PO169752 DOI: 10.

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Synergistic Properties of Phosphonate

and Polymeric Scale-Inhibitor Blends for
Barium Sulfate Scale Inhibition
S.S. Shaw and K.S. Sorbie, Heriot-Watt University

Summary
Barium sulfate is one of the most-difficult types of scale to inhibit
in oil- and gas-production systems because of its physical hardness and its chemical and thermal stability. Barium sulfate is most
commonly inhibited with either phosphonate or polymeric scale
inhibitors (SIs) deployed at substoichiometric concentrations.
What is less well-known in the oil industry is the effect resulting
from the use of combinations of two (or more) SIs synergistically
for enhanced scale-inhibition performance. A positive
synergistic effect would be one in which, for example, 5 ppm of
A 5 ppm of B performed better than 10 ppm of either A or B. In
this paper, a series of static barium sulfate inhibition-efficiency
(IE) test results are presented, in which a series of pairs of SIs
have been tested to determine their synergistic properties at pH
5.5 and 95 C. Polymers can be blended with phosphonates or,
alternatively, pairs of phosphonates or polymers may be applied.
In all cases, the synergistic IE is compared with the IE of each SI
tested independently at the mass dosage (i.e., the same concentration in mg/L or ppm). Each separate single SI used in the work
has been tested previously for barium sulfate IE at pH 5.5 and
95 C to determine the minimum inhibitor concentration (MIC)
for each species (Shaw et al 2012a, b). Previously, nine phosphonate and nine polymeric SIs were tested individually; in this
work, 34 SI combinations have been tested to examine their synergistic properties. The MICs of the synergistic blends are compared with the normal MICs of the individual SIs. Surprisingly, in
most cases, the IE of the blends is usually higher over the range of
SI concentrations tested (i.e., the MIC of the blend is lower), compared with that of each SI tested separately. Certain pairs of SIs
used together yield a significantly beneficial effect (e.g.,
DETPMP and HMTPMP, both pentaphosphonates). Some mechanistic reasons for these synergistic pairs working particularly well
are suggested.
Introduction
In this paper, the synergistic properties of various combinations of
phosphonate and polymeric barium sulfate scale-inhibitors (SIs)
are investigated. Static barium sulfate inhibition-efficiency (IE)
tests are used commonly to determine the minimum inhibitor concentration (MIC) of SIs (Read and Ringen 1982; Cushner et al.
1988; Graham et al. 1997; Yuan et al. 1997a, b; 1998; Boak et al.
1999; Sorbie et al. 2000; Yuan 2001, 2002; Graham et al. 2002,
2003; Laing et al. 2003; Sorbie and Laing 2004; Shaw 2012;
Shaw and Sorbie 2012; Shaw et al. 2012a, b, c; Boak 2013; Shaw
and Sorbie 2013b, 2014b). MIC is usually defined as that SI concentration, [SI], at which 90% IE or greater is achieved at 22 (or
sometimes 24) hours after mixing the scaling brines, although in
some cases, the 2-hour MICs are quoted. In such tests, a number
of variables can be changedbrine composition (notably Ba2,
Ca2, and Mg2), the barite saturation ratio, salinity, pH, and
temperature (Read and Ringen 1982; Cushner et al. 1988; Graham
et al. 1997, Yuan et al. 1997a, b, 1998; Boak et al. 1999; Sorbie
C 2015 Society of Petroleum Engineers
Copyright V

This paper (SPE 169752) was accepted for presentation at the SPE International Oilfield
Scale Conference and Exhibition, Aberdeen, 1415 May 2014, and revised for publication.
Original manuscript received for review 14 February 2014. Revised manuscript received for
review 16 June 2014. Paper peer approved 28 August 2014.

16

et al. 2000; Yuan 2001, 2002; Graham et al. 2002, 2003; Laing
et al., 2003; Sorbie and Laing, 2004; Shaw 2012; Shaw et al.
2012a, b, c; Shaw and Sorbie 2012; Boak 2013; Shaw and Sorbie
2013b, 2014b). In some cases, [SI] may also be assayed over time
in addition to IEthese experiments are referred to as SI-consumption tests (Shaw 2012; Shaw and Sorbie 2013b). In this
work, all tests were conducted at pH 5.5, taking this as a typical
reservoir pH; pH is an important variable because it affects the
speciation of SIs in aqueous solution (Oddo and Tomson 1990;
Browning and Fogler 1995; Stone et al. 2002; Shaw and Sorbie
2012, 2013c, 2014a, c, d). In all static IE tests described in this paper, Nelson Forties formation water having a [Ba2] 269 ppm
was used, which, with North Sea seawater, gives a moderately
severe scaling-brine mixture.
In previous work, MICs for all the individual SIs were determined under a variety of test conditions, including those chosen
for the synergistic tests presented in this paper (Shaw 2012; Shaw
et al. 2012a, b). The names and chemical structures (except PFC)
of the 13 SIs tested in this work are given in Shaw and Sorbie
(2013a, Table 1). Of these 13 products, eight are phosphonate SIs
and five are polymeric SIs. In order for the best IE results to be
obtained in synergistic tests, it is usually best to test two SIs of
comparable IE together [e.g., HMTPMP and DETPMP (both pentaphosphonates) and EDTMPA and HMDP (both tetraphosphonates]. However, the present work will demonstrate that there are
sometimes notable exceptions; see the test results involving
HEDP (a diphosphonate).

