Managing Unconventional Treatment Technology by Paul Ziemkiewicz, PhD

WEST VIRGINIA UNIVERSITY WV Water Research Institute

Managing Unconventional Treatment Technology

Paul Ziemkiewicz, PhDWater Research InstituteWest Virginia University


FLOWBACK/PRODUCED WATER RECYCLING

If major local well completions: Hydrofracturing is a net consumer of water


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


THE ALKALINE METALS


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


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


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


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


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


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.


SOLIDS SEPARATIONCuttings pit

Flowback pit

Plate and frame filter press

Bag filters

Flowback tank


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


MEMBRANE METHODS

• Reverse/forward osmosis• Electrodialysis• Membrane distillation


REVERSE OSMOSIS


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


THE PROBLEM WITH REVERSE OSMOSIS,NANO FILTRATION-REJECT RATES

Salt solubility limits:.


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


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.


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


ELECTRODIALYSIS• High reject rate• Fouling at anode/cathode


MEMBRANE DISTILLATION: VARIATIONSDirect membrane distillation Sweep gas membrane dist.


THERMAL PROCESSES

• Multi stage flash distillation• Multiple effect evaporation• Vapor compression distillation• Co-generation


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


MULTIPLE EFFECT EVAPORATION

Advantages/disadvantages• Can produce a dry salt

cake-minimal reject• High energy requirement• Produces water/low

pressure steam


VAPOR COMPRESSION DISTILLATION

• Compresses produced steam to raise temperature

• Heat exchange with boiler feed-reduced energy requirement

• Operational with crystallizing brines


TREATMENT OPTIONS-EXPERIMENTAL

• Electro-coagulation $2-$4bbl• Capacitive deionization• Chlor-alkali


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?


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


FOR MORE INFORMATION PLEASE CONTACT:

Paul Ziemkiewicz, DirectorWVU Water Research Institute304 293 [email protected]

mailto:[email protected]

Managing Unconventional Treatment Technology by Paul Ziemkiewicz, PhD

Science

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