5 - Theory of Scale Inhibitor Squeeze Treatments: Ken Sorbie

5 – Theory of Scale Inhibitor
Squeeze Treatments
Ken Sorbie
Shell, Houston, 10-12 December 2013

Plan of presentation
• Fundamentals of inhibitor adsorption
- static adsorption
- the adsorption isotherm, (C)
- sensitivities (pH, [Ca2+], T)
- kinetic adsorption
• Transport of scale inhibitor through porous media

- the transport equation
- equilibrium and kinetic adsorption
- the role of the adsorption isotherm
- modelling core floods
- other sensitivities in field core floods
- examples of reservoir condition core floods
Section 4: Slide 2 of 96
- static adsorption

Static Adsorption
Volume = V
Initial conc. (at t = 0) = co
Mass = m
UNITS:
c – mg/L
V – Litre (L)
m –g
 – mg/g
Static Adsorption
Volume = V
Final conc. (as t  ) = ceq

(ceq = the equilibrium conc.)
Mass = m
UNITS:
c – mg/L
V – Litre (L)
m –g
 – mg/g
Static Adsorption
Volume = V
Final conc. (as t  ) = ceq

(ceq = the equilibrium conc.)
Mass = m
Adsorption level,  (mg SI/g rock)
UNITS:
c – mg/L V (c0  ceq )
V – Litre (L) 
m –g
 – mg/g
m
The Adsorption Isotherm, (C)
Max. ads.
Inhibitor
Level
Adsorption max
Level

(mg/g)
Inhibitor Conc.
rock grains + INHIBITOR
Max. ads.
Inhibitor
Level
Adsorption max
Level

(mg/g)
Slope at threshold conc. ?
mg inhibitor d
g rock  dC
c1
Inhibitor Conc.
rock grains + ADSORBED inhibitor, (c)
Mobile phase inhibitor conc., c1 Section 4: Slide 8 of 96

How the equilibrium adsorption isotherm is reached…
Initially, c = c0; Mass of SI (conserved) = V.c0
Volume = V
c = c0
INITIALLY all the SI
= is in the aq. Phase
(c) and c = c0  = 
(mg/g)
Mass = m
c0
UNITS: SI conc., c 
c – mg/L
V – Litre (L)
m –g
 – mg/g
Initially, c = c0 (mg/L); Mass of SI (conserved) = V.c0 (mg)
IF ALL SI was adsorbed (c=0)
Volume = V 0 then , 0 = V.c0 /m (mg/g)
c=0
 = 0
(c)
(mg/g)
Mass = m
c0
c – mg/L
V – Litre (L)
m –g
 – mg/g
Volume = V 0
c = ?? THIS is the line of

equal mass (V.c0 );
 = 
(c) Its equation is ..
   0  V .c
(mg/g)
Mass = m
c0
c – mg/L
V – Litre (L)
m –g
 – mg/g
Volume = V 0
c = ceq eq THIS is the point

which satisfies both
 = eq
(c) the isotherm (c)
AND material balance
(mg/g)
Mass = m
ceq c0
c – mg/L
V – Litre (L)
m –g
 – mg/g
Volume = V 0
c = ceq eq THIS is the point

which satisfies both
 = eq
(c) the isotherm (c)
AND material balance
(mg/g)
Mass = m
ceq c0
SI conc., c 
THIS is the equilibrium adsorption level
-it is found numerically by solving the following equation for ceq
Mass in system  Vc0  m eq (ceq )  V .ceq Section 4: Slide 13 of 96
Adsorption Sensitivities
• LEVEL OF ADSORPTION MAY DEPEND ON

SEVERAL FACTORS
- scale inhibitor type (phosphonate, PPCA, PVS..)
- the brine composition [Ca2+] and pH ([H+] )
` - temperature
- mineral substrate type
e.g. quartz, kaolinite, chlorite …
- rock wettability
Examples …..
Effect of mineral substrate and pH on 
 mg/g
Kaolinite
Quartz
(Jordan et al, NACE, 1994)

Effect of mineral substrate and pH on 
 mg/g
Kaolinite
SI Adsorption on clay is approx.