Experimental Procedure
The experimental procedure followed to conduct the synergistic
tests was very similar to that used in regular inhibition-efficiency
(IE) tests. The only difference was that two scale inhibitors (SIs)
were added to the North Sea seawater (NSSW) brine before the
mixing stage, rather than just one. In static IE experiments, the
first step involves preparing synthetic brines and performing brine
filtering. Filtering brines removes any physical particles before
use in IE tests. The filter-paper pore size is 0.45 lm for brine filtering. Appropriate volumes of brine are then measured into the
test bottles. SI is added to the NSSW brine. Buffer solution is also
added to the test bottles before the mixing stage. A brine mixing
ratio of 60:40 NSSW/formation water (FW) was chosen for these
tests. This brine mixing ratio gives the highest barium sulfate saturation ratio (SR) for the resultant brine mix (Shaw 2012; Shaw
et al. 2012a, b, c; Shaw and Sorbie 2012), where SR is given by
SR

Ba2   SO2
4 
; . . . . . . . . . . . . . . . . . . . . . . . 1
Ksp

where Ksp is the solubility product of the barium sulfate. SR for

barite depends on a number of experimental conditions, mainly the
NSSW/FW mixing ratio, but also temperature, pH, and ionic
strength, all of which were fixed in the tests described in this paper.
The NSSW and FW compositions (ppm) are given in Table 1.
In all tests, the temperature was 95 C and the mix pH was 5.5,
which was achieved with a sodium acetate/acetic acid buffer, as
in the standard IE-test method. The brine mix molar ratio of
Ca2/Mg2 was equal to 0.57 in all experiments; this factor
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Ion

NSSW (ppm)

FW (ppm)

Na+

10,890

31,275

Ca2+

428

2,000

2+

Mg

1,368

739

K+

460

654

Ba2+

269

Sr2+

771

SO42

2,960

Cl

19,773

55,279

Table 1NSSW and FW brine compositions used in this work.

influences the IE performance of phosphonate SIs strongly, particularly Type 2 phosphonates (Shaw et al. 2012a, c).
For each experiment conducted, two blank test bottles were
used, and each [SI] was tested in duplicate. Sampling was performed at 2 hours and 22 hours after the mixing of the brines. One
milliliter of sample was extracted from the supernatant liquid in
each test bottle, and added to 9 mL of potassium chloride (KCl)/
PVS quenching solution in a test tube. The quenching solution
prevents any further precipitation from occurring. The quenching
solution contains 1,000 ppm of commercial PVS SI and 3,000
ppm of potassium (as KCl) in distilled water, adjusted to pH 8 to
8.5. The solution of 1,000 ppm of PVS has been shown to effectively stabilize (or quench) the sample and thus prevent further
precipitation. The potassium is included in this solution to act as
an ionization suppressant for the atomic absorption determination
of barium. This is only included in current work for emergencies
because the standard analytical approach currently used within
the Flow Assurance and Scale Team laboratories for barium is
inductively coupled plasma spectroscopy. IE (as %) is defined as
follows:
IE 100 

Ct  Cb t
; . . . . . . . . . . . . . . . . . . . . . 2
C0  Cb t

Polymer

Phosphonate

where C(t) is the test sample barium concentration at time t in

ppm, C0 is the control barium concentration at time t 0 in ppm,
and Cb(t) is the barium concentration in the blank solution (no SI)
at time t in ppm. Because the IE calculation depends on the solution [Ba2] only, it is straightforward to compare the IE of brine
mixtures containing only one SI with mixtures containing two or
more SIs. Thirty-four combinations of SIs were tested synergistically in static barium sulfate IE tests, as shown in Fig. 1.
All phosphonate SI formulations were supplied in acid form,
except OMTHP (hexaphosphonate) and HMDP (tetraphosphonate). OMTHP was supplied as a sodium salt solution and HMDP
was supplied as a potassium salt solution. However, the precise
nature of the SI formulation has little bearing on the IE-test results
because all test solutions are buffered to pH 5.5, and only a very
small volume of the SI stock solutions are added to the test brines.
Of the polymers tested, most were supplied as near-neutral-pH

