managing unconventional treatment technology by paul ziemkiewicz, phd
TRANSCRIPT
WEST VIRGINIA UNIVERSITY WV Water Research Institute
Managing Unconventional Treatment Technology
Paul Ziemkiewicz, PhDWater Research InstituteWest Virginia University
WEST VIRGINIA UNIVERSITY WV Water Research Institute
FLOWBACK/PRODUCED WATER RECYCLING
If major local well completions: Hydrofracturing is a net consumer of water
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Chloride ion balances nearly all of the cation charges
mg/L meqTDS 71,103.3
Na 18,469.2 803.0Ca 6,408.3 319.6Sr 1,167.5 26.7Mg 733.8 60.4Ba 405.1 5.9K 241.1 6.2Fe 60.6 3.3Mn 5.2 0.4Al 0.4 0.0Zn 0.1 0.0
sum 1225.4
Cl 40,656.7 1145.3Br 424.8 5.3
HCO3 191.3 3.1
SO4 42.0 0.9sum 1209.0
anion/cation sum 94%Cl/cation sum 93%
average, n=12
cations
anions
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THE ALKALINE METALS
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IN FPW CHLORIDE IS THE DOMINANT ANION:SOLUBILITY VS. SULFATE AND CARBONATE MINERALS
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WATER TREATMENT TECHNOLOGIES FALL INTO SIX MAIN CATEGORIES:
treatment1. Bulk filtration2. Lime softening3. Sulfate addition4. Nano filtration5. Reverse osmosis6. Thermal technologies
removes1. suspended solids2. Mg, Ca –as carbonates
3. Sr, Ba, Ra- as sulfates4. multivalent ions: Fe, Mg, Ca, Sr, Ba,
SO4
5. All ions6. All inorganic ions
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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
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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
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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
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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.
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SOLIDS SEPARATIONCuttings pit
Flowback pit
Plate and frame filter press
Bag filters
Flowback tank
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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
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MEMBRANE METHODS
• Reverse/forward osmosis• Electrodialysis• Membrane distillation
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REVERSE OSMOSIS
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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/LNa2SO4: 195,000 mg/LNaCl: 357,000 mg/LCaCl2: 813,000 mg/L
semi-permeable membrane-passes
water, not salt
salt + waterSalt lowersfree energy,
salt concentrates
wateradd force, pressure
flow direction
reject brine
If water is near the salt solubility limit, the reject rate will increase or membranes will clog
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THE PROBLEM WITH REVERSE OSMOSIS,NANO FILTRATION-REJECT RATES
Salt solubility limits:.
CaSO4: 2,505 mg/LNa2SO4: 195,000 mg/LNaCl: 357,000 mg/LCaCl2: 813,000 mg/L
1,000 bbl Feed waterNaCl: 140,000 mg/L water
65% water recovery350 bbl brine reject
NaCl: 400,000 mg/L
55% water recovery450 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 bblfeed volume 158,970 LNaCl conc. 140,000 mg/LNaCl mass 22,256 kg
water recovery 55%clean water 550 bblreject brine 450 bblreject conc. 311,111 mg/L
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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/LNa2SO4: 195,000 mg/LNaCl: 357,000 mg/LCaCl2: 813,000 mg/L
semi-permeable membrane-passes
water, not salt
Na, Ca, Mg, Sr, Ba, Cl, Br + water
Draw solutionWater +
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
unitWater
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ELECTRODIALYSIS• High reject rate• Fouling at anode/cathode
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MEMBRANE DISTILLATION: VARIATIONSDirect membrane distillation Sweep gas membrane dist.
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THERMAL PROCESSES
• Multi stage flash distillation• Multiple effect evaporation• Vapor compression distillation• Co-generation
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TREATMENT OPTIONS-THERMAL SYSTEMS
Evaporation/crystallization Vacuum distillation
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MULTI STAGE FLASH DISTILLATION• Designed for water
recovery from sea water• ~80% brine reject• Heat exchangers• Scaling at higher salt
concentrations
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MULTIPLE EFFECT EVAPORATION
Advantages/disadvantages• Can produce a dry salt
cake-minimal reject• High energy requirement• Produces water/low
pressure steam
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VAPOR COMPRESSION DISTILLATION
• Compresses produced steam to raise temperature
• Heat exchange with boiler feed-reduced energy requirement
• Operational with crystallizing brines
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TREATMENT OPTIONS-EXPERIMENTAL
• Electro-coagulation $2-$4bbl• Capacitive deionization• Chlor-alkali
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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?
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SPR may have reported a bad Selenium dose number, by 16x
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FOR MORE INFORMATION PLEASE CONTACT:
Paul Ziemkiewicz, DirectorWVU Water Research Institute304 293 [email protected]