8x >> than on quartz in mg/g but
surface area is 10x greater in m2/g
Quartz
(Jordan et al, NACE, 1994)

Effect of [Ca2+], pH and Temperature on phosphonate ads. on quartz
 mg/g pH 2, 428 ppm Ca
pH 2, no Ca pH 4, 428 ppm Ca
pH 4, no Ca
(Yuan et al, Adv. Oilfield Chem., 1994)

Effect of pH on phosphonate adsorption on crushed core; 95oC
 mg/g
(Jordan et al, NIF Geilo, Norway, 1994) Section 4: Slide 18 of 96

Effect of pH on – full static(C)phosphonate ads. on crushed core
(C) mg/g
(Yuan et al, Adv. Oilfield Chem., 1994) Section 4: Slide 19 of 96

Adsorption Sensitivities - summary
SEVERAL FACTORS
- the brine composition [Ca2+] and pH ([H+] )
` - temperature
- mineral substrate type
e.g. quartz, kaolinite, chlorite …
- rock wettability
THEREFORE, strictly for a given SI and mineral substrate

 (C) = (C, [Ca2+], [H+], T)
Adsorption Sensitivities - summary
SEVERAL FACTORS
- the brine composition [Ca2+] and pH ([H+] ) etc….
DETPMP adsorption (mg SI/g core)
DETPMP adsorption (mg SI/g core)

5000 ppm DETPMP 5000 ppm
SW (with/without Ca) DETPMP
pH 2, 4 and 6 SW (with Ca)
Calcium conc. (ppm)

T = 25oC pH 2, 4 and 6;
T=25oC
SI Ads. SI
(with Ca) Ads.
[Ca] stock 415ppm
SI Ads.
(No Ca) [Ca]
pH pH
Form of Adsorption Isotherms
Some empirical forms for the adsorption isotherm, (c):
Freundlich (c)   .c n
Langmuir  .c. max

 (c ) 
 1   .c 
For which we can define a fractional coverage, f or (c)
  eq (c)
f  (c ) 
(c)
 max
Langmuir
1.2
adsorption isotherm – fractional coverage
Langmuir isotherm..
1.0
 .c. max

Fractional Adsorption
  
0.8
 1   .c 
  0.6
Fractional
  max 
0.4 Keq = 15,900 M-1
C50 = 62.7  M
adsorption is..
 =0
   .c
  
0.2 2

capacity = 0.15  mol/m
0.0
 max  1   .c 
0.000001 0.00001 0.0001 0.001 0.01 0.1
Supernatant Concentration, M
Experimental data for DETPMP on kaolinite at pH 7 fits by the

Langmuir curve; from Funkhouser and Gdanski (NIF Geilo, Norway, 2001)
Langmuir adsorption isotherm – fractional coverage
1 Langmuir isotherm..
0.9
 .c. max
0.8

0.7
= 1.0
 1   .c 
Fraction coverage
   0.6
   = 0.1 Fractional
  max 
0.5
0.4
 = 0.01
adsorption is..
0.3
  .c
0.2 = 0.001   
0.1  max  1   .c 
0
0.1 1 10 100 1000 10000
SI concentration (ppm)
 ) vs. SI conc., c (ppm) for a Langmuir adsorption
Fractional coverage ( 
isotherm with  values 1.0, 0.1, 0.01 and 0.001. Note that  = 0.5 at c = 1/.
(Sorbie and Gdanski, SPE95088, 2005)

Langmuir adsorption isotherm – fractional coverage
1 Langmuir isotherm..
1
Note that  0.5
0.9
 at c 
.c. max
0.8
 
0.7
= 1.0
 1   .c 
Fraction coverage
   0.6
   = 0.1 Fractional
  max 
0.5
0.4
 = 0.01
adsorption is..
0.3
  .c
0.2 = 0.001   
0.1  max  1   .c 
0
0.1 1 10 100 1000 10000
 ) vs. SI conc., c (ppm) for a Langmuir adsorption
Fractional coverage ( 
isotherm with  values 1.0, 0.1, 0.01 and 0.001. Note that  = 0.5 at c = 1/.

