Importance of Complex Fluids and Intefacial Behavior in EOR
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1 IV ESCUELA DE VERANO PRODUCTIVIDAD DE YACIMIENTOS Medellín, 2015 VI ESCUELA DE VERANO Recobro y Productividad: La Agenda para Afrontar la Curva de Declinación de Hidrocarburos en Colombia Medellín, Mayo 2017 Importance of Complex Fluids and Intefacial Behavior in EOR Vladimir Alvarado, PhD University of Wyoming
2 Outline Alvarado s group research focus Motivation to study complex fluids and interfaces Is waterflooding all that simple? Why is interfacial dynamics important? Smartwater flooding example Closing remarks
3 Slide 3 Research focus Alvarado s group valvarad@uwyo.edu Professor Department Head Chemical Engineering University of Wyoming Multiphase flow & EOR Research focus Interfacial mechanisms effects on multiphase flow transport and emulsion stability Rock-fluid interactions Complex fluid flow in porous media and rheology. Emulsions & polymers. Interfacial Behavior Elastic modulus (mn/m) Time evolution of interfacial elasticity- 1% salinity 35 Na 30 2 SO 4 CaCl 2 25 NaCl Time (hrs)
4 Leading Strategy Slide 4 a) b)
5 Slide 5 Motivation Chemical Enhanced-Oil Recovery (ceor)
6 % Residual Oil Saturation Slide 6 What is target of CEOR? Sor M Carbonates Typical sandstone Well sorted sand + Oil Water Polymer slug Typical Waterfloods Nc Ultra low IFT M < 1 Favorable
7 micro micro CEOR (ASP) Surfactant Screening Slide 7 Oil 24 hr Brine + surfactant Initial interface Pipette (bottom sealed) Varying parameter Parameter Salinity Surfactant blend ratio Soap/surfactant ratio Winsor Type - I Winsor Type - III Winsor Type - II Optimal parameter
8 ASP Design in WY Slide 8 Crude Oil Surfactant Polymer Alkali Core Viscosity at 48 o C = 83 cp 0.75wt%PS13-D wt%PS3B Flopaam-3330s 2000 ppm (ASP) 1000 ppm (P) Berea: (ASP 1) L= cm D= 3.73 cm PV= cc Φ= 25.62% K air = md 1wt% NaOH Minnelusa: (ASP 2) L= cm D= cm PV= cc Φ= 21.43% K air = md 8
9 Designed Water: Chem. Flood Slide 9 Gregersen et al., Fuel, 2013 Model Rock Designed Brine Traditional Design Anhydrite-Rich Rock WF ASP P WF 9
10 The Challenge of Anhydrite Slide 10 Observed precipitation at effluent samples: Ca Spectrum 1 Cl Na O K Ca S K Cl Si Cl K Ca Full Scale 4240 cts Cursor: (82 cts) kev Spectrum 4 Ca Cl Cl K O Ca Na Si S Cl K K Ca Full Scale 5549 cts Cursor: (361 cts) kev As expected secondary minerals occurred (calcite and sulfur are evidence for anhydrite dissolution)
11 Is waterflooding all that simple? There is more to it than we imagine
12 Timeline of waterflooding Slide 12 Alvarado, V. et al. Hughes et al. (1947) Williamson, H. (1926) 1900 ends Reservoirs pressure decreasing 1947 Fresh water vs. Salty water coreflooding Morrow, N. (1990) 515 citations 2014 Snap-off vs. coreflooding 1859 Drake oil well 1920 Bradford field waterflooding Leach et al Wettability 1990 Wettability vs. coreflooding
13 Percolation and ganglion dynamics of n-decane and water Slide 13 Water Coreflooding Oil Connected oil X-Ray Window Residual oil Ganglion dynamics Shock Front Rücker et al. (2015)
14 Sulfate as interface-stabilizing ion & smart-water flooding in carbonate Garcia-Olvera and Alvarado, Fuel (under review)
15 Slide 7 Interfacial Visco-elasticity σ t = γ o [G ω sin ωt + G " ω cos ωt ] G ω : elastic modulus G " ω : viscous modulus 15 Moradi & Alvarado, SPE Journal, Under Review
16 Main experiments Slide 16 The AR-G2 rheometer (TA instruments) with DWR to measure shear interfacial rheology An FDS pendant drop apparatus to measure interfacial tension (IFT) SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
17 Results- Background Asphaltenes Effect Slide 17 WG crude oil IS = M (Na 2 SO 4 ) (SPE ) SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
18 Results- Background - Ions Effect Slide 18 GB crude oil Brine IS = M (OTC-26293) SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
19 1. Rock Indiana Limestone L~11, D~ Oil Materials Core Porosity Swi Kw (%) (%) (md) IL-G IL-K IL-ZD IL-ZD IL-ZD IL-ZD IL-ZD IL-ZD IL-ZD Crude Oil Density Viscosity Pentane-Asphaltenes (gr/cm3) (cp) (wt%) GB K ZD Slide 19 SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
20 Materials Slide Brines LS Brine TDS (ppm) ph SO 4 (ppm) Ionic Strength (M) SW 35, , SW3S 36, , SW0S 34, SW5S 37, , SW3CM 30, , SW0CM 37, , SW 17, , SW 3, SW0S 17, SW0S 3, SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
21 Results Slide 21 ZD oil-brine IFT at 25ºC SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
22 Results Slide 22 G (mn/m) G (mn/m) ZD-10SW ZD-SW3S ZD-SW ZD-SW0S SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
23 Results -HS Slide 23 SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
24 Results-HS Slide 24 Oil recovery factor for IL-K1, IL-ZD1 and IL-G1 SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
25 Results-HS Slide 25 Optimum So for smart WF? 1.5 SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
26 Results-HS-LW Slide 26 SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
27 Results-HS-LS Slide 27 Recovery factor and pressure drop data for IL-K1 coreflooding SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
