Equilibrating Water Utilization in Shale Gas

Operations Through Water Treatment Technologies

Scott LaRue
Water Treatment Technologies Operations Manager
US Land
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 Emerging Shale Gas Plays in USA

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 Water = Scarce Resource

 Growing Population

 Changing Environment

 Consumption

 Industrial Utilization

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 Regulations

Meet Ch. 95 discharge standards

TDS 500 mg/L as AML; 1,000 mg/L as MDL

Chloride 250 mg/L as AML; 500 mg/L as MDL
Total Barium 10 mg/L as AML; 20 mg/L as MDL
Total Strontium 10 mg/L as AML; 20 mg/L as MDL

Monitor for NORM

Radium
Alpha

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 Water Recycling

Goals:

• Recycle/Reuse flow back and produced

waters
• Reduce fresh water consumption
• Reduce disposal cost
• Reduce trucking cost
• Environmentally safe

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 Integrated Oil Field Water
On Site
Management M-I SWACO Water Treatment

Central Location
M-I SWACO Water Treatment

CONFIDENTIAL INFORMATION ©2009 M-I L.L.C.

 Water Treatment Technologies

 Filtration

 Reclamation

 Disinfection / Bacteria Control

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 Aqualibrium Systems for Water Recycling

Aqualibrium Filtration System

• Filtration of total suspended solids
• 99.9% water recover for reuse
• Inexpensive with all flow back and
produced waters
• Low energy consumption
• Highly mobile
Aqualibrium Reclamation System
• Chemical precipitation of contaminates
• Filtration of total suspended solids
• 99 to 90% water recover for reuse
•Adaptable to changes in feed water
chemistry
• Low energy consumption
• Highly mobile

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 Aqualibrium Filtration System - Dirty

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 Aqualibrium Filtration System - Processed

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 Contaminant Issues
Concerns Culprits Potential Impact
Hardness Ca, Mg, Ba, Sr Creates borate cross links, may contribute to norm
Friction Reducer Multivalent Ions (Fe, Ca, Can reduce friction reducer effectiveness, drive up horspower costs
Effectiveness Mg, Ba, Sr)
Scaling calcium carbonate, Equipment fouling, can clog flow lines, form oily sludges that must be removed, and form
calcium sulfate, barium emulsions that are difficult to break
sulfate, strontium
sulfate, and iron sulfide
Bacterial Corrosion Bacteria and Can clog equipment and pipelines and accelerate corrosion and form slime. Can reduce viscosity to effectively transport
Microbacteria propant. Slimes and oxides can plug formations and reduce permeability. They can also form difficult-to-break emulsions and
hydrogen sulfide, which can be corrosive.

Metals Principally Iron Potential toxicity, can cause production problems (iron in produced water can react with oxygen in the air to produce solids,
which can interfere with processing equipment, such as hydrocyclones), and can plug formations during injection, or cause
staining or deposits at onshore discharge sites
Low pH Can disturb the oil/water separation process and can impact receiving waters when discharged. Many chemicals used in scale
removal are acidic.
Norm Sulfates, Barium, Sulfate concentration controls the solubility of several other elements in solution, particularly Barium and Calcium. Barium,
Strontium, Calcium, Calcium and Strontium sulfates are larger compounds, and the smaller atoms, such as Radium 226 and Radium 228 can fit into
Chloride the empty spaces of the compound and be carried through the flowback fluids. Radioactive elements may precipitate,
endanger public water supplies. The real issue is with accumulation in equipment, which is also difficult to measure
accurately. Typically not a problem in situ, unless concentrated. Barium / Barium Sulfate is acid insoluble and has to be
removed mechanically (drilled out). Barium is highly soluble in Chloride, which can precipitate quickly with sulfates.
Too Saline (High TDS) Any salt, but principally Can impair friction reducer and drive up costs of additives and drive up cost of horsepower for pumping. Some claim
Chlorides freshwater may dissolve reservoir salts for better production (Highly contested and debated topic). Freshwater preferred if
not clay content. KCL can also adversely sensitize the shale by removing calcium such that fresh water can be damaging.
Clay Swelling - Not enough Insufficient salt Some salt preferred if formation has clay. If injected water is less saline than formation water, can cause clay swelling and
Salt for clay formations reduce permeability. 1-3% KCL typically used as clay stabilizer to prevent swelling
Iron fines, scale, SRB and H2S Fe Dispersed Iron can consume the scale Inhibitor, can act as metabolic source for Sulfate Reducing Bacteria, may combine oxygen
to produce insolluble iron fines
Reservoir Production Oil wetting can wet the shale, causing problems
Gel Stability Divalent cations Too high divalent cations can conflict with gel stability to support proppant conduction
H2S Bacteria Sulfate Reducing Bacteria (most common) can produce H2S; Strong environmental and safety concerns for H2S
Transport Costs TDS, Chlorides Like to keep less than 3,000 so can use irrigation lines for transport. Potential to seep out of irrigation lines, could prohibit use.
Reservoir Performance Chlorides Want to keep under 40K to not impair friction reducer effectiveness. 20J-25K ppm will adversely affect gel performance.