- static adsorption

Adsorption Kinetics
Initial conc.
Volume = V co
[SI]
ceq
Time, t 
Mass = m
Adsorption level, 
(mg SI/g rock)
V (c0  ceq )

m Section 4: Slide 27 of 96
Adsorption Kinetics
Volume = V co
[SI]
ceq
Time, t 
Mass = m
 Equilibrium
adsorption
Adsorption level,  level
(mg SI/g rock)
  ceq 
V (c0  ceq )

m Time, t  Section 4: Slide 28 of 96
Adsorption Kinetics
Rate of phosphonate adsorption onto quartz
Phosphonate (I1) static adsorption onto quartz

6 (c0 = 5000 ppm active, no Ca, pH 2, 95oC); data
replotted from Jordan et al, SPE27389, 1994
SI ads.
 (mg/g)
4
5 10 15 20 25
(Jordan et al, SPE27389, 1994) Time, hours  Section 4: Slide 29 of 96
Adsorption Kinetics
Rate of phosphonate adsorption onto quartz
Phosphonate (I1) static adsorption onto quartz

6 (c0 = 5000 ppm active, no Ca, pH 2, 95oC); data
replotted from Jordan et al, SPE27389, 1994
SI ads.
 (mg/g)
4
Adsorption complete in
~3 – 5 hours
2
5 10 15 20 25
(Jordan et al, SPE27389, 1994) Time, hours  Section 4: Slide 30 of 96
Adsorption Kinetics
Kaolinite,no Ca, pH 2, 95oC
Kaolinite,no Ca, pH 2, 25oC
Quartz,no Ca, pH 2, 95oC
Phosphonate (I1) static adsorption onto quartz and kaolinite under various
conditions (c0 = 5000 ppm active); Jordan et al, SPE27389, 1994
Adsorption Kinetics
Showing how the equilibrium isotherm arises from the
form of the adsorption and desorption rate expressions …
FREUNDLICH
- Adsorption rate Ra  ka .c n
- Desorption rate Rd  kd .(c)
At Equilibrium => Ra = Rd
Adsorption Kinetics
FREUNDLICH
At Equilibrium =>
Ra  Rd => ka .c  kd (c)
n
Adsorption Kinetics
FREUNDLICH
At Equilibrium =>
Ra  Rd => ka .c  kd (c)
n
which rearranges to ( = constant)
(c)   .c n
   ka / kd 
Adsorption Kinetics
LANGMUIR Fractional coverage, f

- Adsorption rate Ra  ka .c(1  f ) 
f  (c ) 
 eq (c)
 max
- Desorption rate Rd  kd . f
At Equilibrium => At Equilibrium => Ra = Rd
Ra  Rd => ka .c(1  f )  kd . f
which rearranges to ( = constant)
 .c. max    ka / kd 

 1   .c  Section 4: Slide 35 of 96
Adsorption Kinetics
Empirical kinetic expressions used in literature

e.g.
Sorbie et al (SPE-PE, Aug. 1992) – HW model
  
      eq   
 t 
Gdanski and Funkhouser (NIF, Geilo, Norway, 2001)- GF model

(desorption only – adsorption instantaneous)
d 
   kd     eq  
2

 dt 
(Sorbie and Gdanski, SPE95088, 2005) Section 4: Slide 36 of 96
Adsorption Kinetics
Empirical kinetic expressions used in literature
HWmodel Approach to equilibrium (desorption)

C mobile vs. time for the HW and
GF models – initial rates matched.
  
      eq    0.14 Rate law – Eq. 14 =(0.03)
= 0.03)
 t 
S. rate equn. (kappa
0.12
Mobile phase conc. C
0.1
Series1
0.08
Series2
GF model G-F rate equn. (k =2)
0.06 Rate law – Eq. 17
15 (k = 2.0) Series3
d 
  kd    eq  
2 0.04

 dt  0.02
0
0 200 400 600 800 1000
Time,tT
Time, -->

- static adsorption

Transport of SI Through Porous Media
Schematic illustration of convection and dispersion
and the CD Equation (for an inert tracer)
agine an inert tracer
ing transported through
e porous medium:
Frontal spreading of
e tracer is DISPERSION
The velocity of the tracer

ont (CONVECTION) is:
 Q 
v 
 A.  The Convection-Dispersion (CD) Equation is
 c    2c   c 
The tracer concentration    D 2   v 
 t   x   x 
c ( x, t ) Dispersion Convection
Injection of a 1 PV TRACER slug through a core

