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
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