitigation, FM) that
can potentially enable (as shown in Figure 2)-
1. Simplification of the upstream processes
2. Simplify or potential eliminate the need for topside treatment

Figure 2Schematic diagram introducing the concept of multifunctionality

For example, radium present in the flowback water can contaminate the equipment and result in
generation of radioactive waste topside that needs to be treated or concentrated (see Figure 2) before disposal
via underground injection or specialized landfills. The H2S gas produced downhole can corrode the pipelines
and cause extensive equipment damage.
This paper describes the preparation and scavenging ability of multi-functional resin coated proppants
for Radium removal and H2S capture. In batch experiments, multifunctional resin coated proppants with
Radium-capturing abilities (proppant slurried at 20-33 wt% in brine) showed 2350-24000 pCi Ra-226
capture from synthetic brine /lb proppant used (water containing 5.0 wt% NaCl, 2.6 wt% CaCl2 and/or
0.07 wt% BaCl2.2H2O spiked with Ra-226). The capture was found to be dependent upon: concentration
of salts in brine, initial concentration of Ra-226 (2500-35000 pCi/L), brine temperature (70-90 C), and
duration of exposure (1h - 1week). Furthermore, proppants were also designed to deliver only Radium
contaminant-capturing abilities. In this case, and under same experimental conditions, we observed up
to 22000 pCi Radium capture/ lb proppant used. This more economical approach can be used to impart
only waste capturing functionality to proppants. This is the first demonstration of truly multifunctional
resin coated proppants that successfully capture radium waste from synthetic brine. In batch experiments,
multifunctional resin coated proppants for H2S capture (20% proppant slurried in water) showed 66-100%
capture from water containing 100 ppm [H2S] (initial concentration in liquid phase at equilibrium,
experimental capacity demonstrated ~1.1E-03 lb S removed/lb proppant used) at 70C after 1 hour of
exposure. Analogous H2S capture experiments in tetradecane solvent (simulated hydrocarbon) showed a
slower rate of capture.
SPE-184853-MS 7

Methods
Method A for experimental measurement of radium capture
The following procedure was used for R1. Proppant samples were treated with a synthetic brine solution
consisting of 5% sodium chloride, 2.6% calcium chloride, 0.07% barium chloride and 1043 pCi/sample of
226
Ra. The granular material was suspended in the synthetic brine solutions using a 7 day leach period at 90
C. The brine solution (160 g, 6520 pCi/L) was added to 40 g of the solid granular media in a 500 ml amber
glass container. The container was placed in an oven to maintain the temperature at 90C with occasional
agitation through each 24 hour period for a total of 7 days. At the end of the mixing period the solid and
liquid phases were separated by pressure filtration. Resulting solid and liquid phases were then analyzed
for radium 226 activity by high purity gamma spectrometry. The proppant samples were screened prior to
testing to determine if any native 226Ra was present as naturally occurring radioactive material (NORM).
No activity was detected above the background.
The following procedure was used for R3. Two test solutions containing certified amounts of 226Ra
traceable to the National Institutes of Standards and Technologies (NIST). Standard number 0299-H
containing 2467 dpm/mL of Ra-226 was aliquoted with 1.2 mL to yield a test solution of 1333 pCi/sample.
A second higher activity standard was created using 2.5 mL of the same standard yielding a known activity
of 2778 pCi/sample. These two standards were added to separate synthetic brine solutions containing 2.6%
calcium chloride and 5% sodium chloride. 250 grams of the solid media was added to a one liter amber
glass container with 500 mL of the liquid standard solution; this would yield approximately 2700 and 5560
pCi/L radium solutions depending on which standard were used. The container was placed in an oven to
maintain the temperature at 70 C with occasional agitation over a 24 hour period. At the end of the mixing
period the solid and liquid phases were separated by vacuum filtration using a 0.45 micron filter. Resulting
solid and liquid phases were then analyzed for radium 226 activity by high purity gamma spectrometry.

Method B for experimental measurement of radium capture

The following procedure was used for R2, C1, and R4. Proppant samples were treated with a synthetic
brine solution consisting of 5% sodium chloride, 2.6% calcium chloride, 0.07% barium chloride spiked
with 226Ra (35 nCi/L). Proppant (90 g) was combined with brine (360 g) in a 1 L glass container. The
container was placed in an oven to maintain the temperature at 90C with occasional agitation periodically.
The solid and liquid phases were separated by filtration through a fritted column under gravity and the
radium concentrations were measured by high purity germanium gamma spectroscopy. Resulting solid and
liquid phases were then analyzed for radium 226 activity by high purity gamma spectrometry.

