From mud to worms…

the rheology and colloid science

of oil recovery

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Geoffrey Maitland
Schlumberger Cambridge Research
 Acknowledgements
Schlumberger: Trevor Hughes, Jian Zhou, Tim Jones, Gary Tustin, Isabelle Couillet,
Seth Hartshorne, John Crawshaw, Edo Boek, Neil Alderman, Paul Reid

Cambridge University: Malcolm Mackley, Rachel Cooke

Strasbourg ICS, CNRS
Twente University:
Dusseldorf University:
Delaware University:
Bristol University:
Utrecht University:
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Francoise Candau, Jean Candau
Wim Briels, Johan Padding
Harmut Loewen, Arben Jusufi
Eric Kaler, Shrinivasa Raghavan
Terence Cosgrove, Vania Croce
Henk Lekkerkerker, Annemieke ten Brinke,
Marcel Vogel
 Drilling an Oilwell and Treating the Reservoir

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 From mud to worms…

z How do you predict the HTHP rheology of drilling muds

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- and control their rate/extent of gelation?

z How do you make shower gels operate in deep hot wells?

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 The HTHP Rheology of Drilling Fluids

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Controlling Gelation

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 Drilling Fluids…mud, glorious mud
z Oil-based muds:
– Water-in-oil invert emulsions
– Organophilic clays

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– Emulsifers/wetting agents

z Water-based Muds:
– Bentonite Clay (Na+/Ca2+ Montmorillonite) φ ~ 0.02
– Heavy Mineral Weighting Agent (eg Barytes) φ up to 0.5
– Polymers as dispersants, fluid loss additives
– Mineral Cuttings
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 Water-based Muds…highly thixotropic

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Bentonite
Suspension:
6% w/w φ = 0.024

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 High Temperature-Pressure Rheology
z Operating Range
– Temperatures 20 -150 oC
– Pressures 1-1000 bar
z Flow curves follow Herschel-Bulkley model

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τ = τy + Kγn
z Model based on τy, n and ηHB = nK(1000)n-1
z The HTHP behaviour is dominated by
– The T,P dependence of the continuous phase viscosity
– Changes in emulsion/particle packing fraction as T,P changes
z All OBMs show significant pressure dependence
z Only weighted WBMs show significant pressure dependence
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 Suspension viscosity - solids volume fraction

Krieger-Dougherty equation: ηsusp = ηsolvent (1 - φ/φm) -[η]φm

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ηsusp

α(φ)

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φ φm
4/7/2005
 Temperature variation – model prediction

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 Pressure variation – model prediction

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 WBMs – Creep and Stress Relaxation

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Bentonite Suspension 2.5%w/v, φ = 0.01
Apparent yield stress = 5 Pa
Stress: a = 0.6 Pa, b = 3.9 Pa, c = 4.4 Pa
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 WBMs - Low shear behaviour
Bentonite mud, 6%w/w (vol fn = 0.024)

140000
Effective viscosity/Pa s

120000

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100000
80000
Mud A
60000
40000
20000
0
0.00001 0.0001 0.001
Shear rate /s
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 Gelation of mixed colloid drilling fluids on
cessation of flow
z

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 Manipulation of viscoplastic profile
+- - - - - - - -- +
- - - -
+ - -+ - ++ - +- + +
Bentonite platelet with negative faces.
Edge charges are pH-dependent. + Hexagonal plates, aspect ratio ~ 10
+ +

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VISPLEX crystals: ++ + Diameter ~100nm, Mg/Al ~ 1.0
positive charge due to 1 micron
electron-deficient lattice 100000

Apparent Viscosity (mPa s)

10000

Clay-based WBM
MMH Fluid
1000

100
0.1 1 10 100
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4/7/2005
P I Reid et al, SCR
1:2 Mg:Al MMH, High Temperature Rheology
200

150

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Shear stress (Pa/2)

T= 25C
T= 125C, 16hrs
100 T= 125C, 32hrs
T= 150C, 16hrs
T= 190C, 16 hrs
50

0
0 100 200 300 400 500 600 700
Shear rate (sec-1)

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P I Reid et al, SCR
 Gel Strength vs Time/Composition
60

50

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Gel Strength (Pa/2)

40
Mg:Al = 1:1
Mg:Al = 2:1
30
Mg:Al = 3:1
20
Mg:Al = 4:1

10

0
1 2
(1) 10 sec (2) 10 min Gel Strength

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P I Reid et al, SCR
 Gibbsite: TEM image

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200 nm

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Marcel Vogel, University of Utrecht
 Gibbsite-Bentonite Mixtures

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Gibbsite

19 JG-Rideal-Apr2005 Marcel Vogel, University of Utrecht

4/7/2005
 Schlumberger Public
Shower Gels for Deep Hot Wells
Wormlike Micelles at >150oC

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 Viscoelastic Surfactant Fracturing Fluids

z
• hydrophobic tail
• C22 chain
• cis double bond
at C13

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• hydrophilic head
group
Erucyl bis (2-hydroxyethyl) methyl ammonium chloride • quaternary
— ammonium with
H H Cl 2 hydroxyethyl
CH 2 –CH 2 –OH
groups
C C
+ • derived from
CH 3 –(CH 2 ) 7 (CH 2 ) 11 –CH 2 –N–CH 3
rape seed oil
CH 2 –CH 2 –OH
• blended with
iso-propanol