 Q 
Frontal velocity v    ; Dimensionless conc. C = c/c 0
Q  A. 
brine + tracer
Conc. = c0
Effluent profile ….
brine + tracer
c/c0
1
brine + tracer
brine only
1 2
PV 
brine only
brine only In tail, (c/c0)  0 in < 1PV

Injection of a 1 PV SCALE INHIBITOR slug through a core

 Q 
Frontal velocity < v    ; Dimensionless conc. C = c/c 0
Q  A. 
brine + SI
Conc. = c0
Effluent profile ….
brine + SI
c/c0
1
brine + SI
SI
brine only
+ ADS. SI 1 2
PV 
brine only
+ ADS. SI
brine only
+ ADS. SI
In tail, (c/c0)  0 in < 1PV
Injection of a 1 PV SCALE INHIBITOR slug through a core

 Q 
Frontal velocity < v   profile
Effluent  ;of
Dimensionless
adsorbing SIconc. C = c/c
over long postflush
 A. 
0
Q
brine + SI 104
Conc. = c0 [SI] (ppm)
103
brine + SI NB
log scale 102 (100s – 100s PV)Long period in
PV of low [SI]
brine + SI 10
1
brine only
+ ADS. SI (100s – 100s PV)
PV injected 
brine only
+ ADS. SI
OVER MANY PVs
brine only
+ ADS. SI
Schematic of rig to perform SI core floods
Core oil reconditioned &

waterflooded to Sor
Oven (110oC)
Reservoir
Core
Pump
x
x BPR
Pressure Tappings
Brine Inhibitor
Solution
Example experimental SI return profiles over very long postflush period

up to 700 PV (reservoir core, T = 110oC; 3 phosphonate inhibitors)
10000
Flood T2, inhibitor I1

Flood T3, inhibitor I1a
Flood T4, inhibitor I1b
Inhibitor 1000
Conc.
(ppm)
100
10
0 100 200 300 400 500 600 700 800
Brine Postflush (PV) --> Section 4: Slide 44 of 96

Example experimental SI return profiles over very long postflush period

up to 700 PV (reservoir core, T = 110oC; 3 phosphonate inhibitors)
10000
X
Flood T3, inhibitor I1a
Inhibitor 1000
Conc. NOTES
1. Long tail due to SI-core interaction e.g. (c)
(ppm) 2. Many [SI] points measured in tail (100s)
3. There is a high [SI] spike at X
100
10
0 100 200 300 400 500 600 700 800
Brine Postflush (PV) --> Section

(Sorbie 4: Slide 451994)
et al, SPE28885, of 96
Theory – transport equation with Adsorption (or precipitation)

Q 10000
[SI] (ppm) Flood T2, inhibitor I1

brine only Flood T3, inhibitor I1a
+ ADS. SI 1000
brine only
+ ADS. SI
100
brine only
+ ADS. SI
10
0 100 200 300 400 500 600 700 800
PV 
CD Eq. With ADSORPTION/RETENTION

 c   2
c  c     
   D 2   v    
 t   x   x    t 
DISPERSION CONVECTION ADSORPTION
(kinetic)
Design- Unitsof SI M assSIper Formof therate
ation adsorption rockvolum e, VT terminEq. 1
3
[ref.] (cm) where c=>
 c    2c   c     
   D  2  v      (mg) g/Lm g/cm3
 t   x   x    t 
A mg SI AVT or*  
  A
[3] grock A 1 rgVT  t 
Sorbie et al (1992)
B mgSI BVT 
1 B 
 
Lofporespace 1000 t 
1000
C mg SI CVT  
 C 
[6] cm3 ofporespace  t 
Gdanski & Funkhouser (2001)
D mg SI DVT 1 D
Lof rock
  