EDTMPA
HMDP
HEDP
NTP
HPAA
OMTHP
DETPMP
HMTPMP
PPCA
PVS
VS-Co
PCF
SPPCA

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8

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salt solutions (PFC, PVS, and VS-Co) and the others were acidic
(PPCA and SPPCA).
In all cases, in the synergistic tests, the mixtures of two SIs
were tested at one-half the concentration at which they were
tested independently. For example, DETPMP and HMTPMP were
tested individually at 10, 20, and 30 ppm in regular IE tests. In the
synergistic test, DETPMP and HMTPMP were tested together at
55, 1010, and 1515 ppm. Note that such mixtures of two SIs
are not tested in a 50:50 molar ratio [because of variations in the
molecular weights (MWs) of the products]; however, the tests are
nevertheless synergistic and indicative of synergistic properties of
specific SI blends. If the MW of the two-blend SIs is similar, as in
the case of DETPMP (MW573.25 g/mol) and HMTPMP
(MW685.49 g/mol), then the synergistic blend would in any
case contain approximately a 50:50 molar blend of the two SIs.
However, even if there is a large difference in the MWs of the
two-blend SIs [e.g., DETPMP (MW573.25 g/mol) and HEDP
(MW206.03 g/mol)], the blend still contains one-half the molar
concentration of each individual SI tested separately, and such
blends are usually still synergistic. Note that all [SI]s (ppm) stated
in this work refer to active SI concentrations.
Experimental Results
Experimental results will be discussed in a systematic order.
Three categories of synergistic test can be performed, depending
on the nature and combination of the scale inhibitors (SIs) (i.e.,
phosphonate/phosphonate, phosphonate/polymer, or polymer/
polymer), as shown in Fig. 1. Only one polymer/polymer combination has been tested to date; however, this work might be
expanded in the future. All individual SI and SI-blend 2- and 22hour barium sulfate inhibition-efficiency (IE) results (%) are listed
in Appendix A. Only limited IE results will be shown graphically
because of space constraints. Note that to see all barium sulfate
IE-results charts (i.e., individual SIs and synergistic blends), you
should refer to SPE-169752-MS (Shaw and Sorbie 2014e).
Phosphonate/Phosphonate Synergistic Tests. DETPMP (a commonly applied conventional pentaphosphonate SI) was tested
synergistically with four other phosphonate productsHMTPMP
(a long-carbon-chain pentaphosphonate), EDTMPA (tetraphosphonate), HMDP (a long-carbon-chain tetraphosphonate), and
HEDP (diphosphonate). It was clear from all four results that
there was a synergistic benefit in the use of all four SI combinations. The most surprising results were obtained when testing
DETPMPHMDP and DETPMPHEDP, because when HMDP
and HEDP were tested individually, the IE was poor over the concentration range of 10 to 30 ppm. Of Tests 1 through 4, the mostefficient synergistic result was obtained testing DETPMP
HMTPMP; however, this was as expected because both DETPMP
and HMTPMP are pentaphosphonates (i.e., there are more phosphonate functional groups present), and also DETPMP is Type 1
and HMTPMP is Type 2. Figs. 2 through 4 show the results of
Test 1 (i.e., the individual DETPMP IE, the individual HMTPMP

Test Matrix With Test Numbers

9
11

2
5
16
20
25

3
6
17
21
26

22
28

31

32

33

EDTMPA

HMDP

HEDP

10

12
13

27

NTP HPAA OMTHP

Phosphonate

1
14
18
23

15
19
24

29

30

DETPMP

HMTPMP

34
PPCA

PVS

VS-Co PFC
Polymer

SPPCA

Fig. 1Combinations of SIs tested synergistically in barium sulfate IE experiments (the numbers in the boxes refer to the experiment numbers).
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PO169752 DOI: 10.2118/169752-PA Date: 13-February-15

DETPMP 60:40 NSSW/FW pH 5.5

22 hours

IE (%)

2 hours

20
[DETPMP] / active ppm

30

Fig. 2DETPMP IE: 60:40 North Sea seawater (NSSW)/formation water (FW), pH 5.5, 95 C, [SI]s of 10, 20, and 30 ppm.

IE (%)

IE, and the synergistic DETPMPHMTPMP IE, respectively).

