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OSTI
LECTURERS:
G M Graham and K S Sorbie, Hertiol Watt University, UK
A Johnston, Nalco Exxon Chemicals, UK
Reproduction is prohibited unless permission from NIF or the Author
-i
DISCLAIMER
7th. NIF International Symposium on Oilfield Chemicals, Geilo, 17-20 March 1996
ABSTRACT
ICP Spectroscopy is recognised as a very effective tool for monitoring ion
compositions in many different waters. It has also been used by a number of
laboratories to determine residual levels of phosphonate (PH) scale inhibitors in
produced waters, based on the phosphorus content. Furthermore, until recently, it
had not been used effectively to monitor phosphino-polycarboxylate (PPCA)
returns; where it had been applied, large errors had frequently been observed. The
poor detection limits and accuracy obtained for PPCA inhibitors relates to the much
lower amount of phosphorus present when compared with a typical phosphonate
inhibitor. For example, 1 ppm active of the penta phosphonate DETPMP contains
approximately ~ 270 ppb phosphorus whereas 1 ppm active PPCA contains ~ 8 ppb
phosphorus, which was previously below the detection limit of commercial ICP
instruments.
However, it has been demonstrated within the OSRG that, with effective pretreatment, very accurate detection and assay of PPCA inhibitors can be readily
achieved. Furthermore, using modern instruments it will be demonstrated in this
paper that pre-treatment stages are no longer necessary. This significantly improves
the effectiveness of ICP detection for PPCA and other phosphorus containing
inhibitors using such instruments.
MASTER
asmeimoN OF THIS DOCUCNT B UIMTED
INTRODUCTION
ICP Spectroscopy is recognised as a very effective tool for monitoring ion
compositions in waters originating from a variety of industrial and natural
processes. It is routinely used in many laboratories in order to determine the ionic
composition of oilfield brines. In this paper, we focus on the accurate detection of
residual concentrations of phosphorus containing chemical species where the total
phosphorus content is at the ppb level. This is of particular importance for scale
inhibitor squeeze treatments since many of the chemical species used contain
phosphorus and these species have to be accurately detected at very low
concentrations. A major advantage of ICP techniques for assaying such inhibitor
species relates to sample throughput and the robustness of the technique to many of
the solution interferences affecting many wet chemical techniques. Automated
sample introduction systems and minimal requirement for sample preparation means
that many samples can be assayed routinely on a day to day basis.
In this paper we concentrate on the ability of modern ICP - AES (Inductively
Coupled Plasma - Atomic Emission Spectroscopy) instruments to accurately
monitor phosphino-polycarboxylate (PPCA) based inhibitor species at the sub ppm
level. This is an important advance in the effective use of ICP for oilfield produced
water analysis since the accurate assay of these polymeric inhibitor species becomes
very fast and simple when compared with more time consuming wet-chemical
techniques. Furthermore, it serves to illustrate how the detection limits for
phosphorus of modern ICP-AES instruments are now significantly lower than
previously reported.
Importance of Accurate Detection of Scale Squeeze Inhibitors: The
minimum inhibitor concentration (MIC) for a given brine chemistry is the level of
scale inhibitor required to prevent scale formation to some acceptable degree in the
field. In many cases, MIC levels are often < 5 ppm and it is therefore important to
be able to accurately monitor the returning inhibitor at these low levels in order to
determine the approach of the end of the squeeze lifetime (possibly some 3-12
months after initial treatment). Alternative approaches, such as monitoring of the
scaling ions themselves, for example [Ba 2+ ], will indicate when re-treatment is
essential, but this approach provides no lead time in order to prepare for the
operation. Furthermore, if successful computer modelling is to be carried out in
order to either optimise the conditions for future squeeze treatments or to predict the
end of the current squeeze lifetime, accurate low concentration return analysis is
essential.1
water, field produced Ula water and synthetic Ula water. Small volumes (< 20 ml)
of each sample were supplied to each ICP demonstrator for assay. In addition to
this, small volumes (again < 20 ml) of high and low standards were also supplied
for calibration purposes. The purpose of only supplying small volumes of sample
was to prevent the operators from calibrating in the different produced waters. This
would ensure that simple (synthetic) brines would have to be used for calibration
purposes.
Results and Discussion:
Examination of Tables 4 and 5 illustrates that
acceptable assay of phosphonate based inhibitors is obtainable using either of the
instruments examined. However, in general, the results obtained were poorer than
those obtained in earlier work using an older ICP instrument (Table 2 and 3). 3
However, this was not thought to be of any consequence since the instrument
operators were not provided with any information as to the origin of the samples
and the instruments would therefore have been optimised using different waters.