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 Oil-responsive Viscoelastic Surfactants
+salt + +
+ +
+oil
+

+
+ + +

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1-4wt% Worm-like Micelles Network of Worm-like Spherical Micelles
Micelles
1.00E+02

1.00E+01
Hydraulic Fracturing
Viscosity (Pa.s)

1.00E+00
40 oC (104 oF)

70 oC (158 oF)
1.00E-01 90 oC (194 oF)

130 oC (266 oF)

150 oC (302 oF)

1.00E-02
1.00E-02 1.00E-01 1.00E+00 1.00E+01 1.00E+02 1.00E+03
Shear Rate (s-1)

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 Screening salt: grows wormlike micelles

104
40 mM EHAC

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77oF
101 − + +
+
η0 (Pa.s)

− −
−
Micellar
100
surface

10-2
10 100 1000

NaCl Concentration (mM)

23 JG-Rideal-Apr2005 S.R. Raghavan and E.W. Kaler

4/7/2005
 4.5 wt% EHAC…no salt

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Spherical Micelles, R ~ 33A
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4/7/2005 Cryo-TEM by Vania Croce, University of Bristol
and Goran Karlsson, Uppsala University
 Add 2% KCl…peak viscosity

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Entangled Wormlike Micelles
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4/7/2005 Cryo-TEM by Vania Croce, University of Bristol
and Goran Karlsson, Uppsala University
 Approaching Maxwell behaviour…

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Data: Vania Croce, Univ of Bristol
4/7/2005
6% KCl …viscosity falling …branched micelles

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Branched Wormlike Micelles
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4/7/2005 Cryo-TEM by Vania Croce, University of Bristol
and Goran Karlsson, Uppsala University
 Approaching Maxwell behaviour…

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Data: Vania Croce, Univ of Bristol
4/7/2005
 Direct Determination of Esciss
1
10

ω min (rad/s)
G''/G'inf G”min/G’inf ~ le/<L>
~exp[-Esciss/2kT]

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0
10
Esciss = 28kT

-1
10
3.2 3.3 3.4 3.5
-1
1000/T (K )
Semi-log variation of G”min/G’inf (●) and ωm (o) as a function of 103/T for a
solution with an active EHAC concentration of 14.1 mM, and 400 mM KCl
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4/7/2005 Data: Isabelle Couillet
 Effect of Temperature

• As T ↑, micellar length L decreases

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heat
exponentially, L ~ exp{Esciss/2kT}
• Shorter micelles relax faster
(reptation time trep ~ L3)
heat
• Viscosity decreases exponentially

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 VES Shear Viscosity
3
10
2.5% Surfactant
25oC
5% KCl
2
10

38oC
Viscosity (Pa.s)
1
10
55oC

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o
100s-1
0 68 C
10

80oC
-1
10
90oC 50 cP
-2
10
-4 -3 -2 -1 0 1 2 3
10 10 10 10 10 10 10 10
Shear Rate (s-1)

z Zero-shear viscosity, η0 decreases as T ↑

z Relaxation time, tR (= 1/γc) decreases as T ↑
z Viscosity at high shear-rates is nearly independent of T
31 JG-Rideal-Apr2005
4/7/2005 S.R.Raghavan
S.R. Raghavanand
andE.W.
E.W.Kaler,
Kaler,Langmuir,
Langmuir,17,
17,300-306,
300-306,2001
2001
Effect of headgroup size and charge distribution
EHAC Erucate
+1

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-1

H H —
Cl
CH 2–CH 2–OH
C C
+
CH 3–(CH 2)7 (CH 2)11 –CH 2–N–CH 3

CH 2–CH 2–OH

Tlim ~ 85oC
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4/7/2005 Tlim ~ 110oC
 Alternative VES Structures
R - X - Y - X -

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Hydrophobic Spacer Spacer
Tail group group Charged group

Hydrophilic head group

z Tune headgroup and tail interactions to increase packing parameter,

P = Vs /la, and so stabilise wormlike phase to higher temperatures

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 Improving Temperature Performance
1000

RHEOLOGY
Viscosity (cP) @ 100 s-1

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100 SPECIFICATION
>50cP @ 100 s-1

10 System A
System B
System C
System D

1
25 50 75 100 125 150 175

Temperature (oC)
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 MD simulation of surfactant packing

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Erucate (ordered) EHAC (less ordered)
Same tail, different heads: different packing behaviour
35 JG-Rideal-Apr2005 Erucate EHAC
4/7/2005
0.93 〈Σi,jsi.sj〉/N2 0.62
 Mesoscopic model of wormlike micelles
z smallest units are pieces of worm of one persistence length

Vbond =
1 KL
(r − l p )2 Vangle =
1
k BTϑ 2
2 lp 2

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z breakup and fusion: scission energy Esc

z input needed from atomistic MD: persistence

length lp , elastic modulus KL and break-up energies
z can now simulate bulk rheology similar to that
observed experimentally; basis for molecular design
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 Conclusions
z The rheology of mineral-based complex fluids and soft
solids can be understood, and sometimes even predicted,

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using the basic principles of colloid rheology
z Understanding the mechanisms of micelle dynamics
enables Chemistry to cope with very hot showers
z MD + Coarse Grained simulations are on the verge of
enabling molecular engineering of fluids and soft solids

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 Schlumberger Public
Congratulations Jim
on your Rideal Lectureship!

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