1000 1000 t 
E mg SI E 1 VT 
(1)E 
[2]
Lof rockgrain 1000   
 t 
Hong & Shuler (1988)
*where =rockdensity(grainandporespace); rg =rockgrain

density; bothg/cm3 Section 4: Slide 47 of 96
Design- Unitsof SI M assSIper Formof therate
ation adsorption rockvolum e, VT terminEq. 1
3
[ref.] (cm) where c=>
 c    2c   c     
   D  2  v      (mg) g/Lm g/cm3
 t   x   x    t 
A mg SI AVT or*  
  A
[3] grock A 1 rgVT  t 
Alternative forms of the Sorbie et al (1992)
adsorption term depending B mgSI BVT 1 B 
  
on the units of adsorption Lofporespace 1000 1000 t 
in the porous medium
C mg SI CVT  
 C 
[6] cm3 ofporespace  t 
Gdanski & Funkhouser (2001)
D mg SI DVT 1 D
Lof rock
  
1000 1000 t 
E mg SI E 1 VT 
(1)E 
[2]
Lof rockgrain 1000   
 t 
Hong & Shuler (1988)
*where =rockdensity(grainandporespace); rg =rockgrain

density; bothg/cm3 Section 4: Slide 48 of 96
- static adsorption

Theory – transport equation AT EQUILIBRIUM ADS.
         c  (chain rule)
At equilibrium …        
  t    c   t 
Substituting this expression into the transport equation ….
         c  (chain rule)
At equilibrium …        
  t    c   t 

 c   2
c  c     
   D 2   v    
 t   x   x    t 
         c  (chain rule)
At equilibrium …        
  t    c   t 

 c   2
c  c     
   D 2   v    
 t   x   x    t 
To obtain …
 c    2c   c       c  REARRANGE …
   D 2   v     
 t   x   x    c   t 

… 1       c    2
c   c 
    D 2   v 
Rearrange to obtain

   c    t   x   x 
Which – ignoring dispersion (D = 0) gives …
 c  v  c   c 
       vc  
 t         x   x 
1   c  
  

… 1       c    2
c   c 
    D 2   v 
Rearrange to obtain

   c    t   x   x 
Which – ignoring dispersion (D = 0) gives …
 c  v  c   c 
       vc  
 t         x   x 
1   c  
  
Velocity of concentration
level c
This equation gives a “retarded velocity” for the SI depending on the

slope of the adsorption isotherm
 c  v  c   c 
       vc  
 t         x   x 
1   c  
  
brine only
LOW conc., c1
+ ADS. SI
  
 
 c c c1
c(x, t1)

v1
c1
c Section 4: Slide 55 of 96

slope of the adsorption isotherm
 c  v  c   c 
       vc  
 t         x   x 
1   c  
  
brine only
HIGHER conc., c2
+ ADS. SI
     
   
 c c c1  c c c2 v2
c(x, t1)
 c2
v1
c1
c c x Section 4: Slide 56 of 96

slope of the adsorption isotherm Because..
 c  v  c    c    
       v c    
 t         x   c cxc1   c c c2
1   c  
   v1 < v2
brine only this profile SPREADS

HIGHER conc., c2
     
+ ADS. SI with time
   
 c c c1  c c c2 v2
c(x, t1)
 c2
v1
c1
c c x Section 4: Slide 57 of 96
Implications in a RADIAL system
WHAT DO THESE RESULTS MEAN IN A RADIAL NEAR-WELL

SYSTEM ?
Implications in a RADIAL system.
Producer Well shut in after SI inj.
X Location of SI slug
after overflush
- to allow adsorption
- 3 hrs. - 24hrs.
Inhibitor Slug after Overflush

1
C
Co
Radial
distance
from wellbore Radial Distance

Inhibitor Slug after Overflush The Adsorption Isotherm
 hi
1
C 
Co
( d )
ct dC ct
Ct
Radial Distance C
Vfluid
VCt =
[ 1 +/C)]