Analysis of the PPCA based inhibitor species in the different brines provides a
clearer indication as to the detection limits of modern ICP instruments. The main
technical result from this selection procedure was that either of the ICP instruments
examined could probably have detected the PPCA inhibitor when the machine was
fully optimised. This is because, for each instrument, a clear peak was obtained for
the high standard (20 ppm commercial PPCA - 42% active) when compared with
the background response.
EXPERIMENTAL STUDY
Since purchasing ICP-AES instruments in summer 1995, both Heriot-Watt and
Nalco/Exxon have worked closely in relation to optimisation of the ICP
instruments. Of particular interest,was the accuracy with which PPCA based
inhibitors could be detected at residual concentrations.
Model:
Mode:
Analytical lines
However, for low level PPCA analysis, the 214.9 nm analytical line was shown to
be too insensitive to PPCA analysis, even at relatively high PPCA concentrations (=
50 -100 ppm PPCA). In order to combat this and to allow both high and low range
calibrations, the more sensitive analytical line is effectively measured over two
calibration ranges as described below. This is a particular advantage of ICP-AES
detection since the complete concentration range may be detected, without prior
dilution into the appropriate concentration range. For instance, the commonly
applied wet chemical Hyamine 1622 technique has a rather limited range in the
region 0 - 1 0 ppm (active) PPCA. Errors in dilution factors for unknown
concentration returns often lead to multiple analysis. By analysing directly using
ICP-AES with two calibration ranges, analytical ranges of the order 0 - 5,000 ppm
(or greater) are readily achieved.
Low concentration range
STD LOW
0 ppm PPCA (active) in appropriate synthetic brine
STD 1
5 ppm PPCA (active) in appropriate synthetic brine
STD 2
50 ppm PPCA (active) in appropriate synthetic brine
accuracy of very low level PPCA analysis in synthetic sea water by repeat analysis.
The results presented in Table 6 clearly show that ppb levels of phosphorus can be
assayed using modern ICP-AES instruments of this type.
Effect of Brine Composition: Following the success of detection of low level
PPCA analysis in synthetic sea water, the ability of the instrument to cope with very
high salinity brines was examined. In order to examine salinity effects, a high
salinity brine with a composition similar to that found in the Ula formation was
examined. This was important since very fine diameter glass nebulisers (Meinhart
nebulisers) are used in our instrument; these nebulisers must be able to cope with
high salinity oilfield brines without causing blockages. We note that the fine bore
"Meinhart" nebulisers used in these instruments do occasionally suffer from
blockages. However, with appropriate flushing between samples the problem can
be minimised and only occasional blockage occurs. The ionic composition of the
brines examined in this study are shown in Table 7. Internal calibrations using the
synthetic Ula type formation brine were then performed and repeat analysis
performed over a range of PPCA concentrations in a similar manner to that for
synthetic sea water, the results obtained are also presented in Table 6.
Synthetic Brines - Results and Discussion: Very good residual detection of
PPCA inhibitors has been achieved in both low salinity (sea water) and high salinity
(Ula formation water) brines. However, the brine salinity has been shown to
influence the results obtained quite dramatically. Pseudo calibration curves
(obtained by monitoring the intensity of the signal obtained in the different brines)
are plotted in Figure 3. This shows that a less sensitive response is obtained in the
high salinity brine. This is indicative of a suppression of the peak height caused by
the brine salinity. Calibration standards should therefore be matrix matched as close
as possible.
(sampled after the test separators). The samples were then filtered using analytical
grade filter paper prior to introduction into the ICP.
Cormorant Field Produced Water: When examining the accuracy of the
analysis of low concentration PPCA in this brine, instrument calibrations were
performed in synthetic sea water. A large number of samples of known
concentration were then examined following each calibration. The results of this
repeat analysis are presented in Table 8.
In addition to this, the effect of sample pre-treatment in order to reduce the levels of
dissolved organics was examined. This involved passing the produced brines
through C18 cartridges at neutral pH prior to introduction into the ICP. These
samples were then examined using synthetic sea water calibration curves. The use
of such techniques has been explained previously.3 Again, the results of this repeat
analysis are presented in Table 8. Examination of the results in Table 8 leads a
number of important results, as follows:
(i)
(ii)
(iii)
(iv)
(iii) and (iv) combined implies that only minimal pre-treatment is required for
properly sampled field produced waters.
