1. Managing Unconventional Treatment
Technology
Paul Ziemkiewicz, PhD
Water Research Institute
West Virginia University

2. FLOWBACK/PRODUCED WATER RECYCLING
If major local well
completions:
Hydrofracturing is a
net consumer of
water

3. Chloride ion
balances
nearly all of
the cation
charges
mg/L meq
TDS 71,103.3
Na 18,469.2 803.0
Ca 6,408.3 319.6
Sr 1,167.5 26.7
Mg 733.8 60.4
Ba 405.1 5.9
K 241.1 6.2
Fe 60.6 3.3
Mn 5.2 0.4
Al 0.4 0.0
Zn 0.1 0.0
sum 1225.4
Cl 40,656.7 1145.3
Br 424.8 5.3
HCO3 191.3 3.1
SO4 42.0 0.9
sum 1209.0
anion/cation sum 94%
Cl/cation sum 93%
average, n=12
cations
anions

4. THE ALKALINE METALS

5. IN FPW CHLORIDE IS THE DOMINANT ANION:
SOLUBILITY VS. SULFATE AND CARBONATE MINERALS

6. WATER TREATMENT TECHNOLOGIES
FALL INTO SIX MAIN CATEGORIES:
treatment
1. Bulk filtration
2. Lime softening
3. Sulfate addition
4. Nano filtration
5. Reverse osmosis
6. Thermal technologies
removes
1. suspended solids
2. Mg, Ca –as carbonates
3. Sr, Ba, Ra- as sulfates
4. multivalent ions: Fe, Mg, Ca,
Sr, Ba, SO4
5. All ions
6. All inorganic ions

7. TREATMENT OPTIONS FOR FLOWBACK
AND PRODUCED WATER
• Underground
injection
• Recycle
• Thermal methods
• Membrane
technologies
Raw flowback:
FeOOH,
organics, salt
After
electro-
coagulation:
Fe
reduction,
organics
removal
After
filtration:
salts
remain

8. MANAGEMENT OPTIONS-PROVEN
• UIC haulage $2-$4/bbl toll: Variable
• Bulk Filtration $1-$2/bbl
• Membranes $0.5-$1/bbl >50% brine reject
and disposal costs not included
• Thermal $5-$7/bbl
• These numbers are not reliable

9. WATER
TREATMENT
Class I wells must inject
hazardous and non-
hazardous wastes below the
lowermost underground
source of drinking water
(USDW).
Injection occurs into deep,
isolated rock formations that
are separated from the
lowermost USDW by layers
of impermeable clay and
rock.
Class I waste water injection well

10. TREATMENT OPTIONS: FIVE TYPES OF
UNDERGROUND INJECTION WELLS
• Class I wells - inject hazardous and non-hazardous wastes below the lowermost
underground source of drinking water (USDW). Injection occurs into deep, isolated rock
formations that are separated from the lowermost USDW by layers of impermeable clay
and rock.
• Class II wells - inject fluids associated with oil and natural gas production operations.
Most of the injected fluid is brine that is produced when oil and gas are extracted from the
earth. Includes production and disposal types.
• Class III wells - inject super-heated steam, water, or other fluids into formations to extract
minerals. The injected fluids are then pumped to the surface and the minerals in solution
are extracted. Generally, the fluid is treated and re-injected into the same formation.
• Class IV wells - inject hazardous or radioactive wastes into underground sources of
drinking water. These wells are banned under the Underground Injection Control (UIC)
program because they directly threaten public health.
• Class V wells - are injection wells that are not included in the other 4 classes. Some Class
V wells are wastewater disposal wells used by the geothermal industry, but most are wells
such as septic systems and cesspools. Generally, they are shallow and depend upon
gravity to drain or "inject" liquid waste into the ground.

