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Abstract
Polymers used in completion and workover operations can
consist of cellulose, cellulose derivatives, guar and guar
derivatives. Normally these polymers are used in completion
and workover fluids consisting of potassium, sodium and
ammonium chloride. As more wells are being completed in
deeper and hotter environments, fluids composed of calcium
chloride, calcium bromide, zinc bromide and combinations of
all three are being used to control well pressures.
Studies were conducted on hydration rates in various
brines for these polymers and are presented in graphical form.
A correlation was also established to predict the hydration
rates and the ultimate viscosity for hydroxyethylcellulose at
temperature based on brine viscosity. These correlations are
particularly useful for field operations during cold
weather months.
Introduction
Water-soluble polymers are extensively used in oil and gas
operations. In high ionic completion fluids, many of these
polymers do not dissolve or require long mixing times to
dissolve and thicken the fluid. Darlington, et al, showed that
dry hydroxyethylcellulose (HEC) added to a 13.0 ppg calcium
chloride/calcium bromide solution had no increase in viscosity
at 511 sec-1 from initial to four hours.1 Scheuerman
determined hydration rates for HEC in completion fluids at
various temperatures and densities and showed a relationship
with time to maximum viscosity with brine density. Basically,
the greater the brine density and the lower the temperature the
greater the hydration time. Since completion fluids can be
prepared with various crystallization temperatures and brine
viscosities having the same density, Scheuermans relationship
can only be used as a rough guide.
SPE 86505
Calibrate
equipment
using
100
centiPoise
calibration oil.
Add completion fluid to be evaluated to
viscometer cup.
Set viscometer to 300 rpm.
Set test temperature.
Allow fluid to stir for 10 minutes to establish
thermal uniformity.
Add liquid polymer to cup.
Begin recording viscosity at one minute intervals
under a constant shear of 511 sec-1.
Maximum time of test was three hours or a viscosity
change of less than 5% in a thirty minute interval.
SPE 86505
= 89.362Ln(brine) + 173.2....(1)
= ultimate viscosity of gelled system in centiPoise at
511 sec-1
brine = the viscosity of the brine at temperature, F
Note that Eq. 1 is independent of temperature, brine type
and composition. All that is needed is the brine viscosity at
temperature and the viscosity for 80 pptg HEC at 511 sec-1 can
be obtained at that temperature. All brine viscosities were
obtained from references 8 through 10. Since the correlation
was established at temperatures of 80 and 120F, care must
be used at temperatures outside this range. On-going work is
being performed for HEC at other concentrations and other
temperatures to extend the range. Correlations for CMHEC as
well as guar are also being developed.
Similar correlations were attempted for the consistency
index and flow behavior index as a function of brine viscosity.
Such a correlation would be useful since viscosities at other
shear rates could be obtained. Although, a similar trend was
observed, more error resulted. The belief is that additional
error is introduced when extrapolating to obtain these power
law parameters as opposed to measuring the viscosity at
constant shear rate.
By knowing the ultimate viscosity, a relationship with
hydration rates can be established. Figure 14 show the percent
hydration at 30 minutes with respect to brine viscosity. Note
that the hydration rate is basically unaffected when the brine
viscosity is less than about 3 centiPoise providing greater than
80% of the ultimate viscosity. Above 3 centiPoise the
hydration rate is reduced and follows the correlation described
by the Eq. 2.
%Ultimate = 88.935(brine)-0.0671..(2)
Where the %Ultimate is the percent viscosity at 30 minutes
based on the ultimate viscosity obtained from the hot rolling
tests. Note that the brine viscosity at temperature is all that is
needed to predict the percent ultimate viscosity. Since the
brine viscosity decreases with increasing temperature, heating
the brine will increase the hydration rate and thus the percent
ultimate viscosity.
To further investigate the effects of the completion fluid on
polymer dispersion and hydration each fluid was separated
into weight percentages of individual ions. The breakdown of
each fluid is shown in Table 7. From this analysis it can be
seen that the maximum viscosity of HEC hydrated in a monovalent fluid is not effected by the salt concentration but the
rate of hydration is. The maximum viscosities of the HEC
dispersed and hydrated in 9.0 and 10.0 ppg sodium chloride
were almost identical, 170 and 169 centiPoise, respectively.
However, thirty additional minutes were required to reach this
viscosity for the polymer hydrated in the 10.0 ppg fluid.
Results in which the polymer was hydrated in a divalent
cationic single salt fluid (CaCl2 or CaBr2) were different. It
was found that as the amount of calcium in the fluid increased,
SPE 86505
Acknowledgments
The authors wish to thank the management of BJ Services
Company for their support and permission to publish
this work.