Method for experimental measurement of H2S capture

Each sand sample (2.0 g coated or uncoated sands) was weighed into a 22-mL headspace GC vial with a
stir bar. Deionized water (10 mL) or tetradecane (10 mL) was then added into each vial and sealed with a
PTFE lined silicon crimp cap. Hydrogen sulfide gas (1.5 mL, STP equivalent to 2.28 mg) was injected into
the headspace of each vial. The vials were then heated at 70 C for testing with water and heated at 110C
for testing with tetradecane in an aluminum heating block on top of a stirring hot plate for 1 h, after which
the vials were cooled and the H2S concentrations in the headspace of the vials were analyzed by headspace
gas chromatography. Two samples were tested for each experiment to ensure repeatability.
8 SPE-184853-MS

Results and Discussion

Evaluation of Multifunctional Proppant for Radium capture
Table 3 outlines the results from testing of different multifunctional proppant samples. Samples R1, R2
and C1 were designed with a primary function of fines mitigation (FM) and medium temperature/pressure
wells and contained 2% of polyurethane where R1 and R2 contained actives for capturing radium and C1
served as control. Sample R3 contained 3% resin and was designed for flowback control (FC) in addition to
radium capture. Sample R4 contained 0.5% resin and was designed for the sole purpose of radium capture
with minimal flowback control functionality. Radionuclide capture testing was performed using 20% by
weight of the proppants at 90 C for entry R1, R2, C1 and R4. The samples were periodically agitated
every 8-12 h. The solid and liquid phases were separated by filtration through a fritted column under gravity
and the radium concentrations were measured by high purity germanium gamma spectroscopy. Sample
entries R1 and R2 showed capture of about 2350-24000 pCi/lb proppant in the presence of BaCl2 depending
on initial radium concentration. The control sample prepared without active for capturing radium showed
capture of about ~4100 pCi/lb proppant in the presence of BaCl2 (when starting Ra concentration was
35000 pCi/L), which can be attributed to adsorption/absorption of radium in the coating. The sample R3
prepared for flowback control primary functionality showed 7700 pCi/lb proppant capture (at low initial
radium concentration 5560 pCi/L) in the absence of BaCl2. The sample R4 prepared for the sole intention
of contaminant removal demonstrated 22050 pCi/lb proppant capture from the synthetic brine containing
BaCl2.

Table 3Radium capture of multifunctional polyurethane coated proppants

Ra-226
Proppant initial BaCl2 in
Sample temperature time captured
Sample level radioactivity media
type (C) (days) (pCi/ lb
(wt. %) (pCi/L) (ppm)
proppant)

R1a FMd 20 90 7 2350 6520 700

R2b FM 20 90 3 23940 35000 700

C1 b
FM 20 90 3 4095 35000 700

R3 a
FC e
33 70 1 7700 5560 -

R4b RCf 20 90 3 22050 35000 700

a
method A was used, 40 g proppant was combined with 160 g of media containing NaCl and CaCl2; BaCl2 was included for entries 1 and 2.
b
method B was used, 90 g proppant was combined with 360 g of media containing NaCl and CaCl2; BaCl2 was included for entries 1 and 2.
c 226
Ra concentrations in the liquid phase were measured using liquid scintillation counting. The variability in the measurement, based on count statistics, was
reported to be 5.5% (one STDEV) on the raw measurements which corresponds to a propagating error of 11.6% on the percent capture,
d
proppant primary functionality fines mitigation,
e
proppant primary functionality flowback control,
f
proppant primary functionality radium capture

Radium capture was not affected by Na+ and Ca2+ concentration in the brine. High levels of radium capture
in the absence of Ba2+ ions (entry R3 vs other samples) indicate strong influence of Ba2+ ions on the Radium
capture. The effect of other ions including Sr2+on radium capture was not investigated in this study but
is expected to influence radium capture by proppants as well. Kinetic studies for radium measurement
performed on one sample in batch experiment indicated that equilibrium was reached within the first 4 hours
of exposure to synthetic brine spiked with Radium. This observation implies that all data presented here
refers to equilibrium radium concentration. Radium concentration measured in the supernatant liquid and
SPE-184853-MS 9

solid proppant obtained after separation for a particular sample usually added up to 100% indicating good
radium balance. The results presented here demonstrate that multifunctional proppants have an experimental
capacity of 2350-24000 pCi Ra/lb proppant from well waters downhole depending on initial concentration
of Ra-226 in the well water, the chemistry of the well waters (concentration of Ba2+, Sr2+ ions), and brine
temperature (70-90 C). This technology has the potential to mitigate/ eliminate radium seen topside thereby
simplifying topside treatment of radium.