Via Field Produced Water: In more severe brines, calibration and subsequent
repeat analysis has been performed using matrix matched calibration standards. For
a sample of Ula produced water, sodium, calcium and magnesium analysis
indicated that the ionic composition of the sample obtained differed considerably
from the synthetic Ula formation water examined above. Calibration standards
were made up in a matrix matched brine as described in Table 7 prior to analysis of
spiked samples.
Furthermore, in order to further examine the importance of matrix matching
calibration standards, the produced Ula water spiked samples were also analysed
based upon synthetic sea water and synthetic Ula water (as used previously). The
results of this examination are presented in Table 9. Clearly, very accurate analysis
is again achieved using appropriate synthetic brine standards.
Examination of the results in Table 9 shows the following:
(i)
As for the lower salinity Cormorant produced water, very accurate PPCA
detection, down to - 0.5 ppm (active), is readily obtainable with minimal
sample pre-treatment using synthetic brine calibration curves.
(ii)
(iii)
This field produced sample had a considerably lower salt concentration than
expected for 100% Ula formation brine. This meant that calibration in
synthetic Ula formation brine gave poor results. However, calibration in
synthetic sea water gave very similar (good) results to that in the matrix
matched synthetic brine. The conclusion here is that only approximate
matrix matching is required.
REFERENCES
1.
Sorbie, K.S., Yuan, M.D., Graham, G.M. and Todd, A.C.: "Appropriate
Laboratory Evaluation of Oilfield Scale Inhibitors", Presented at the
conference Advances in Solving Oilfield Scaling Problems, Organised by
IBC Ltd, Marriott Hotel, Dyce, Aberdeen, 7-8 October 1992.
2.
Graham, G.M., Sorbie, K.S. and Boak, L.S.: "Development and Accurate
Assay Techniques for Poly-Vinyl Sulphonate (PVS) and Sulphonated C0Polymer (VS-Co) Oilfield Scale Inhibitor", Presented at the NIF 6th Int.
Symp. Oil Field Chemicals, held in Geilo, Norway, 19 - 22 March, 1995.
Graham G. M., Sorbie, K.S., Boak, L.S., Taylor, K. and Blilie, L.:
"Development and application of Accurate Detection and Assay Techniques
for Oilfield Scale Inhibitors in Produced Water Samples", SPE 28997,
Presented at the SPE Int. Symposium on Oilfield Chemistry, held in San
Antonio, TX. 14-17 February, 1995.
4.
5.
6.
Appendix 1:
u.v.
(1)
(2)
(3)
Appendix 2:
(5)
(6)
(7)
(8)
(9)
Instrument Parameters
Make:
Jobin Yvon (Instruments S.A.)
Model:
JY 138 Ultrace ICP Optical Emission Spectrometer
Mode:
Sequential
Analytical lines
Phosphorous at 177.4 nm
(Low range calibration)
Phosphorous at 214.9 nm
(High range calibration)
Low concentration range
STD LOW
0 ppm PH (active) in appropriate synthetic brine
STD 1
5 ppm PH (active) in appropriate synthetic brine
STD 2
50 ppm PH (active) in appropriate synthetic brine
High concentration range
STD LOW
0 ppm PH (active) in appropriate synthetic brine
STD 1
50 ppm PH (active) in appropriate synthetic brine
STD 2
500 ppm PH (active) in appropriate synthetic brine
STD 3
2,500 ppm PH (active) in appropriate synthetic brine
PPCA analysis in produced waters
(1)
(2)
(3)
(4)
Instrument Parameters
Make:
Jobin Yvon (Instruments S.A.)
Model:
JY 138 Ultrace ICP Optical Emission Spectrometer
Mode:
Sequential
Analytical lines
Phosphorous at 177.4 nm
(Low range calibration)
Phosphorous at 177.4 nm
(High range calibration)
Low concentration range
STD LOW
0 ppm PPCA (active) in appropriate synthetic brine
STD 1
5 ppm PPCA (active) in appropriate synthetic brine
STD 2
50 ppm PPCA (active) in appropriate synthetic brine
High concentration range
STD LOW
0 ppm PPCA (active) in appropriate synthetic brine
STD 1
50 ppm PPCA (active) in appropriate synthetic brine
STD 2
500 ppm PPCA (active) in appropriate synthetic brine
STD 3
2,500 ppm PPCA (active) in appropriate synthetic brine
4"
0.5
1.0
1.5
Absorbance 890 nm
Figure 2
Molecular Structures of the penta-phosphonate (DETPMP) and
phosphino-polycarboxylate (PPCA) inhibitors examined in this
section.