28 Results Breakup/snap-off and coalescence are the dominant processes responsible for phase connectivity (Doster & Hilfet, 2011; Rücker, 2015) Slide 28 The overall growth in the water drop size can be correlated with coalescence, i.e. ZD-10SW is less stable than SW3S. SPE The Potential of Sulfate as Optimizer of Crude Oil-Water Interfacial Rheology G. Garcia-Olvera
29 Wettability vs. Viscoelasticity Interfacial Wang and Alvarado
30 Slide 30 Capillary Hysteresis Hysteresis refers to the irreversibility or saturation path dependence. Paper SPE MS Effects of Low Salinity Waterflooding on Capillary Hysteresis Xiao Wang
31 1.3 Capillary Hysteresis sources Slide 31 o Contact angle hysteresis o Wettability alteration. Paper SPE MS Effects of Low Salinity Waterflooding on Capillary Hysteresis Xiao Wang
32 1.3 Capillary Hysteresis sources Slide 32 o Trapping of non-wetting phase Piston-type displacement Break-off Convex Interface Imbibition process Snap-off Topology Wettability Selloidal Meniscus Interfacial properties Li and Wardlaw (1985) Paper SPE MS Effects of Low Salinity Waterflooding on Capillary Hysteresis Xiao Wang
33 Apparatus Slide 9 33 Obtain full capillary hysteresis curves in conjunction with 2T and 4T electrical resistivity at reservoir conditions. Pore pressure: 6000 psi Confining pressure: 9950 psi Temperature: 150 C
34 High-temperature (93 o C) experimental conditions Slide Sample ID WY (High salinity) WY (Low salinity) Rock type Minnelusa Minnelusa Diameter (D) and length (L) D=1.5 ; L=1.44 D=1.5 ; L=1.55 Porosity and permeability =16.10%; K=71mD =15.79%; K=75 md Brine High salinity-high salinity High salinity-low salinity (#1) Oil TC crude oil TC crude oil Temperature 93 C 93 C Pc measurement method Static-static Static-static
35 High temperature experimental results Slide o Capillary pressure hysteresis (High Salinity) (Low Salinity) o Resistivity index and hysteresis
36 High-temperature experimental results explanations Slide o Anhydrite dissolution modifies rock surface and results in more contact angle hysteresis. o The brine salinity in the imbibition process is not low enough to build highly elastic interface to hinder snap-off. o Low-salinity brine could alter the rock to be more water-wet and enhance snap-off. Wang & Alvarado, SPE Journal, Under Review
37 Low-temperature (30 o C) Experiments Slide Core ID WY 1-75-B WY 1-75-C Rock Type Minnelusa Minnelusa Porosity and permeability Φ=16%; K=218 md Φ=16%; K=218 md Brine High salinity-high salinity Low salinity (#2)-Low salinity (#2) Recovery Factor 78.87% 93.60% Pc curves
38 2.9 Low-temperature Experimental Results Explanations Slide o Interfacial viscoelasticity Low-salinity brine yields HIGHER visco-elasticity, which can suppress snap-off and enhance the continuity of the oil phase.
39 Wettability effect on resistivity hysteresis Slide Decane Low temperature (30 C) No wettability alteration No hysteresis Low temperature (30 C) No wettability alteration No aging No hysteresis TC crude oil High temperature (93 C) More oil-wet Hysteresis
40 Slide 40 Understanding the crude oil interface using pendant drop experiments 40
41 The pendant drop system Slide 41
42 Interfacial viscoelasticity - IFVE Slide 42 Δ A γ 0 +Δγ γ 0 +Δγ A 0 E = Δγ ΔA/A o E( i ) E'( ) ie"( ). E = Viscoelastic Modulus of the interface E = Elastic Modulus of the interface E = Loss Modulus of the interface Tan δ = E / E = Phase angle
43 Influence of salinity on IFE Slide 43 WG asph cont = 10.2 w% Interfacial elasticity is higher for low salinity
44 Slide 44 The crude oil interface stability in liquid bridge experiments 44
45 The liquid bridge adaptation Slide 45 Hoyer, P. and Alvarado, V. (2016)
46 Liquid bridge Slide 46 Inelastic Elastic Under the same conditions but ageing 46
47 Critical neck diameter (CND) Slide 47 CND CND
48 CND changing with ageing time T Slide 48.Low salinity water stabilizes the interface faster.
49 CND vs. k (relative elasticity) Slide 49 k K K ln( D f / D i ) Bridge stability correlates with interfacial moduli
50 CND vs. k for different ions Slide 50 Different interfacial properties are needed
51 The effect of sulfate Slide 51 Sulfate increases the stability even at higher salinity of other ions
52 Solid-like membrane Longer aging times produce solid-like membranes with very strong stability
53 Why interfacial elasticity stabilizes the interface?
54 Slide 54 Constricted capillary model Modeled with lubrication theory Hoyer, P., Alvarado, V., Carvalho, M.S. (2016)
55 Slide 55 Neck radius time evolution t b k=0.4 55
56 Break-up time k dependence Slide 56 t b Time to breakup increases asymptotically when relative elasticity tends to 1
57 Driving force pressure gradient Slide 57 Less fluid is pumped out from the throat when the elastic modulus is higher
58 Slide 58 Need for disruptive technology? Appropriate brine chemistry may enable several applications Low salinity Increased RF Designed Water Chemistry Efficiency SP & PF Increased RF Decreased Volumes Phase behavior Controlled R-F Interactions & Production Issues Scaling Emulsion Stability O/W separation Form. Damage
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