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PRODUCED WATER CHARACTERISTICS FOR TWO FIELDS IN THE PERMIAN
AND DELAWARE SHALE BASINS
J.M. Walsh, CETCO
Thursday January 19, 2017
The Produced Water Society Seminar 2017
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Sincere thanks to:
Ramesh Sharma, ConocoPhillips Greg McLelland – ConocoPhillips, Barkman-Davidson Tekla Taylor – independent consultant, Geochemisty Josh Hebert – CETCO, project planning & field work Gustavo Garcia – CETCO, field work Joey Rogers – CETCO, field work ConocoPhillips and Shell staff
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Produced Water Characteristics in two fields in the Permian and
Delaware Shale Basins Outline:
background
methods
results Geochemistry
conclusions
Not at liberty to identify the specific formations in this presentation.
Outline
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The four areas of design and operation all depend on the influent water characteristics and the required effluent quality. Water characterization becomes more important as the difference between influent and effluent becomes greater (true for shale).
Equipment Process
Chemical Treatment Operations
Fluid Characterization
Effluent Quality
Why Characterize the Fluids?
Ref: Walsh SPE 2008, SPE 2009, SPE 2010, Tekna 2011
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Which qualities / characteristics are important?
That depends on disposal / reuse options (required effluent quality):
Salt Water Disposal Well: injectivity
Reuse for hydraulic fracturing: injectivity, not
dissolved components (see Ref below)
Surface discharge: rigorous set of quality standards
How can we achieve the required qualities / characteristics?
Briefly discussed at the end
Important Water Qualities
Ref: SPE-163824 (2013):
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Typical Process Flow Diagram
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General direction of flow This is a storage facility with unrealistic oil / water / solids separation
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Methods: on-site particle size analysis
(Jorin, Millipore) particle composition
(NACE TM0173 solvent test, DI water washed, TGA-DSC, SEM)
water chemistry
(on-site Hach & ICP digested samples)
on-site filterability
(Barkman-Davidson)
On-site measurements were made on “fresh” samples (i.e. no exposure to oxygen)
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Technology Pilot Unit / Sampling & Analysis
Jorin MZ4 field unit TSS filtration sample manifold
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Sample Manifold
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Manifold features: PSV pressure gauge ball valves, needle valves flow rate via graduated cylinder eliminates shear
This system is used for: TSS 4-Filter Sieve test Barkman-Davidson Jorin feed
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Inside of the Analytical Trailer
scale
oven
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Particle Size Measurements
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The next few slides provide data on the particle size. All measurements made on-site, on-line, “fresh” samples. Four measurement techniques were used:
Total Suspended Solids – 0.45 micron filter, NACE TM0173 5-Filter Sieve TSS measurement (20, 8, 2, 1.2, 0.45 micron)
Jorin Visual Particle Analyzer (ViPA) – particle count
Barkman-Davidson volume versus time – injectivity test
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The filter holder is connected to an on-line manifold with valves, a pressure gauge, and a graduated cylinder for measuring flow rate.
5-Filter Millipore Apparatus
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5 filter holders stacked one on top of the other
water flow
Millipore size
(micron):
20
8
2
1.2
0.45 5 filter membranes
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5-Filter Millipore Apparatus
This apparatus catches suspended particles in five different size ranges. In theory, particles larger than 20 micron are caught on the 20 micron filter, particles smaller than 20 micron and larger than 8 micron are caught on the 8 micron filter, and so on. Filter cake will trap small particles on large pore filters.
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5-Filter Millipore Apparatus
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Barkman – Davidson Analysis
Volume of water (mL) passing through 0.45 micron filter paper versus square root of time (sec1/2). Feed pressure 20 psi. Steady flow rate (slope of red line) is due to filter- cake formation. B-D similar to NACE TM0173 or Silt Density Index (ASTM 4189-95). Drawbacks:
it only evaluates one impairment mechanism: filter cake buildup for quantitative results (injectivity improvement) it must be correlated to field data
Ref: J.H. Barkman, D.H. Davidson, SPE JPT (1972). J.R. Coleman, W.G. McLelland, SPE – 27394 (1994). W.G. McLelland SPE (2012, 2014, 2015, 2016)
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Barkman – Davidson Analysis for Conventional Fields
B-D Slope is empirically related to “injectivity” of produced water. These correlations are proprietary and will not be shown here.
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Results for produced water in the Delaware Basin:
particle size analysis
water chemistry
filterability (injectivity)
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Water Sample
Sample: 14-Aug 23:00
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TSS Particle Size Analysis – mg/L versus N/L:
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Based on the 4-filter Sieve data the particle concentration (number of particles/mL) was calculated (right hand figure). There is a large number of particles in the range 0.45 to 8 micron.
Relation between mg/L and Number of particles/L
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Jorin Particle Size Analysis - particle concentration
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Jorin does not accurately report results below 3 micron. Above 3 micron the Jorin agrees with the 4-filter TSS.
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Jorin & TSS Particle Size Analysis – Number Average Particle Diameter
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This slide shows that the average (D50) particle diameter is about 1.3 micron. This means that half the particles are greater than 1.3 micron and half are smaller. Triangular points are from TSS 5-filter measurements. Line is from Rosin-Ramler.
D50 particle diameter is
read from here
1.3
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TDS Composition
Digested sample. Gas contains 2 mol % CO2, essentially no hydrogen sulfide.