Evaluation of Multifunctional Proppant for H2S capture

Eight samples were prepared and evaluated for H2S capture at 70 C in water and hydrocarbon (Table 4).
The effect of coated proppant type (flowback control, FC or fines mitigation, FM), active concentration
in the coating, and type of active was investigated. Control polyurethane coated proppants designed for
the sole purpose of providing primary functionality showed 17-19% H2S capture (0.18-0.21E-03 lb S
removed/lb proppant used) in water and 6% capture (0.06E-03 lb S removed/lb proppant used) in tetradecane
(entries C2 and C3). This may be attributed to physical adsorption/absorption of H2S or inherent solubility
of H2S in the polymer. Under these conditions, raw sand captured 20% H2S. Coated proppant for fines
mitigation application captured 66% H2S from aqueous phase (entry HS1), where the coating was designed
to theoretically capture 2E-03 lb S /lb proppant and about 0.7E-03 lb S capture/lb proppant was observed.
Proppant samples corresponding to entries HS2-5 are intended for low temperature / flowback control
applications. Increasing the loading of active agent in the coating resulted in increase in H2S capture in
1 h (88 vs 100%, entries HS2 and HS3). The experimental capacity corresponding to entry HS3 was
0.95E-03 lb S /lb proppant which is 47.5% of the theoretical capacity. In contrast, the experimental capacity
corresponding to entry HS2 was >1.08E-03 lb S /lb proppant which is >27% of the theoretical capacity. This
observation indicated that the proppant may not be fully saturated and has the capacity to capture more H2S
until saturation is attained. Difference in surface modification of the actives had an effect on capture: entry
HS4 showed 11% less capture than entry HS3 in 1 h. This observation suggests that surface modification
of the active can be used to enhance the rate of H2S capture. Experiments conducted in tetradecane showed
a similar trend across coated proppants although the rate of capture was slower.

Table 4H2S Capture by Multifunctional Polyurethane Coated Proppants

H2S capture from H2S capture from

theoretical H2S capture H2S capture from
tetradecane at tetradecane at
sample ID a
Sample type capacity (mg from water water at 70 C (lb
110 C (%, mg 110 C (lb S/
S/ g proppant) at 70 C (%)b S/ lb proppant)
S/ g proppant)b lb proppant)

C2 FMd - 19 0.21E-03 6 0.06E-03

C3 FC e
- 17 0.18 E-03 6 0.06E-03

HS1 FM 2.0 66 0.71E-03 26 0.28E-03

HS2 FC 3.9 100 >1.08E-03 67 0.72E-03
HS3 FC 2.0 88 0.95E-03 43 0.46E-03
HS4 FC 2.0 77 0.83E-03 56 0.61E-03

HS5 FC 3.9 88 0.95E-03 n.e c

n.ec

a
All experiments were carried using 2 g proppants and 10 mL of media.
b
2.3 mg of H2S was injected into 22 mL GC vials in each experiment resulting in an initial headspace concentration 3133 ppmv after vapor-liquid equilibrium
was attained. H2S capture was calculated based on the vapor phase concentration remaining after 1 h assuming vapor-equilibrium had been reached.
c
not evaluated,
d
proppant primary functionality fines mitigation,
e
proppant primary functionality flowback control
10 SPE-184853-MS

The results presented here demonstrate that multifunctional proppants designed for H2S capture can
theoretically be designed to capture anywhere from 2-~10E-03 lb S /lb proppant depending on the
concentration of the active in the coating. On investigation of coated proppants designed with theoretical H2S
removal capacity of 2-4 E-03 lb S /lb proppant, within 1 hour of capture the maximum experimental capacity
of H2S capture was observed to be ~50% (experimental capture of 1E-03 lb S /lb proppant) indicating
dependence of capture on type of active/surface modification of active, coating permeability (HS1 vs HS3),
temperature of brine, type of media (aqueous or hydrocarbon), and duration of capture.

Conclusions
Wastewater management is, and will continue to be, an important process as long as hydraulic fracturing is
used to extract oil and gas from shale basins. Since the shale formations containing black shale are relatively
rich in uranium and thorium ores, radium levels are high in flowback and produced waters. In this paper, we
have shown that it is possible to use resin coated proppants to capture radium at different temperatures from
bulk solutions containing salts at fairly high concentrations. We demonstrated that multifunctional resin
coated proppants with Radium-capturing abilities in batch experiments (proppant slurried at 20-33 wt% in
brine) showed 2350-24000 pCi Ra-226 capture from synthetic brine /lb proppant used. The capture was
found to be dependent upon: concentration of salts in brine, initial concentration of Ra-226 (2500-35000
pCi/L), brine temperature (70-90 C), and duration of exposure (1h - 1week). Furthermore, proppants
were also designed to deliver only Radium contaminant-capturing abilities. In this case, and under same
experimental conditions, we observed up to 35% Radium capture. This more economical approach can
be used to impart only waste capturing functionality to proppants. This is the first demonstration of truly
multifunctional resin coated proppants that successfully capture radium waste from synthetic brine.
We also demonstrated that it is possible to use resin coated proppants to capture H2S from water and
hydrocarbons. In batch experiments, multifunctional resin coated proppants for H2S capture (20% proppant
slurried in water) showed 66-100% capture from water containing 100 ppm [H2S] (initial concentration in
liquid phase at equilibrium, experimental capacity demonstrated ~1.1E-03 lb S removed/lb proppant used)
at 70C after 1 hour of exposure. Analogous H2S capture experiments in tetradecane solvent (simulated
hydrocarbon) showed a slower rate of capture. The multifunctional proppants for H2S capture presented
here can be designed to capture upto 2-~10E-03 lb S / lb proppant.
These technologies could enable significant reduction in topside waste concentrations, enable waste water
reusability, mitigate pipeline corrosion, and limit worker exposure by keeping key contaminants down-hole
(Ra 226 or H2S) in the fractures and therefore simplify waste management operations and reduce expenses
in fracking operations. These novel technologies still possess desirable primary functions of proppants such
as flow back control and fines mitigation.