This phosphonate/phosphonate blend is definitely synergistic.
HMTPMP was tested synergistically with EDTMPA and
HMDP. Only one of these synergistic combinations (HMTPMP
EDTMPA) yielded an improvement in the IE. It is possible that the
two long-chain phosphonates (i.e., HMTPMPHMDP) do not
work well synergistically because both products operate by very
similar inhibition mechanisms. Indeed, both of these products
showed striking similarities when tested in standard IE tests, varying Ca2/Mg2 (Shaw et al. 2012a, c) [e.g., both had similar minimum-inhibitor-concentration (MIC) levels and similar sensitivity to
Ca2 and Mg2 cations]. The EDTMPA is structurally similar to
DETPMP (Shaw and Sorbie 2013a, Table 1), which is probably
why the HMTPMPEDTMPA combination was successfulthe
HMTPMPEDTMPA combination is analogous to HMTPMP
DETPMP. EDTMPA was tested synergistically with HMDP and
HEDP. These two results were very similar; both SI combinations
resulted in positive synergy. The EDTMPA worked well with the
long-carbon-chain tetraphosphonate (HMDP); this result was similar to the DETPMPHMDP combination. It could be the case that
DETPMP and EDTMPA inhibit barite by similar mechanisms. The
HEDP, when used synergistically with EDTMPA, improved the
22-hour IE.
NTP (triphosphonate) was tested synergistically with HEDP
(diphosphonate), and HPAA (a monophosphonate and monocarboxylate). Note that in the NTPHPAA synergistic test, the blend
[SI]s were 2020, 2525, and 3030 ppm, whereas in the
NTPHEDP synergistic test, they were 55, 1010, and 1515
ppm (see Appendix A). This is because the HPAA individual
MIC is greater than the HEDP individual MIC; therefore, higher
[SI]s had to be used in the NTPHPAA synergistic test. There
was some synergy in the NTPHEDP test in the 1515-ppm synergistic blend. Both the 2- and 22-hour IEs were improved. The

100
90
80
70
60
50
40
30
20
10
0

Synergistic 50:50 SI mix: DETPMP and HMTPMP

60:40 NSSW/FW pH 5.5 95C

2 hours

22 hours

5+5
10 + 10
15 + 15
[DETPMP] + [HMTPMP] / active ppm

Fig. 4Synergistic DETPMP/HMTPMP IE: 60:40 NSSW/FW, pH

5.5, 95 C, [SI]s of 515, 10110, and 15115 ppm.
18

100
90
80
70
60
50
40
30
20
10
0

2 hours

10

10

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HMTPMP 60:40 NSSW/FW pH 5.5

95C

IE (%)

100
90
80
70
60
50
40
30
20
10
0

Stage:

95C

22 hours

20
[HMTPMP] / active ppm

30

Fig. 3HMTPMP IE: 60:40 NSSW/FW, pH 5.5, 95 C, [SI]s of 10,

20, and 30 ppm.

NTP and HPAA combination also exhibited synergy, although at

higher [SI]s. The 2525-ppm and 3030-ppm NTPHPAA
blends were definitely synergistic. The HEDP has now been
shown to work well synergistically with DETPMP, EDTMPA,
and NTP. The HEDP and HPAA have similar chemical structuresboth are low-molecular-weight molecules (Shaw and Sorbie 2013a, Table 1). When HEDP and HPAA were used together,
it did not result in positive synergy, again indicating that similar
products do not work well synergistically (i.e., products which
might operate by similar inhibition mechanisms). The
HMTPMPHMDP synergistic result provided another example
of this behavior. In static IE tests with varying Ca2/Mg2 and in
SI-consumption tests, the HEDP and HPAA gave extremely similar results (Shaw 2012; Shaw et al. 2012c; Shaw and Sorbie
2013b).
OMTHP (hexaphosphonate) was tested with DETPMP and
HMTPMP. In these two tests, the range of [SI]s tested had to be
reduced significantly because the OMTHP individual MICs are
less than 10 ppm (see Appendix A). Neither Test 12 nor Test 13
showed a positive synergistic result. In both cases, the synergistic
IE was approximately the same or worse than the individual
OMTHP IE at the same total [SI]. Again, it appears to be best to
test SIs of comparable standard. The results of Tests 12 and 13
were broad, as expected, because when one-half of the hexaphosphonate (ppm) was replaced by a pentaphosphonate (i.e., in
the blend), the IE was approximately the same or lower.
Phosphonate/Polymer Synergistic Tests. Phosphonate products
DETPMP, HMTPMP, EDTMPA, and HMDP were tested synergistically with PPCA. In the case of DETPMPPPCA, there was
no synergistic enhancement of IE; however, the blend IE was
approximately the same as the individual DETPMP IE, and was
better than the average of the DETPMP and PPCA individual IE
levels. Tests 15 through 17 did yield some synergistic benefits.
The HMTPMPPPCA combination resulted in an enhancement
in 2- and 22-hour IE. Interestingly, when PPCA was tested with
EDTMPA, only the 2-hour IE was enhanced marginally, whereas
the 22-hour synergistic IE was lower than the individual
EDTMPA IE. These observations are most likely indicative of the
predominant mechanism by which PPCA operates, which is probably mainly by nucleation inhibition, although PPCA is still capable of some crystal-growth-inhibition properties, as stated in the
literature (Yuan et al. 1998; Sorbie et al. 2000; Sorbie and Laing
2004; Boak 2013; Shaw and Sorbie 2013b). Generally, most polymers function mainly by nucleation inhibition, and this results in
the 2-hour IE often being significantly better than the long-term
IE (e.g., 22 hours). In the HMDPPPCA test, the synergistic 2hour IE was the same as or lower than the individual PPCA IE,
whereas the synergistic 22-hour IE was higher than the individual
PPCA IE. In this case, the enhancement in the 22-hour IE was
definitely a result of the presence of HMDP in the synergistic
blend. Phosphonates are known to operate mainly by crystalFebruary 2015 SPE Production & Operations

