Residual Disinfection

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Details of Treatment. Oxidizing vs. Non-Oxidizing Biocides. Non-Oxidizing Biocides. • No compatibility issues. • Potentially lower cost. • No effect on Iron or Sulfides. • No real time monitoring. • Bacterial resistance concerns. • Efficacy concerns in produced water *. Oxidizing Biocides. • Compatibility issues. • Potentially higher ...

Basic Treatment Requirements What Are Your Goals Constituent

Slickwater

Guar (Linear)

Guar (XL)

Hybrids (XL)

140K (anionic) No Limit (cationic)

60K

60K

60K

50K

20K

20K

20K

Iron (ppm)

25

10

10

10

Oil (ppm)

100

50

50

50

TSS (ppm)

100

100

100

100

No Limit

10

10

No Limit

100

100

100

100

Chlorides (ppm) Total Hardness (ppm)

Boron (ppm) Bacteria (cfu/ml)

Water Treatment Requirements Scale Inhibition

Microbial Control

Filtration

Water Treatment Requirements

Aeration • Bacterial Control • Iron Oxidation • Sulfide Oxidation

Oxidation • Bacterial Control via Oxidation • Iron Oxidation • Sulfide Oxidation Filtration • Solids Control

Details of Treatment Filtration

Contaminants Targeted: • TSS • Bacteria • Iron • Turbidity

Bag Filtration What are the Basics ?

• Bag Filtration • Bag Fit • Filter Pod Quality • TSS Goals • TSS Size Distribution • Micron Size • TSS loading

Bag Filtration What Micron ? Particle Size Distribution Particle Size Distibution for Produced Water Samples 120.0%

97.9%

100.0% 84.2%

Percentage

80.0%

60.0%

40.0%

20.0% 9.3%

5.4% 0.0% 0.0%

0.0% 0.0%

> 10

5 - 10

0.7%

1.0% 0.8%

0.6%

0.0% 1.5 - 5

1 - 1.5

Particle Size, µm

0.45 - 1

< 0.45

Bag Filtration What Micron ? TSS, Turbidity and Size Distribution Table 1: Filtration Test #1 Filter size

Turbidity

TSS

1

2

Ave

1

2

Ave

None

5.52

5.17

5.345

2

1

1.5

10 µm

5.49

5.33

5.41

4

5

4.5

5 µm

5.37

5.66

5.515

3

1

2

1.5 µm

0.87

0.87

0.87

0

0

0

1 µm

0.58

0.56

0.57

0

0

0

0.45 µm

0.51

0.52

0.515

0

0

0

Details of Treatment Aeration

• Air Driven • Submersible or Floating • Submersible better for oxidation and solids control

Floating

Submersible

Aeration via Submersible Mixer

Details of Treatment Oxidation

Contaminants Targeted: • Bacteria • Iron • Sulfides

Details of Treatment Oxidizing vs. Non-Oxidizing Biocides Non-Oxidizing Biocides • No compatibility issues • Potentially lower cost • No effect on Iron or Sulfides • No real time monitoring • Bacterial resistance concerns • Efficacy concerns in produced water *

Oxidizing Biocides • Compatibility issues • Potentially higher cost • Oxidizes Iron and Sulfides • Real time monitoring • No bacterial resistance concerns • No efficacy concerns in produced water

* ”Produced Water Exposure Alters Bacterial Response to Biocides”, Vikram, A.; Lupus, D.; Bibby, K.; Univ. of Pittsburgh

Disinfection vs. Compatibility Oxidant

Oxidation Half-Life Potential, @ 20OC V

Hydroxyl Radicals

2.8

< 1 sec

Ozone

2.3

20 min.

Hydrogen Peroxide

1.8

Hours

Chlorine Dioxide

1.5

93 min.

Chlorine

1.4

140 min.

Disinfection

Compatibility

Disinfection vs. Compatibility Friction Testing – Chlorine Dioxide Baseline + 0.5 gpt FR

ClO2 Treated Water

ClO2 Treated Water + 0.5 gpt FR

40%

30%

% Friction Reduction

20%

10%

0%

-10%

-20%

-30%

-40% 0

2

4

6

8

10

Time, min

12

14

16

18

20

Disinfection vs. Compatibility Friction Testing – Ozone Untreated+ 0.5 gpt FR

Treated

Treated + 0.5 gpt FR

60%

50%

% Friction Reduction

40%

30%

20%

10%

0%

-10% 0

2

4

6

8

10

Time, min

12

14

16

18

20

Disinfection vs. Compatibility Slickwater: HZO vs. Biocide vs. Chlorine Dioxide 0.040