Nomenclature
B1
cP
F1
mls
R1
rpm
n
K
ppm
mg/l
cP
pptg
= Viscometer Bob
= centiPoise
= Viscometer Spring
= milliliters
= Viscometer Rotor
= Rotations per Minute
=lb(f)/(ft2)(sec)
= lb(f)secn/ ft2
= parts per million
= milligrams/liter
= viscosity, centipoise
= centiPoise
= pounds per thousand gallons
E+00=C
E+00=Pa*s
E-01=kg
E-03=m3
References
1.
8. Kestin J., Khalifa, H. E., Ro, S. T., and Wakeham, W., A.,
"Preliminary Data on the Pressure Effect on the Viscosity
of Sodium Chloride-Water Solutions in the Range 10
40C, J. of Chemical and Engineering Data, Vol. 22,
No. 2 (1977) 207.
9. Ershaghi, I., Abdassah, D., Bonakdar, M., R., and Ahmad,
S., "Estimation of Geothermal Brine Viscosity," Journal
of Petroleum Technology (March 1983) 621.
10. Ortego, A. M., and Vollmer, D. P., Viscosities for Completion
Fluids at Temperature and Density, paper SPE 86506 presented
at the 2004 Formation Damage Control Symposium and
Exposition, Lafayette, Feb. 18-20.
11. Davidson., R. L.: Handbook of Water-Soluble Gums and Resins,
McGraw-Hill Book Company, New York (1980) 6.
SPE 86505
400
350
300
250
200
150
100
50
0
0
20
40
60
80
100
120
Time (min)
Fresh Water
Figure 1. 80 pptg HEC Hydration Rate (80F / Fluid Density < 12.0 ppg)
Fluid
Fresh Water
9.0 ppg NaCl
9.0 ppg KCl
9.5 ppg KCl
10.0 ppg NaCl
10.0 ppg CaCl2
11.0 ppg CaCl2
11.7 ppg CaCl2
13.5 ppg CaBr2
14.2 ppg CaCl2/CaBr2
(standard blend)
14.2 ppg CaBr2 (pure)
16.5 CaBr2/ZnBr2
KCl
ppm
Na
ppm
Ca
ppm
Zn
ppm
42,200
Br
ppm
TCT
F
Viscosity (cps)
80F / 120F
21
20
47
23
1
1.03 / 0.682
1.11 / 0.74
1.26 / 0.86
1.65 / 1.07
2.13 / 1.43
383,100
59
-37
8.32 / 4.95
4.17 / 2.51
267,100
414,800
491,000
59
0
-36
26.65 / 15.38
6.00 / 3.60
8.63 / 5.35
65,000
59,400
99,200
155,900
136,700
206,000
242,100
65,500
109,400
101,000
77,300
116,500
136,800
96,100
149,600
104,000
72,800
Cl
ppm
146,300
82,000
SPE 86505
200
180
160
140
120
100
80
60
40
20
0
0
20
40
60
80
100
120
140
160
180
200
Tim e (m in)
13.5 ppg C aB r2
14.2 ppg C aB r2
16.5 C aB r2/ZnB r2
Figure 2. 80 pptg HEC Hydration Rate (80F / Fluid Density > 12.0 ppg)
300
250
200
150
100
50
0
0
50
100
150
200
250
T im e (m in )
F re s h W a te r
9 .0 p p g N a C l
1 0 .0 p p g N a C l
1 1 .0 p p g C a C l2
1 1 .7 p p g C a C l2
Figure 3. 80 pptg HEC Hydration Rate (120F / Fluid Density <12.0 ppg )
300
SPE 86505
350
300
200
150
100
50
0
0
50
100
150
200
250
300
T im e ( m in )
1 3 .5 p p g C a B r2
1 4 . 2 p p g S ta n d a r d B l e n d C a C l 2 /C a B r 2
1 4 .2 p p g C a B r2
1 6 . 5 p p g C a B r 2 /Z n B r 2
Figure 4. 80 pptg HEC Hydration Rate (120F / Fluid Density > 12.0 ppg)
250
250
200
150
100
50
0
0
20
40
60
80
100
120
140
160
180
200
Time (min)
Fresh Water
Figure 5. 80 pptg CMHEC Hydration Rate (80F / Fluid Density < 12.0 ppg)
SPE 86505
250
200
150
100
50
0
0
50
100
150
200
250
T i m e (m i n )
1 3 . 5 p p g C a B r2
1 4 . 2 p p g S t a n d a rd B le n d C a C l2 / C a B r2
1 4 . 2 p p g C a B r2
1 6 . 5 p p g C a B r2 / Zn B r2
