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11/4/2010 Confidential Information 2010 M-I SWACO1

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

Integrated Oil Field WaterManagement

Central Location

M-I SWACO Water Treatment

On Site

M-I SWACO Water Treatment


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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

Effectiveness

Multivalent Ions (Fe, Ca,

Mg, Ba, Sr)

Can reduce friction reducer effectiveness, drive up horspower costs

Scaling calcium carbonate,

calcium sulfate, barium

sulfate, strontium

sulfate, and iron sulfide

Equipment fouling, can clog flow lines, form oily sludges that must be removed, and form

emulsions that are difficult to break

Bacterial Corrosion Bacteria and

Microbacteria

Can clog equipment and pipelines and accelerate corrosion and form slime. Can reduce viscosity to effectively transport

propant. Slime s and oxides can plug formations and reduce permeabil ity. They can also form difficult- to-break emulsions and

hydrogen sulfide, which can be corrosive.

Metals Principal ly I ron Potential tox ici ty, can cause production problems ( iron in p rodu ced water can react wi th ox ygen in th e ai r to pro duce sol ids,

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,

Strontium, Calcium,

Chloride

Sulfate concentration controls the solubility of several other elements in solution, particularly Barium and Calcium. Barium,

Calcium and Strontium sulfates are larger compounds, and the smaller atoms, such as Radium 226 and Radium 228 can fit into

the empty spaces of the compound and be carried through the flowback fluids. Radioactive ele ments 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 insolu ble and has to be

removed mechanically (drilled out). Barium is highly soluble in Chloride, which can precipitate quickly with sulfates.

Too Sal ine (High TDS) Any salt, but principally

Chlorides

Can impair friction reducer and drive up costs of additives and drive up cost of horsepower for pumping. Some claim

freshwater may dissolve reservoi r 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

Salt for clay formations

Insufficient salt Some salt preferred if formation has clay. If injected water is less saline than formation water, can cause clay swelling and

reduce permeability. 1-3% KCL typically used as clay stabilizer to prevent swelling

Iron f ines, scale, SRB and H2S Fe Dispersed Iron can consume the scale Inhibitor, can act as metabol ic source for Sulfate Reducing Bacteria, may combine oxygen

to produce insolluble iron fines

Reservoir Production Oil wetting can wet the shale, causing problems

Gel Stabi li ty Divalent cation s To o high divalent cations can co nf li ct w ith ge l s tabi li ty to su pport proppant co nduction

H2S Bacteria Sul fate Redu cing Bacteria (most commo n) can p rod uce H2S; Stron g env ironmental and safety concerns for H2S

Transport Costs TDS, Chlorides Like to keep less than 3,000 so can use irrigat ion l ines for transport . Potential to seep out of irrigation l ines, 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 andfracing 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 smaller3 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 OverviewDisinfection Mechanism

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.

From DuPont, June 2009


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Field Trial 2 Endurance TestBacteria Plate Count

Detection Limit

< 1.0 CFU/mL

Detection Limit

< 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 substancethat 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

Bag Filter Absorptive Powder

Dissolved Air Flotation (DAF) SystemFilter Cartridges


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Nanofiltration for water hardness reduction.

Nanofiltration, in concept and operation, is much the same as reverse osmosis. Thekey 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

Typical membrane rejection characteristics

Microfiltration

Ultrafiltration

Nanofiltration

Reverse Osmosis


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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

Hydrocarbon Removal-Gravity Separation

-Air Assisted Separation

-Centrifuge

-Oil Absorbing Media

-Flocculation

-Bioreactors

Biological Treatment-Chemical Biocides

-Filtration

-Ultra Violet Exposure

-Electro Coagulation

Hardness Reduction-Ion Exchange

-Nano-Filtration

Deionization-Reverse Osmosis

-Electro Dialysis

-Thermal

Particulate Removal-Bag filter

-Depth Filter

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