1. Reactive Proppant to Immobilize Metals and Radionuclides
in the Subsurface During Fracking
Zi Ye and Valentina Prigiobbe*
Civil, Environmental, and Ocean Engineering Department
Introduction
Hydraulic fracturing (or fracking)
Stevens Innovation Expo
April 27, 2016
www.stevens.edu/expo
Our approach
We are working on the development of a new method to adsorb
selected heavy metals and radionuclides in the produced water
onto a reactive proppants
such as silica beads coated
with goethite (FeOOH).
*Contact information: Dr. Valentina Prigiobbe, Assistant Professor in Civil, Environmental, and Ocean Engineering Department, Nicoll Lab,
office 105, email: valentina.prigiobbe@stevens.edu. Ph.D. Student: Zi Ye, zye4@stevens.edu.
References
[1] Elise Barbot, et al., Spatial and Temporal Correlation of Water Quality Parameters of Produced Waters from Devonian-Age Shale following Hydraulic
Fracturing, Environ. Sci. Technol., 2013, 47 (6), pp 2562–2569.
[2] Ying Xu, Lisa Axe., Synthesis and characterization of iron oxide-coated silica and its effect on metal adsorption, Journal of Colloid and Interface Science 282
(2005) 11–19.
[3] M. Sajih, et al., Adsorption of radium and barium on goethite and ferrihydrite: A kinetic and surface complexation modelling study, Geochimica et
Cosmochimica Acta 146 (2014) 150–163.
[4] Yao-JenTu, et al., Application of recycled iron oxide for adsorptive removal of strontium, Journal of the Taiwan Institute of Chemical Engineers, 53(2015)92–
97.
[5] Stjepko Krehula, et al., The effects of In 3+ doping on the properties of precipitated goethite, Journal of Alloys and Compounds
Volume 658, 15 February 2016, Pages 41–48.
Future work
Water
99.2%
Silica beads
coated with
goethite
Water
99.9%
A technology to
recover oil and gas
from unconventional
shale reservoirs.
Ba2+
Sr2+ Ra2+
We are building a column
flood system to study the
transport of barium
through a porous medium
containing goethite as a
reactive material. The
system simulates flow
within a fracture.
Flood system setup
Fractures in the shale formation are
created during the fracking process
using a fluid and a proppant. Proppant
is a solid material injected into to
maintain the fractures open during the
gas production.
Silica Beads
The produced material was used
to run experiments to determine
adsorption of barium at various
values of pH and ionic strength (I,
mole/kg). The data agree with the
literature. Further investigation is
ongoing.
Experimental results
SEM images of glass and FeOOH-coated beads
Fractures
Proppant
Injected water Produced water
Chloride
61.036%Sulfate
0.075%
Barium
2.363%
Calcium
7.671%
Strontium
1.801%
Bromine
0.543%
Magnesium
0.671%
Sodium
61.036%
Fe Total
0.081%
Radium228
0.001%
Radium226
0.127%
CHART TITLEAcid
9%
Corrosion
Inhibitor
6%
Friction
Reducer
6%
Clay Control
4%
Crosslinker
4%
Scale
Inhibitor
3%Breaker
3%
Iron Control
1%
Biocide
0%
Gellant
64%
CHART TITLE
Silica beads of FeOOH coated
0.2 mm diameter silica beads
Acknowledge
This research project used microscope resources partially funded by the National Science Foundation via Grant DMR-0922522
0.2 mm
Adsorption onto Goethite
Modeling
Chemical reactions for proton and barium adsorption
𝑆 + 𝐻+
→ SH+
logKh = 4.8
4S + Ba2+
→ 𝑆4 𝐵𝑎 2+
logKb = 3.8
Kh =
𝑆𝐻+
𝑎 𝐻+ ∙ 𝑆
𝑒 ψ𝐹 𝑅𝑇
𝐾𝑏 =
𝑆4 𝐵𝑎 2+
𝑎 𝐵𝑎2+ ∙ 𝑆 4
𝑒 2ψ𝐹 𝑅𝑇
𝑍 𝑇𝑜𝑡𝑎𝑙 = 𝑆 + 𝑆4 𝐵𝑎 2+ + 𝑆𝐻+
𝜎 =
𝐹
𝐴𝑆
𝑆𝐻+
+ 2 𝑆4 𝐵𝑎 2+
𝜎 = 0.1174𝑐1 2sinh(19.46𝑍ψ)
Site balance
Charge balance
Charge potential relationship
Parameters: S - Solid concentration (g/l); Kh - Equilibrium constant for proton; Kb - Equilibrium constant for barium;
ψ - Potential at the surface (in volt); 𝜎 - Surface charge density (C/m2); A - Specific surface area (m2/g).
Adsorption experiments
using FeOOH-coated beads
Goethite was
produced and coated
onto silica beads with
approximately 1 μm of
thickness.
Data
recording
pH meter
Samples
collected
for offline
analysis