Figure 6. 80 pptg CMHEC Hydration Rate (80F / Fluid Density > 12.0 ppg)
250
200
150
100
50
0
0
50
100
150
200
250
300
Time (min)
Fresh Water
Figure 7. 80 pptg CMHEC Hydration Rate (120F / Fluid Density < 12.0 ppg)
SPE 86505
250
150
100
50
0
0
50
100
150
200
250
300
T im e (m in )
1 3 .5 p p g C a B r2
1 4 .2 p p g S ta n d a rd B le n d C a C l2 /C a B r2
1 4 .2 p p g C a B r2
1 6 .5 p p g C a B r2 /Z n B r2
Figure 8. 80 pptg CMHEC Hydration Rate (120F / Fluid Density > 12.0 ppg)
160
140
120
Viscosity (cps) @ 511 sec-1
200
100
80
60
40
20
0
0
10
20
30
40
50
60
70
80
90
100
Time (min)
Fresh Water
Figure 9. 80 pptg Guar Hydration Rate (80F / Fluid Density < 12.0 ppg)
10
SPE 86505
30
25
20
15
10
0
0
10
20
30
40
50
60
70
80
T i m e (m i n )
1 3 . 5 p p g C a B r2
1 4 . 2 p p g S t a n d a rd B le n d C a C l2 / C a B r2
1 4 . 2 C a B r2
1 6 . 5 p p g C a B r2 / Z n B r2
Figure 10. 80 pptg Guar Hydration Rate (80F / Fluid Density > 12.0 ppg)
160
140
120
100
80
60
40
20
0
0
20
40
60
80
100
120
140
160
180
200
Time (min)
Fresh Water
Figure 11. 80 pptg Guar Hydration Rate (120F / Fluid Density <12.0 ppg)
SPE 86505
11
14
12
10
0
0
10
20
30
40
50
60
70
T im e (m in )
1 4 .2 p p g C a B r2
1 4 . 2 p p g S ta n d a r d B le n d C a C l2 / C a B r 2
1 3 .5 p p g C a B r2
Figure 12. 80 pptg Guar Hydration Rate (120F / Base Fluid Density > 12.0 ppg)
28
14
124
67
180
150
123
189
<1
47
90
67
<1
42
2
137
59
180
30
108
<1
<1
28
15
Base Fluid
Fresh Water
9.0 ppg NaCl
9.0 ppg KCl
9.5 ppg KCl
10.0 ppg NaCl
10.0 ppg CaCl2
11.7 ppg CaCl2
13.5 ppg CaBr2
14.2 ppg
CaCl2/CaBr2
14.2 ppg CaBr2
16.5 ppg
CaBr2/ZnBr2
<1
<1
<1
<1
2
1
27
7
<1
<1
<1
10
12
SPE 86505
8 0 p p tg H E C
500
450
400
350
300
250
y = 8 9 .3 6 2 L n (x ) + 1 7 3 .1 9
R 2 = 0 .9 7 7 8
200
150
100
50
0
0
10
15
20
25
30
B r in e V is c o s it y , c p .
8 0 p p tg H E C
1 0 0 .0
9 0 .0
y = 8 8 .9 3 5 e -0 .0 6 7 1 x
R 2 = 0 .8 8 4 7
% Ultimate at 30 min.
8 0 .0
7 0 .0
6 0 .0
5 0 .0
4 0 .0
3 0 .0
2 0 .0
1 0 .0
0 .0
0
10
15
20
B r in e V is c o s ity , c p .
25
30
SPE 86505
13
K
(lb(f)secn/ft2)
Apparent Viscosity
@ 511 sec-1
0.294
0.308
180 cps
0.287
0.405
228 cps
0.273
0.731
375 cps
0.320
0.401
277 cps
0.265
0.733
358 cps
0.291
0.861
497 cps
0.334
0.436
327 cps
n 7. Weight Percent K
Table
(lb(f)secn/ft2)
Apparent Viscosity
@ 511 sec-1
0.318
0.210
143 cps
0.321
0.260
180 cps
0.256
0.678
314 cps
0.394
0.204
223 cps
0.296
0.511
303 cps
0.280
0.769
412 cps
0.368
0.294
273 cps
14
SPE 86505
Completion
Fluid
Total Salt
Weight %
Na
Weight %
Ca
Weight %
Zn
Weight %
Cl
Weight %
Br
Weight %
Water
Weight %
Maximum
Viscosity
(cp)
Time to
maximum
Viscosity
(min)
9.0 ppg
NaCl
10.0 ppg
NaCl
10.74
25.69
4.22
10.10
14.2 ppg
CaBr2
14.2 ppg
CaCl2
/CaBr2
16.5 ppg
CaBr2 /
ZnBr2
21.39
37.89
47.92
51.88
56.30
64.58
7.73
13.68
9.51
10.40
14.96
7.28
8.20
6.50
15.59
13.67
24.21
14.63
38.31
41.48
26.71
49.1
89.26
74.31
78.61
62.11
52.08
48.12
43.70
35.42
170
169
85
353
147
189
123
67
91
67
96
80
95
150
180
90