Ref: SPE-163824 (2013) This study – Delaware Basin
Ref: R. Perry, R. Bosch, SPE ATW Dallas-Ft Worth (2013) R. Sharma, personal communication (2017)
Play iron (mg/L) Woodford 30 Wolfcamp 100 Haynesville 150 Eagle Ford 70
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Analytical Results – Unknowns Analysis
The following tests were carried out on the filter samples: XRF, XRD, FESEM, FTIR, XEDS Results are:
iron oxides and iron carbonate <1 to 3 micron precipitated NaCl (from drying) 1 to 3 micron silica (sand) 1 to 20 micron shale fines 1 to 10 micron
SEM SEM Frac Tank (iron)
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Analytical Results – Filter Material Solvent Wash
XRD analysis carried out on filter material Following the NACE-MR0173 method.
Roughly 9 to 20 wt% of filter material is soluble in DI water (NaCl); there is essentially no wax or asphaltene. Most of the sample is silica fines. There is significant iron.
XRD analysis carried out on filter material:
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Three settling stages of a sample
1 hour after sampling 1 day after sampling 2 days after sampling
Settling times indicate colloid chemistry (DLVO). Not intended for design purposes.
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Barkman – Davidson Analysis for Conventional vs Shale Field
conventional produced water shale well in Delaware Basin
According to the B-D Slope, this location will have injectivity problems – verified by operator.
B-D Slope is a measure of the rate at which water passes through a Millipore filter once a filter cake has built up. This can be correlated quantitatively to injectivity. A tight filter cake composed of small closely packed particles has a low B-D Slope value and indicates that injection wells will plug.
Good Injectivity
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Summary of Results for Delaware Basin:
Very small particles of iron
compounds, crushed sand
Limited presence of oily solids. No indication of organics adhered to solids
Low filterability (injectivity)
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Next: Results for produced water in the Permian:
particle size analysis
water chemistry
filterability (injectivity)
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TSS Particle Size Analysis
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The above graph shows the number of particles per mL captured by the Millipore filter (5 Millipore are used with pore size: 0.45, 1.2, 8, 20, 60). There is a large number of particles in the range 0.45 to 8 micron.
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30 Sample: 28-Sept 15:00
Original sample (left) and same sample with hexane added (right). Note that the contaminant is completely extracted into the hexane phase. This indicates that the solids are coated with oil.
Produced Water Appearance
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31 Sample: 24-Sept 16:00
Note the droplets hanging just below the hexane/water interface. These hexane droplets are coated with oily solids that are interfacially active. The oily solids prevent coalescence with the hexane phase.
Produced Water Appearance
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Solids Composition – TGA-DSC:
Spent HF polymer – typical DSC ~ 300 to 400 C Kerogen – 400 to 500 C
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Solids Composition in Feed Water (NACE TM0173):
Carbonates are likely iron carbonate. HCl solubles are likely iron oxide compounds. No indication of sulfide. Acid insolubles are likely kerogen, shale, silica, clay. Data courtesy of Tom Tekavic, Shell.
insoluble acetic acid xylene HCl
Example filter
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Barkman – Davidson Analysis for Conventional vs Shale Fields
conventional reservoir Permian Basin
Low B-D Slope – low filterability (injectivity)
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Geochemistry
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Is there a Geochemical source of iron?
Not at liberty to identify specific formations in this presentation. Geochemist (Tekla Taylor) has reviewed the specific formations and compared them to the known Geochemistry of these basins and found them to be consistent (water composition, iron, shale composition, carbonate content). Base of Rocky mountains with adjacent shallow sea marshes:
Igneous (volcanic) Rock (high iron content) Shales formed by Eolian (wind driven) processes which preferentially
transport very fine grains of silica, clay and magma into shoreline marshes and lagoons (same process as desert varnish).
Marsh vegetation trapped within the sediment, forming organic rich shale. Hydraulic fracturing and production:
Fine particles of shale rock & kerogen is then suspended in produced fluids via hydraulic fracturing. Also, high CO2 dissolves iron and other minerals.
Desert Varnish
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Summary & Conclusions: Delaware Basin field: small particles composed of iron compounds,
crushed silica (proppant sand), fine (fractured) shale particles without significant organic coating, clay, very poor filterability (injectibility).
Permian field: similar to above but with considerably more organics (spent polymer and kerogen).
Options to remove particles, for both types of fluid: • fine filtration; • oxidize the iron to create a filter floc (sludge blanket) or use a
high rate clarifier; • chemically precipitate the iron (Fentons, ozone, ClO2, peroxide); • coagulate / flocculate and settle / filter the solids; • electro-coagulate the solids and settle, float or filter
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The End
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Why are produced water characteristics important?
most produced water is disposed in SWD disposal costs (pumping, cleanout) depend on the
injectivity of the water
some produced water is recycled (injected into a shale formation) the success of the fracturing operation depends on
the water quality
Which characteristics / qualities are important? How can we achieve the required characteristics?
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Injection of Produced Water
Injectivity is a function of: Quality of the drilling and completion operations Porosity and permeability of formation – Karmen-Cozeny
approach Integrity of the formation (fines migration) Compatibility of injected water with formation & formation water Pore plugging characteristics of injection water
Produced Water Plugging Characteristics:
Core flush – fresh core, onsite, realistic pressures, expensive Measure TSS, Oil-in-Water, oil density – inexpensive, does not
correlate with injectivity Measure filterability