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Reprint R-1014
ABSTRAST
Produced water and brackish well water are the main
boiler feedwater sources for the steam assisted gravity
drainage oil recovery process. Contaminants in these
two water sources differ. Water separated from the
produced oil emulsion (produced water) is high in
silica and in soluble organic compounds. Brackish
well water can be high in hardness ions (calcium and
magnesium). The combination of these waters can be
unstable and can produce a variety of mineral scales.
The primary location of scaling is dependent on the
process scheme employed. For systems with extensive
pretreatment, deposition is most likely in preheaters
and evaporators. For other systems, deposition can
occur in the steam generation equipment. In addition
to mineral scales, carbon deposition can occur in
steam generation equipment. Analytical data on the
water sources is discussed, along with the composition
of deposits from preheaters, evaporators and steam
generation equipment. This can provide some insight
into the processes of formation and strategies for inhibition of those deposits. Strategies for inhibiting scale
formation are discussed.
Drum
Parameter
OTSG
Boiler
Hardness
(mg/l as CaCO3)
0.2 0.2
*
Conductivity (S/cm)
2,000 10,000 150
Silica (mg/l as SiO2)
20 50
2
Non-volatile TOC (mg/l C)
200 600
0.2
INTRODUCTION
Steam assisted gravity drainage (SAGD) facilities
inject steam into geologic formations to facilitate the
production of heavy hydrocarbon. Northern Alberta
(Canada) is one area where this process has been extensively deployed to produce bitumen (the term used
to describe the heavy hydrocarbon from this region).
This process uses pairs of horizontal wells the upper
well is used to inject steam and the lower well is used
to extract a complex emulsion of bitumen in water.
Cyclic steam stimulation (CSS) is a similar process
using only a single well. Periods of production alternate with periods of steam injection. This process
also produces an oil-water emulsion.
Environmental considerations limited make-up
water availability and lack of discharge options
Presented at the International Water Conference in San Antonio, Texas, October 24-28, 2010.
Component
Ca (mg/l)
Mg (mg/l)
K (mg/l)
Na (mg/l)
SiO2 (mg/l)
TOC (mg/l)
NH3 (mg/l)
Cl (mg/l)
pH (s.u.)
M alkalinity
(mg/l as CaCO3)
The OTSG option typically includes warm lime softening (WLS) for partial removal of silica and hardness.
WLS is typically followed by filtration to reduce
suspended solids and ion exchange using weak acid
cation exchange (WAC) resins for additional hardness
removal. In some cases, hot lime softening is used
in place of WLS. Figure 1 shows the WLS process
scheme.
A second option is to use conventional drum boilers.
As compared to OTSGs, these boilers require lower
contaminant concentrations in the boiler feed water.
The WLS WAC approach cannot meet the requirements, specifically for conductivity (total dissolved
solids, TDS) and non-volatile TOC. Wastewater
evaporators are typically used for pretreatment. The
condensate produced from these evaporators typically
meets the water quality requirements for drum boilers.
Figure 2 illustrates this scheme.
Minimum
1
1.6
14
130
11
170
11
48
7.3
Maximum
52
14
240
3000
260
430
64
4800
8.8
140
1400
WATER QUALITY
Table 2 illustrates the wide variation in the concentration of selected contaminants in produced water.
Examination of these data suggests that the produced
water from some facilities may be close to saturation
with respect to several species, particularly silica and
calcium carbonate. In fact, some of these samples seem
over-saturated with calcium carbonate. For example,
the concentration of carbonate in equilibrium with
52 mg/l calcium at 100C is ~10 mg/l (M alkalinity
expressed as CaCO3 equivalents).
Table 3 shows similar data for well water. As compared to produced water, well water is typically much
lower in silica and TOC. Calcium concentrations cover
roughly the same range, but trend toward the higher
end of the range.
TREATMENT TARGETS
WLS-OTSG OPTION WLS removes hardness by
precipitation of calcium carbonate, dolomite (calcium
magnesium carbonate), and magnesium hydroxide.
Typically, lime is added to raise pH and promote
precipitation of the carbonate species.
Anything that would reduce the solubility of key species could lead to precipitation or scale formation. For
example increasing pH, increasing temperature, or
any concentrating process (evaporation or boiling) will
magnesium). These systems typically produce effluent meeting the hardness target for OTSG feed water.
The WAC step has no effect on soluble silica.
Component
Ca (mg/l)
Mg (mg/l)
K (mg/l)
Na (mg/l)
SiO2 (mg/l)
TOC (mg/l)
NH3 (mg/l)
Cl (mg/l)
M (mg/l as CaCO3)
Minimum
2.0
1.5
2.2
700
8
nd
nm
480
880
Maximum
45
32
250
3700
10
5
nm
5300
1200
EVAPORATOR-DRUM BOILER OPTION Evaporators are capable of routinely meeting the feedwater
quality requirements for a drum-type boiler. These
units produce a condensate essentially free of dissolved solids. A purge stream removes contaminants
from the system. The purge is typically 2-5% of the
incoming flow; these systems operate at concentration ratios (feed flow rate / purge flow rate) of 20-40.