HIGH SI conc.
 hi moves fast
1
- low (d/dC)
C 
Co
( d )
ct dC ct
Ct
Radial Distance C
Vfluid
VCt =
[ 1 +/C)]

LOW SI conc.
 hi moves slow
1
- high (d/dC)
C 
Co
( d )
ct dC ct
Ct
Radial Distance C
Vfluid
VCt =
[ 1 +/C)]

Inhibitor Slug after
Producer  hi
- back on production Overflush
1
C HIGH CONC.
Co FAST RETURN
ct
Radial Distance
104 “spike”
SI Conc.
in produced 103
brine
[SI] (ppm) 102
10
1
Time or Cumulative water production

Producer
1
C MEDIUM CONC.
med
Co SLOWER RETURN
 ct
Radial Distance
104
SI Conc.
in produced 103
brine
[SI] (ppm) 102
10
1

Producer
1
C LOW CONC.
Co
V. SLOW RETURN
 ct
Radial Distance
104
SI Conc.
in produced 103
brine
[SI] (ppm) 102
10
1
- static adsorption

Modelling of SI Core Floods
Can match core flood SI effluents to obtain the dynamic adsorption isotherm
Experiment: Derive
Core Flood Inhibitor Adsorption
Effluent Profile Adsorption
Isothermisotherm
(C)
C SQUEEZE (C)
Modelling
Time (PV) C
(Method in => Sorbie et al, SPE-PE, Aug. 1992) Section 4: Slide 67 of 96

Core flood return curves of [SI] vs. PV

10000
Corresponding dynamic adsorption isotherms
[SI]
Flood T3, inhibitor I1a (c) (mg/g) vs. c (ppm)
Flood T4, inhibitor I1b 3.0
1000
(c)
2.5
100
2.0
1.5
10
0 100 200 300 400 500 600 700 800 1.0
Brine Postflush (PV) --> Flood T3, inhibitor I1a
0.5 Flood T4, inhibitor I1b
0.0
0 100 200 300 400 500 600 700 800 900 1000
(Method in => Sorbie et al, SPE-PE, Aug. 1992)

Section 4:(ppm)
Inhibitor Concentration Slide 68
 of 96
Modelling flood C3
Points + – data Dynamic adsorption isotherms
Solid line - model (c) (mg/L)* vs. c (ppm)
8000
(c)
7000
6000 Flood C3
Adsorption (mg/L)
Flood C4
5000
Flood C7
4000 Flood C10
Flood C11
3000
Flood C13
2000
Modelling flood C4 1000
Points + – data 0
Solid line - model 0 1000 2000 3000 4000 5000
*Note UNITS of  mg/L – see table for

conversion to mg/g
Examples isotherms from SI core floods in reservoir cores - see below

4
Adsorption,  (C) (mg inhibitor/g rock)
NOTE – all show the characteristic steeply rising behaviour in

the low conc. region
(c)
0
0 100 200 300 400 500
Active Inhibitor concentratiuon (ppm) Section 4: Slide 70 of 96
Examples of SI Core Floods in Reservoir Core
5 practical examples of field SI core floods
Example 1: A comparison of 2 generically different scale inhibitors in

core floods in field core (Jordan et al, SPE27607, 1994)
Example 1: Examples of comparative core floods in field core
I1 and I3 are 2 generically

different SI types
I1
I3
(Jordan et al, SPE27607, 1994) Section 4: Slide 72 of 96

I1 and I3 are 2 generically Note

different SI types 1. Very clear differences between I1
and I3.
2. I1 shows some variation from core
to core
(about 6 months work on this slide!)
I1
I3
(Jordan et al, SPE27607, 1994)


Example 2: A comparison of a hexaphosphonate (adsorption) and

a sulphonated acrylate (pptn.) (Jordan et al, SPE31125, 1996)
Note: longer return time to

2ppm but depends on the
required MIC values
Hexa phosphonate
(adsorption)
Sulphonated acrylate
(precipitation)



Example 3: A comparison of DETPMP (ads. & pptn) and PPCA (pptn.) in

Etive field core (Jordan et al, SPE31125, 1996)
Example 3: Core floods comparing DETPMP (ads. & pptn) and PPCA (pptn.) in field core
DETPMP – pptn.
DETPMP – ads.
PPCA – pptn.