HUCH
CHj
m
fcoOH
OH
CHj-H
HO-P-CH2
CH2P-OH
NCHJCH2NCH2CH2N
|H
COOH
\H2X
HOPOH
II
O
Penta-phosphonate (DETPMP)
5000-
100
200
300
400
500
600
Table 1
[PH]*(active)
0
1
2
3
4
0
1
2
3
4
Table 2:
0.345
0.449
0.613
0.771
0.961
0.128
0.422
0.716
1.009
1.282
0.692
0.760
0.879
1.003
1.177
0.144
0.440
732
1.025
1.274
1.104
1.129
1.192
1.259
1.429
0.164
0.465
0.750
1..040
1.256
0.197
0.512
0.779
1.050
1.243
0.00
0.00
0.00
1.00
1.00
1.00
5.00
5.00
-0.04
0.11
-0.01
0.48
0.49
0.61
2.76
2.69
0.10
0.07
0.06
0.08
0.08
0.04
0.19
0.09
137.90
32.67
234.40
8.67
8.78
3.72
3.85
1.91
0.00
0.00
0.00
1.00
1.00
1.00
5.00
5.00
Produced Water C
0.00
0.04
0.00
0.02
0.00
0.04
0.55
1.11
0.55
1.05
0.55
1.13
2.75
4.43
2.75
4.16
0.02
0.01
0.02
0.61
0.58
0.62
2.43
2.29
0.03
0.08
0.11
0.11
0.09
0.06
0.12
0.07
70.84
318.40
307.70
9.78
8.40
5.41
2.71
1.59
0.00
0.00
0.00
1.00
1.00
1.00
5.00
5.00
Produced Water D
0.00
0.05
0.00
0.00
0.00
0.00
0.55
0.73
0.55
0.93
0.55
0.87
2.75
4.49
2.75
4.60
0.03
0.00
0.00
0.40
0.51
0.48
2.47
2.53
0.17
0.08
0.09
0.14
0.04
0.12
0.21
0.07
365.00
174.40
701.30
19.34
4.00
14.31
4.65
1.49
Table 3
0.00
2.00
2.00
5.00
5.00
0.01
0.78
0.78
2.11
2.08
0.03
0.05
0.03
0.03
0.06
126.10
2.59
1.73
0.53
1.29
0.00
2.00
2.00
5.00
5.00
Produced Water C
0.00
0.03
0.84
2.26
0.84
2.24
2.10
5.03
2.10
5.04
0.01
0.95
0.94
2.11
2.12
0.03
0.04
0.05
0.06
0.06
129.70
3.87
2.00
1.09
1.25
0.00
2.00
2.00
5.00
5.00
Produced Water D
0.00
0.03
0.84
2.01
0.84
2.02
2.10
5.02
2.10
5.00
0.01
0.84
0.85
2.11
2.10
0.04
0.04
0.04
0.07
0.12
145.70
1.96
1.91
1.36
2.43
Table 4
i.
0.00
0.70
1.80
5.30
15.60
Known
Deternine [PPCA ppm
[PPCA] ppm UlaP.W.
Brent P.W. SAW.
0.00
< blank
0.32
< blank
1.30
< blank
1.79
3.4397
2.40
1.18
3.14
2.42
5.20
3.44
5.68
5.18
14.70
12.88
15.89
14.67
Brent-treat
< blank
1.02
2.24
4.05
13.75
Known
Determine [PPCA] ppm
[PPCA] ppm UlaP.W.
Brent P.W. SAW.
(Bk + 2 stds) (Bk +1 std) (Bk + 1 std)
0.00
<Mank
0.40
0.10
1.30
1.02
0.24
5.51
2.40
3.07
0.79
4.98
5.20
5.02
2.98
6.95
14.70
14.10
14.17
15.28
Nota:
Known
Determme [PPCA] ppm
!PPCA)ppm UlaP.W. Brent P.W. SAW. (Bk + 1 std)
UAN.
213.6nni
177.4un
0.00
21?
-5.43
-6.59
1.30
-0.81
0.77
-2.10
2.40
2.15
3.51
7.34
5.20
3.59
-7.42
-13.78
14.70
12.90
-3.87
-4.76
All samples prepared as active inhi rilor (i.e. PPCA - 4 2 * active. PH - 50% Active).
All samples prepared in filtered brine.
|
"Brent - treat" refers to pre-treated samples viz - clean up and concentration 5.
All samples analysed using Phosphorous line at - 177.4 nm.
Varian also examined Phosphorous line at -213.6 nm.
Generally only blank and 1 standard (20ppm) used. Were 2 sub indicated a 5.2 ppm staiidardwasals 0 included.
U S N. indicates the use of Ultra-sonic nebuliser. However this caused
additional problems due to blockages and was replaced with standard type lebuliser.
