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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
http://www.google.com/imgres?imgurl=http://www.degremont-technologies.com/IMG/jpg/Nanofiltration-global.jpg&imgrefurl=http://www.degremont-technologies.com/dgtech.php?article457&h=521&w=560&sz=62&tbnid=gT9jmLPnwYqRyM:&tbnh=124&tbnw=133&prev=/images?q=nanofiltration+pictures&zoom=1&q=nanofiltration+pictures&hl=en&usg=__RT4__NMCBMEwy1MtPtrjrhJKUjs=&sa=X&ei=w6rSTOGDJMWblgeazPiGDg&ved=0CCUQ9QEwAA8/8/2019 002.Scott LaRue
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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