Example 4: Comparison of Hexa-phosphonate and Penta-phosphonates

Return profiles in field core (Jordan et al, SPE31125, 1996)
Note: quite different profiles

for penta- and hexa-
Penta phosphonate phosphonates – need (c) to
(adsorption) assesss in field (see below)
Hexa phosphonate
(adsorption)

Example 4: Isotherms for the Penta- and Hexa-phosphonates
F3: Penta phosphonate

(adsorption)
?? F10: Hexa phosphonate

(adsorption)

Low concentration
region
F3: Penta phosphonate
F4
(adsorption)
F10: Hexa phosphonate

(adsorption)

Conclusions on Penta-/Hexa- Phosphonates
- as seen from return curve

=> Hexa-P gives a long LOW conc. tail ([SI] ~1 - 2 ppm)
=> Penta-P gives higher intermediate conc.
- requirement depends on MIC (the scaling problem)
- to assess field performance use the derived

adsorption
isotherm (see below)
 Use different products for different types

of scaling problem Section 4: Slide 82 of 96



Example 4: Comparison of Hexa-phosphonate and Penta-phosphonates

Return profiles in field core (Jordan et al, SPE31125, 1996)
Example 5: Does the core flood return curve (PV postflush to MIC)
correlate with the static adsorption level ? (Jordan et al, 1994, 1995)
correlate with the static adsorption level ?
Static scale inhibitor adsorption on crushed core (mg/g)
All 6 cases are penta phosphonates
Pore volumes of postflush to threshold [SI] in consolidated cores

Static scale inhibitor adsorption on
crushed core (mg/g)
(Jordan et al, NIF Geilo, Norway, 1994) Section 4: Slide 85 of 96

Static scale inhibitor adsorption on
crushed core (mg/g)

Practically, there is reasonable agreement between the
no. PV to threshold level in a core and the static SI
adsorption on the coresponding (Jordan crushed core
et al, NIF Geilo, Norway, 1994)
Applying the Adsorption Isotherm in the Field
To Design SI Squeeze Treatments
How do we use this information in designing field

scale inhibitor squeeze treatments??
• How do we assess the isotherm in the field ?

Field Squeeze
Laboratory (C) Predictions
C Sensitivities
(C) SQUEEZE
Modelling
Time
C
Section
SENSITIVITIES => inhibitor conc., slug size, overflush volume, 4: Slide 88 of 96
etc.....
Calculating Sensitivities to various factors to optimise squeeze treatment
Scale 104 sensitivities

Inhibitor 0.5 - 2 years
Conc. in 103
Produced Base Case
Brine 102
[SI]
100
MIC
1
SENSITIVITIES => inhibitor conc., slug size, overflush volume, etc....
DISCUSSED IN DETAIL LATER IN THIS COURSE ….. Section 4: Slide 89 of 96

Other Processes – Further Complications
-“Precipitation” or “Phase separation” squeeze treatments

(Malandrino et al, SPE29001, 1995)
- Coupled adsorption depending on several factors

i.e. (C) = (C, [Ca2+], [H+], T)
(Sorbie et al, SPE25165, 1993)
- Rate/non-equilibrium effects
i.e. d(C)/dt = various rate laws
(Zhang et al, SPE64744, 2000; Sorbie and Gdanski, 2005)
Review of models for adsorption and precipitation squeeze treatments
Results for Precipitation Squeeze Treatments
Modelling of precipitation core floods using models of varying complexity
from Malandrino et al, SPE29001, 1995

-“Precipitation” or “Phase separation” squeeze treatments

- Coupled adsorption depending on several factors

i.e. (C) = (C, [Ca2+], [H+], T)
(Sorbie et al, SPE25165, 1993)
- Rate/non-equilibrium effects
i.e. d(C)/dt = various rate laws
(Zhang et al, SPE64744, 2000; Sorbie and Gdanski, 2005)
Coupled adsorption depending on several factors
i.e. (C) = (C, [Ca2+], [H+], T)
Inhibitor adsorption
as a function of
pH ([H+]) and [SI]
(Sorbie et al, SPE25165, 1993) Section 4: Slide 94 of 96