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 Water Disinfection Technologies

• Chlorine Dioxide

• Ozonation

• Hypochlorous Acid

• Ultra Filtration (size exclusion technology)

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 Types of Bacteria

Common Types of Bacteria in flowback and

fracing waters:

a. Iron Reducing Bacteria (IRB)

b. Slim Forming Bacteria (SLYM)

c. Sulfate Reducing Bacteria (SRB)

d. Acid Producing Bacteria (APB)

e. Aerobic Bacteria

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 Why is Disinfection Required?

The presence of bacteria in fracturing fluids can cause:

• Microbial Induced Corrosion

• Reservoir Souring
• Odor Issues/Sulfide Production (QHSE Issues)
• Plugging
• Disinfection Level:
o General Statement : Complete kill
• What is currently used: biocides

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•Log Reduction
•1 log reduction means the number of germs is 10 times smaller
•2 log reduction means the number of germs is 100 times smaller
•3 log reduction means the number of germs is 1000 times smaller
•4 log reduction means the number of germs is 10,000 times smaller
•5 log reduction means the number of germs is 100,000 times smaller
•6 log reduction means the number of germs is 1,000,000 times smaller
•7 log reduction means the number of germs is 10,000,000 times smaller

•M-I SWACO Bacteria Disinfection Criteria – 3 log reduction

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 Chlorine Dioxide Overview
Disinfection Mechanism

From DuPont, June 2009

ClO2 can penetrate biofilm in a selective oxidation mode:

- Helped by small size of the molecule, attraction to amino acids and reaction speed.
- ClO2 can penetrate the cell walls inside the biofilm in search of these chemical functionalities.
- Other indiscriminant oxidizers simply react with the C=O double bonds on the cell surface leaving
the oxidized organics to form a protective layer on top of the biomass.

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 Field Trial 2 – Endurance Test
Bacteria Plate Count

Detection Limit Detection Limit

< 1.0 CFU/mL < 3.0 CFU/mL

Detection Limit
< 3.0 CFU/mL

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 Ozone

The ozone molecule is a very powerful oxidizer

and sanitizer. It oxidizes any organic substance
that it comes in contact with, faster and more
effectively than anything else available. And
when the sanitation is complete, or if ozone finds
nothing to oxidize, it becomes molecular oxygen
(from 3 oxygen atoms to 2 oxygen atoms).

Simple Ozone Generator

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 Comparison between ClO2 and WDM

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 Hypochlorous Acid
Hypochlorous acid is a weak, unstable acid with the chemical formula HOCl. It occurs only in solution and is used
as a bleach, an oxidizer, a deodorant, and a disinfectant.
In aqueous solution, hypochlorous acid partially decomposes into the hypochlorite anion ClO - (also known as the
chlorate(ClO2) anion) and the proton H+. The salts of hypochlorous acid are also called hypochlorites. One of the
best known hypochlorites is household bleach, sodium hypochlorite (NaClO).
When pure chlorine is added to water, it forms hypochlorous acid and hydrochloric acid (HCl):
Cl2 + H2O → HOCl + HCl

Hypochlorus acid generator (electrolysis of NaCl)

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 Various Water Treatment Technologies

• Particulate removal (TSS and Bacteria)

• Microfilters, and Nanofilters
• Pod Filters
• Clarifiers

• Removal of dissolved solids

• Ultrafilters, Nanofilters and Reverse Osmosis
• Cold lime softening

• Oil removal
• Absorptive media filters
• Hydrocyclones
• Dissolved Air Floatation

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 Oil-Water Separation Methods

Filter Cartridges
Dissolved Air Flotation (DAF) System

Bag Filter Absorptive Powder

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 Nanofiltration for water hardness reduction.

Nanofiltration, in concept and operation, is much the same as reverse osmosis. The
key difference is the degree of removal of monovalent ions such as chlorides.
Nanofiltration membranes’ removal of monovalent ions varies between 50% to 90%
depending on the material and manufacture of the membrane

Microfiltration

Ultrafiltration

Nanofiltration

Reverse Osmosis

Typical membrane rejection characteristics

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 Reverse Osmosis

Reverse osmosis occurs when the water is moved across the membrane against the
concentration gradient, from lower concentration to higher concentration. To conceptualize,
imagine a semipermeable membrane with fresh water on one side and a concentrated
aqueous solution on the other side. If normal osmosis takes place, the fresh water will cross
the membrane to dilute the concentrated solution.

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 Technology Treatment Chain Possibilities

Particulate Removal Hydrocarbon Removal Biological Treatment Hardness Reduction Deionization

-Bag filter -Gravity Separation -Chemical Biocides -Ion Exchange -Reverse Osmosis
-Depth Filter -Air Assisted Separation -Filtration -Nano-Filtration -Electro Dialysis
-Centrifuge -Ultra Violet Exposure -Thermal
-Oil Absorbing Media -Electro Coagulation
-Flocculation
-Bioreactors
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