Acknowledgments
The authors thank Rajat Duggal, Abhijit Namjoshi, William Koonce, Bob Goltz, and David Babb for helpful
discussions. The authors thank Siaka Yousuf for help in performing the radium measurements, and Sweta
Somasi for initial help in determining the kinetics of radium capture.

References
1. Montgomery, C. T.; Smith, M. B. History of an enduring technology. J. Pet. Technol. 2010, 62,
26-28, 30-32.
2. Hydraulic fracturing: How it works. http://fracfocus.org/hydraulic-fracturing-process.
3. Report Instructions for the Permits Issued Detail Report.
SPE-184853-MS 11

4. Lutz, B. D.; Lewis, A. N.; Doyle, M. W. Generation, transport, and disposal of wastewater
associated with Marcellus Shale gas development. Water Resour. Res. 2013, 49, 647-656.
5. Class II Wells - Oil and Gas Related Injection Wells (Class II). http://water.epa.gov/type/
groundwater/uic/class2/index.cfm.
6. Warner, N. R.; Christie, C. A.; Jackson, R. B.; Vengosh, A. Impacts of Shale Gas Wastewater
Disposal on Water Quality in Western Pennsylvania. Environ. Sci. Technol. 2013, 47,
11849-11857.
7. Unconventional Oil And Gas Development: Key environmental and public health requirements
for Office, U. S. G. A.2012.
8. Rowan, E. L.; Engle, M. A.; Kirby, C. S.; Kraemer, T. F. Radium content of oil- and gas-field
produced waters in the northern Appalachian basin (USA): summary and discussion of data
2011.
9. Landsberger, S.; Brabec, C.; Canion, B.; Hashem, J.; Lu, C.; Millsap, D.; George, G.
Determination of 226Ra, 228Ra and 210Pb in NORM products from oil and gas exploration:
Problems in activity underestimation due to the presence of metals and self-absorption of
photons. J. Environ. Radioact. 2013, 125, 23-26.
10. Steinhaeusler, F. Radiological impact on man and the environment from the oil and gas industry:
Risk assessment for the critical group. NATO Sci. Ser., IV 2004, 41, 129-134.
11. Zhang, T.; Hammack, R. W.; Vidic, R. D. Fate of Radium in Marcellus Shale Flowback Water
Impoundments and Assessment of Associated Health Risks. Environ. Sci. Technol. 2015, 49,
9347-9354.
12. Technologically-Enhanced, Naturally-Occurring Radioactive Materials. http://www.epa.gov/
radiation/tenorm/.
13. Technologically Enhanced Naturally Occurring Radioactive Materials (TENORM) Study Report
for Perma-Fix Environmental Services Inc.: Harrisburg, PA2015.
14. A regulators guide to the management of radioactive residuals from drinking water treatment
technologies2005.
15. Eden, B.; Laycock, P. L.; Fielder, M. Oilfield Reservoir Souring for Executive, H. a. S.1993.
16. Brondel, D.; Edwards, R.; Hayman, A.; Hill, D.; Mehta, S.; Semerad, T. Corrosion in the Oil
Industry. Oilfield Review1994.
17. Nasr-El-Din, H. A.; Al-Humaidan, A. Y.: Iron Sulfide Scale: Formation, Removal and
Prevention. In nternational Symposium on Oilfield Scale; Society of Petroleum Engineers:
Aberdeen, UK, 2001.
18. Kahrilas, G. A.; Blotevogel, J.; Stewart, P. S.; Borch, T. Biocides in Hydraulic Fracturing Fluids:
A Critical Review of Their Usage, Mobility, Degradation, and Toxicity. Environ. Sci. Technol.
2015, 49, 16-32.