Table 5
Known
Determine (PPCA PP
[PPCAlppm UlaP.W.
Brent P.W. SAW.
2.00
3.42
2.05
2.02
5.00
6.93
2.26
5.05
10.00
11.32
10.87
9.71
20.00
21.82
19.67
45.10
50.00
48.00
50.87
19.90
Known
DeterBtme[PPCA PP
[PPCAlppm UlaP.W.
Brent P.W. SAW.
2.00
5.00
10.00
20.00
50.00
Ul.
2.02
4.86
9.48
18.22
44.79
2.45
5.39
10.58
19.42
46.67
2.16
5.17
9.98
19.62
47.18
<btank
< Nank
13.38
20.14
44.81
< blank
< blank
11.56
19.69
44.34
<Mank
< blank
19.03
46.67
Iota:
2.00
5.00
10.00
20.00
50.00
Known
Deternine [PPCA ppm
[PPCA] ppm UlaP.W.
Brent P.W. SAW.
213.6 am
2.00
1.18
< blank
2.58
5.00
4.84
<Uank
6.61
10.00
9.56
<blank
11.83
20.00
19.06
22.19
22.57
50.00
43.21
52.82
5335
2.38
4.90
10.47
47 JO
2.12
5.36
10.08
19.66
50.61
2.01
5.33
9.81
6.95
50.68
Table 6:
mean*
0.64
2
2
1.97
1.76
1.87
5
5
5
5
4.59
4.56
4.84
4.69
4.57
4.77
50
50
47.86
47.86
47.86
500
500
500.06
498.06
499.06
mean of 2 readings
Na+
Ca2+
Mg2+
K+
Sr2+
Ba2+
SO 4 2 -
ci-
sw
(ppm)
10,890
428
1,368
460
UlaFW
(ppm)
52,225
34,675
2,249
3,507
1,157
1.97
2.08
2.04
1.93
2.02
5
5
5
5
4.57
4.84
4.78
4.66
4.70
50
50
50
50
50.04
49.84
49.06
49.06
49.94
500
500
500
500
501.24
506.24
506.26
506.26
503.74
2,960
91
19,766
153,000
Cormorant1"
(ppm)
6,350
145
25
140
25
20
10,400
0.39
2
2
2
2
Ion
mean*
0.36
1.99
4.72
49.06
506.26
Table 8:
No C18 pre-treatment
Known [PPCA] Determined
mean*
active ppm
active ppm
0.60
0.5
0.56
0.5
0.65
Cl 8 pre-treatment
Determined
active ppm
mean*
0.79
0.78
0.78
2
2
2.15
2.11
2.13
2.60
2.39
2.50
5
5
5.63
5.60
5.61
5.54
5.68
5.61
50
50
50
50
54.00
57.14
54.31
56.10
55.57
54.43
55.97
53.89
58.05
55.20
55.20
55.97
Note 2:
Table 9:
mean
-0.04
mean
-0.03
0.5
0.5
0.53
0.50
0.52
0.5
0.5
0.37
1.44
0.91
2
2
2.06
2.09
2.08
2
2
3.39
3.46
3.43
5
5
5.09
5.30
5.19
5
5
11.18
10.96
11.07
50
50
54.51
51.94
53.22
50
50
90.38
88.35
89.36
0.5
0.5
0.42
0.54
0.48
2
2
2.04
1.96
2.00
5
5
5.29
4.85
5.07
50
50
52.57
52.67
52.62
Table 10:
Unknown Sample
Spiked [PPCA]
IJ>.
[as supplied]
[active]
1
7
15
3
4
14
6
8
12
5
11
13
2
9
10
Recorded concentrations
A
B
[as supplied] [as supplied]
[active]
[as supplied]
ppm
mean
mean
ppm
0.66
0.73
0.12
0.20
0.84
0.00
0.7
0.10
A
[as supplied]
mean
0.10
[active]
mean
0.02
0.00
0.00
0.00
0.00
0.00
0.00
2.50
2.50
2.50
0.43
0.43
0.43
3.09
2.74
1.89
2.57
0.44
1.50
1.30
1.40
0.24
9.50
9.50
9.50
1.62
1.62
1.62
10.36
11.5
9.35
10.40
1.77
7.80
8.70
7.20
7.90
1.34
20.00
20.00
20.00
3.40
3.40
3.40
23.37
20.67
20.85
21.63
3.68
18.90
18.05
3.07
725.00
725.00
725.00
123.25
123.25
123.25
799.33
837.76
836.73
824.61
758.60
128.96
17.20
140.18
758.60