Friction Reducer Concentration, % in mass

Hydrozonix 0.035 0.030

Biocide ClO2

0.025 0.020 0.015 0.010 0.005 0.000 2012/10/18

2012/12/7

2013/1/26

2013/3/17

2013/5/6

2013/6/25

2013/8/14

2013/10/3

2013/11/22

Fracturing Date

Water Treatment Technology Biocide ClO2 Hydrozonix

# of Wells 22 9 27

FR Concentration, % in mass 0.0123 0.0146 0.0042

• 80- 110 BPM Capacity • Environmentally Friendly • Small Footprint • Eliminates use of Biocide, Scale Inhibitor • Reduces use of Friction Reducer, Gel, Breaker

Over 90,000,000 bbls treated

Testing Program • Unique Hydrozonix Feature • Real Time Water Quality Testing • Creates certainty for treatment verification • Includes testing Hydrocarbons, Iron, TSS and Bacteria • Test all key parameters once per shift, more frequently when water quality changes • Inline probes for ORP and pH • Hydrozonix has developed proprietary sample prep procedures

InfraCal 2 ATR-SP EPA Method 1664

HACH DR 900 for TSS and iron

ATP Kit for Real Time Bacteria

Bacteria Testing Where do I Sample ? • Influent/Effluent of Treatment System • MPN • ATP • Continuous Testing • Residual Disinfection / Working Tanks • ATP • Continuous Testing • Source Water • ATP • MPN • Baseline Testing

Influent & Effluent

Source Water Testing

Working Tank Monitoring

Real Time Testing: Residual Disinfection Residual Disinfection - Free Chlorine and ATP 0.8

500

ATP, pg/mL

0.7

Free Chlorine

0.6

ATP, pg/mL

400

0.5

300

0.4 0.3

200

0.2 100

0.1

0

0 0

1

2

3 4 5 Time after treatment, hr

Tests were conducted at Bold Johnson 56-T1-34 #1H

6

7

8

Free Chlorine, mg/L

600

Residual Disinfection: Working Tank Monitoring Residual Disinfection - Free Chlorine and ATP ATP Levels in the Treated Water 700

600 Working Tanks

Clean Buckets

ATP, pg/ml

500

400

300

200

100

0 0

2

4

6

8

Time after Samples Were Taken, hr

10

12

14

Working Tank Monitoring Biocide Dose Monitoring ATP Level in the Working Tanks 6000 5147 5000

ATP, pg/ml

4000 2996 3000 2000

1932

1822 1466

1452

1529

1000

436

158

0 Water Delivered

    

Day 1

Day 2

Day 3

Biocide -15 min

Biocide - 2 hr

Biocide - 24 hr

Hydrozonix-Day1 Hydrozonix-Day2

Untreated impaired was delivered to the working tanks, the initial ATP level was around 1,452 pg/ml. Bacteria level increased as the water was stagnant in the tanks, after 3 days, the ATP level went up to 5,147 pg/ml. 0.5 gpt of biocide was dosed into the working tanks, this brought the ATP level down to 2,996 pg/ml 15 min after the dosing. The ATP level stabilized to be around 1,500 pg/ml 24 hr after the dosing, which indicated that the bacteria level in the biocide treated water was still high. After treated water form Hydrozonix treatment system sent to the working tank for one stage, the ATP level went down to 436 pg/ml. This was further reduced to be at 158 pg/ml after the treatment had continued for another day.

Disinfection Monitoring Flowback Testing

Sampling Locations

APB, MPN/ml

GHB, MPN/ml

Well Head

4

6

Gas Separator

3

3

Heater Treater

460

1,100

Storage Tank

11,000

11,000

Proppant Monitoring Residual Disinfection – Proppant Testing with ATP

Samples

ATP, pg/mL

0.1 lb/gal sand + Distilled Water

1.8

0.2 lb/gal sand + Distilled Water

2.3

• Proppant does not appear to be source of bacteria • Result within error for ATP test • Result is essentially zero

Key Takeaways • Low Cost – Less than $0.40/bbl for a complete program of aeration, filtration, oxidation and real time monitoring.

• Superior Disinfection/Scale Inhibition – Effective over wide range of water quality, including 100% produced water as a biocide and scale inhibitor replacement. Real time testing helps optimize

• Mixing/Aeration – Improved water quality while in storage.

• Capable of Handling Varying Water Quality – Produce Water can change quickly and over a wide spectrum

• Improved Compatibility – While other techniques can cause incompatibility we actually improve it

• Better Mass Transfer/Mixing – Most techniques use one point of mixing, we rely on 5 points of mixing

• Real Time Testing – Most water treatment approaches provide no real time testing, they rely on a “hope for the best” approach

28

www.hydrozonix.com

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