11. SOLIDS SEPARATION
Cuttings pit
Flowback pit
Plate and
frame filter
press
Bag filters
Flowback tank

12. Commercial Desalination
processes
Membrane
distillation
Electro-
dialysis
Reverse
osmosis
MembraneThermal
Multi stage
flash dist.
Multiple
effect dist.
Vapor
compression
evaporation
Co-
generation
‘Commercial’ means the
technology is Deployed in a
commercial setting. Many of
these are engineered for
recovering drinking water from
sea water, others are for
separating solid products from
liquid streams.
• Different economics
• Rejects may not be
problematic
Forward
osmosis

13. MEMBRANE METHODS
• Reverse/forward osmosis
• Electrodialysis
• Membrane distillation

14. REVERSE OSMOSIS

15. REVERSE OSMOSIS,
NANO FILTRATION
as salt concentration
increases in the left cell
the amount of force
required to overcome free
energy depression also
increases.
Also, salt concentrations
will eventually exceed the
solubility limit and cause
membrane clogging.
CaSO4: 2,505 mg/L
Na2SO4: 195,000 mg/L
NaCl: 357,000 mg/L
CaCl2: 813,000 mg/L
semi-permeable
membrane-passes
water, not salt
salt + water
Salt lowers
free energy,
salt concentrates
water
add force,
pressure
flow direction
reject
brine
If water is near the salt solubility limit, the
reject rate will increase or membranes will clog

16. THE PROBLEM WITH REVERSE OSMOSIS,
NANO FILTRATION-REJECT RATES
Salt solubility limits:.
CaSO4: 2,505 mg/L
Na2SO4: 195,000 mg/L
NaCl: 357,000 mg/L
CaCl2: 813,000 mg/L
1,000 bbl Feed water
NaCl: 140,000 mg/L water
65% water recovery
350 bbl brine reject
NaCl: 400,000 mg/L
55% water recovery
450 bbl brine reject
NaCl: 311,111 mg/L
650 bbl
water
550 bbl
water
Membrane fouling
will occur
Prudent water
recovery rate
feed volume 1,000 bbl
feed volume 158,970 L
NaCl conc. 140,000 mg/L
NaCl mass 22,256 kg
water recovery 55%
clean water 550 bbl
reject brine 450 bbl
reject conc. 311,111 mg/L

17. FORWARD OSMOSIS
Free energy gradient
achieved by high salinity in
the draw solution.
Also, salt concentrations
will eventually exceed the
solubility limit and cause
membrane clogging.
CaSO4: 2,505 mg/L
Na2SO4: 195,000 mg/L
NaCl: 357,000 mg/L
CaCl2: 813,000 mg/L
semi-permeable
membrane-passes
water, not salt
Na, Ca, Mg, Sr, Ba,
Cl, Br + water
Draw
solution
Water +
NaCl
flow direction
reject
brine
If water is near the salt solubility limit, the
reject rate will increase or membranes will clog
NaCl
solution
reject
brine
Reverse
osmosis
unit
Water

18. ELECTRODIALYSIS
• High reject rate
• Fouling at anode/cathode

19. MEMBRANE DISTILLATION: VARIATIONS
Direct membrane distillation Sweep gas membrane dist.

20. THERMAL PROCESSES
• Multi stage flash distillation
• Multiple effect evaporation
• Vapor compression distillation
• Co-generation

21. TREATMENT OPTIONS-THERMAL SYSTEMS
Evaporation/crystallization Vacuum distillation

22. MULTI STAGE FLASH DISTILLATION
• Designed for water
recovery from sea water
• ~80% brine reject
• Heat exchangers
• Scaling at higher salt
concentrations

23. MULTIPLE EFFECT EVAPORATION
Advantages/disadvantages
• Can produce a dry salt
cake-minimal reject
• High energy requirement
• Produces water/low
pressure steam

24. VAPOR COMPRESSION DISTILLATION
• Compresses produced
steam to raise
temperature
• Heat exchange with boiler
feed-reduced energy
requirement
• Operational with
crystallizing brines

25. TREATMENT OPTIONS-EXPERIMENTAL
• Electro-coagulation $2-$4bbl
• Capacitive deionization
• Chlor-alkali

26. SUMMARY-DESAL TECHNOLOGIES IN THE
SHALE GAS SECTOR
• Commercial means the technology is deployed in a commercial setting-
not necessarily shale gas.
• Many are engineered for recovering drinking water from sea water,
others are for separating solid products from liquid streams.
• Different feed water and economics in conventional desal
• Rejects may not be problematic in conventional desal
• Few technologies have been proven/documented in the context of
treating flowback/produced water.
• Very little cost/performance data based on field experience.
• Perhaps this could be a task for MSEEL?

27. SPR may have reported a bad
Selenium dose number, by 16x

28. FOR MORE INFORMATION
PLEASE CONTACT:
Paul Ziemkiewicz, Director
WVU Water Research Institute
304 293 6958
pziemkie@wvu.edu