At such high concentration ratios, the contaminants
can become insoluble. Typically, caustic soda (NaOH
solution) is added to raise the pH and increase silica
solubility. This has the undesirable effect of decreasing the solubility of calcium carbonate and of several
metal silicates.
nd = not detected
nm = not measured
Generally the overflow from the WLS is near equilibrium with respect to calcium carbonate. Thus, the
residual soluble calcium carbonate concentration
depends on the carbonate concentration (as well as
on the temperature and ionic strength). For systems
deficient in carbonate, soda ash is added as a source
of carbonate. For any system, increasing the carbonate concentration decreases the soluble calcium
concentration.
Some evaporator systems use two evaporators operated in series. The first evaporator operates at a
concentration ratio of 2 it evaporates roughly onehalf of the water. The second evaporator uses the
concentrated brine from the first evaporator as feed
and operates at a concentration ratio of approximately
20. The two evaporators produce roughly the same
amount of condensate, but the recirculating brine in
the second evaporator is much more concentrated.
WLS is not capable of reaching the calcium concentration target for OTSG feed. The WAC step removes
the remaining soluble hardness ions (calcium and
Component
Ca (mg/l)
Mg (mg/l)
Ba (mg/l
Na (mg/l)
K (mg/l)
SiO2 (mg/l)
TOC (mg/)
NH3 (mg/l)
Cl (mg/l)
pH (s.u.)
M alkalinity
(mg/l as CaCO3)
DEPOSIT ANALYSES
OTSG Table 5 shows analytical results for deposits from several OTSG systems. These data suggest
that several contaminants contribute to the deposit
silica, hardness ions (calcium and magnesium),
carbonate ions, and organic compounds (dissolved
compounds or TOC; suspended hydrocarbon, or both).
Comparing the results from several sites indicates
that, while the relative abundance of these components may vary in the deposit, they are all present for
all of the sites represented. One possible contributing
factor to deposit formation in OTSGs is variation in
the performance of upstream treatment equipment.4
880
nm = not measured
EVAPORATORS Table 5 also includes the analytical results from deposits in two evaporator systems.
Note that the deposit samples were taken from several
different places in the system. System 1 uses two
evaporators in series. E1 and E2 samples were from
the sumps of evaporator 1 (E1) and evaporator 2 (E2)
respectively. System 2 is one stage.
Table
Analytical
results for
depositsfor
fromdeposits
OTSG and evaporator
systems.
Table5 5:
Analytical
results
from OTSG
and
Si
Fe
Mg
Ca
evaporator systems.
P
% as CO2
OTSG Systems
Site 1 Pigging Sample
70
89
74
87
15
49
65
13
12
45
56
34
32
36
14
32
28
30
11
32
33
32
12
32
37
34
12
21
42
47
34
13
19
13
16
47
27
<1
7.4
17
57
13
<0.5
22
nm
neg
55
8.8
20
nm
41
31
<0.5
12
nm
neg
neg
59
<0.5
10
20
neg
OTSG
63
7.2
18
neg
OTSG
53
10
21
neg
OTSG
25
20
<0.5
23
40
neg
Evaporator Systems
System 1 Feed Pump
49
20
9.5
25
neg
System 1 Preheater
10
40
<0.5
nm
41
33
System 1 Preheater
46
18
<0.5
7.8
29
System 1 Preheater
44
18
<0.5
8.6
31
System 1 E1
18
36
<1
11
36
26
System 1 E1
42
15
10
<0.5
10
27
System 1 E1
20
33
<0.5
11
35
24
System 1 E2
50
<0.5
12
<0.5
5.4
21
neg
System 1 E2
58
<0.5
11
<0.5
3.4
20
System 2
53
0.5
2.4
22
mn
nm
pos
nm = not measured
neg = negative in qualitative carbonate test
pos = positive in qualitative carbonate test
Figure 4 shows the scaling tendency at pH 8.8. Comparing Figure 4 with Figure 3 illustrates the result
of caustic addition to the feed tank. Increasing the
pH results in an increase in the calcium carbonate
scaling tendency both in the feed tank (~75C) and in
the preheater (~90C).
Figure 9 shows the transport across E2 after introduction of the calcium carbonate and silica inhibitors.
As compared to Figure 8, this shows much improved
silica transport, although a bit less than 100%.
Deposit analysis from this period showed 58% SiO2,
11% CaO, 1% MgO, and 3% carbonate (as CO2).
ACKNOWLEDGEMENT
Thanks to Dr. Jasbir Gill for helpful discussions and
for reviewing this manuscript.
REFERENCES
1. Consensus on Operating Practices for the Control of Feedwater and Boiler Water Chemistry in
Modern Industrial Boilers, American Society of
Mechanical Engineers, New York, NY (1994).
Figure 9 Transport Evaporator 1 to Evaporator 2.
CONCLUSIONS
A detailed investigation was undertaken into deposit
formation in a two-stage evaporator system treating
produced water and well water. The mixture of produced water and well water is unstable with respect
to the formation of calcium carbonate. This instability is increased by increasing pH and by increasing
temperature, both of which were initially present
in the feedwater system. Introducing a calcium
carbonate inhibitor and moving the pH adjustment
point downstream of the preheater was successful
in eliminating scale formation in the feed tank and
piping and in the preheater.
2. Standard Methods for the Examination of Water and Wastewater, 20th Ed., pp 2-26 to 2-28,
American Public Health Association, Washington,
DC (2008).
3. The Chemistry of Silica, R, K. Iler, pp 47-49,
John Wiley & Sons, New York, NY (1979).
4. Godfrey, M. R.; IWC 09-36 (2009).
5. ScaleSoftPitzer from Rice University.