Closing Remarks - Summary
- static adsorption

Points to Note
• Adsorption isotherm, (c), is very important
• Adsorption depends on several factors and

strictly, (C) = (C, [Ca2+], [H+], T)
• The SI transport equation (convection/disperson/

adsorption) is important => importance of (d/dc)
• Equilibrium (c) important - kinetic effects play role
• Core flood experiments - [SI] return profiles => (c)
• Can translate (c)  field squeeze treatment (later)
• Additional “complications” – pptn. sqz, coupled ads. ...


5 - Theory of Scale Inhibitor Squeeze Treatments: Ken Sorbie

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5 - Theory of Scale Inhibitor Squeeze Treatments: Ken Sorbie

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5 – Theory of Scale Inhibitor

Shell, Houston, 10-12 December 2013

• Transport of scale inhibitor through porous media

• Transport of scale inhibitor through porous media

Final conc. (as t  ) = ceq

Final conc. (as t  ) = ceq

rock grains + INHIBITOR

rock grains + ADSORBED inhibitor, (c)

Mobile phase inhibitor conc., c1 Section 4: Slide 8 of 96

c = ?? THIS is the line of

c = ceq eq THIS is the point

c = ceq eq THIS is the point

• LEVEL OF ADSORPTION MAY DEPEND ON

(Jordan et al, NACE, 1994)

SI Adsorption on clay is approx.

(Jordan et al, NACE, 1994)

 mg/g pH 2, 428 ppm Ca

(Yuan et al, Adv. Oilfield Chem., 1994)

(Jordan et al, NIF Geilo, Norway, 1994) Section 4: Slide 18 of 96

(Yuan et al, Adv. Oilfield Chem., 1994) Section 4: Slide 19 of 96

THEREFORE, strictly for a given SI and mineral substrate

DETPMP adsorption (mg SI/g core)

Calcium conc. (ppm)

[Ca] stock 415ppm

Some empirical forms for the adsorption isotherm, (c):

Langmuir  .c. max

Experimental data for DETPMP on kaolinite at pH 7 fits by the

(Sorbie and Gdanski, SPE95088, 2005)

(Sorbie and Gdanski, SPE95088, 2005)

• Transport of scale inhibitor through porous media

Phosphonate (I1) static adsorption onto quartz

Phosphonate (I1) static adsorption onto quartz

Kaolinite,no Ca, pH 2, 25oC

Quartz,no Ca, pH 2, 95oC

which rearranges to ( = constant)

LANGMUIR Fractional coverage, f

Empirical kinetic expressions used in literature

Gdanski and Funkhouser (NIF, Geilo, Norway, 2001)- GF model

HWmodel Approach to equilibrium (desorption)

(Sorbie and Gdanski, SPE95088, 2005)

• Transport of scale inhibitor through porous media

The velocity of the tracer

Injection of a 1 PV TRACER slug through a core

brine only In tail, (c/c0)  0 in < 1PV

Injection of a 1 PV SCALE INHIBITOR slug through a core

Injection of a 1 PV SCALE INHIBITOR slug through a core

Schematic of rig to perform SI core floods

Core oil reconditioned &

Example experimental SI return profiles over very long postflush period

Flood T2, inhibitor I1

Brine Postflush (PV) --> Section 4: Slide 44 of 96

Example experimental SI return profiles over very long postflush period

Brine Postflush (PV) --> Section

Theory – transport equation with Adsorption (or precipitation)

[SI] (ppm) Flood T2, inhibitor I1

CD Eq. With ADSORPTION/RETENTION

*where =rockdensity(grainandporespace); rg =rockgrain

*where =rockdensity(grainandporespace); rg =rockgrain

• Transport of scale inhibitor through porous media

Theory – transport equation AT EQUILIBRIUM ADS.

Substituting this expression into the transport equation ….

Theory – transport equation AT EQUILIBRIUM ADS.

Substituting this expression into the transport equation ….