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HMDP 60:40 NSSW/FW pH 5.5

2 hours

95C

IE (%)
10

20
[HMDP] / active ppm

30

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PFC 60:40 NSSW/FW

22 hours

IE (%)

100
90
80
70
60
50
40
30
20
10
0

Stage:

100
90
80
70
60
50
40
30
20
10
0

2 hours

10

pH 5.5

95C

22 hours

20
[PFC] / active ppm

30

Fig. 6PFC IE: 60:40 NSSW/FW, pH 5.5, 95 C, [SI]s of 10, 20,

and 30 ppm.

growth inhibition, meaning that their long-term (e.g., 22-hour) IE

is often very good. The HMTPMPPPCA and HMDPPPCA
synergistic results are examples of positive synergistic phosphonate/polymer combinations. The similarities between the Test-15
and Test-17 synergistic results, again, is because of the structural
similarities of HMTPMP and HMDP, resulting in similar chemical behavior of these products.
Phosphonate products DETPMP, HMTPMP, EDTMPA,
HMDP, and HEDP were tested synergistically with PVS. In the
case of PVS, the HMTPMPPVS, HMDPPVS, and HEDP
PVS combinations showed some levels of synergy. In all three
cases, the synergistic IE at 2 and 22 hours was better than either of
the two components tested individually at the same total [SI], with
very few exceptions. Yet again, the HMTPMP and HMDP phosphonates were behaving similarly. The HEDP also showed similar
synergistic properties to the HMDP (see Appendix A), despite the
two chemical structures being different. Even the individual IEs
and MICs for HMDP and HEDP were very similar (see Appendix
A). The DETPMPPVS and EDTMPAPVS combinations were
not synergistic at 22 hours, although the EDTMPAPVS showed
some synergy at 2 hours only, unlike the former combination.
These synergistic results (i.e., DETPMPPVS and EDTMPAPVS) were very similar to those obtained when testing these
two phosphonates with PPCA. It appears to be the case that phosphonates DETPMP and EDTMPA do not work well synergistically with polymers. Again, the DETPMP and EDTMPA are
similar chemically, giving similar results. The two long-chain
phosphonates (i.e., HMTPMP and HMDP) and HEDP work well
with PVS. In these positive-synergy cases, it is most likely that the
PVS enhances the IE at 2 hours and the phosphonate improves the
IE at 22 hours in the blend. Also, in the EDTMPAPVS results, it
is probably the PVS that is enhancing the 2-hour IE in the blend.
PVS is known to be the polymeric SI that operates almost entirely
by nucleation inhibition (Yuan et al. 1998; Sorbie et al. 2000; Sorbie and Laing 2004; Shaw 2012; Shaw et al. 2012b; Boak 2013;
Shaw and Sorbie 2013b).

Phosphonate products DETPMP, HMTPMP, EDTMPA,

HMDP, NTP, and HEDP were tested synergistically with VS-Co.
VS-Co is similar to PVS, except VS-Co also contains carboxylic
acid functional groups. The percentage of sulphonate and carboxylic acid groups on the VS-Co polymer may be approximately
50:50; indeed, SI analysis work performed by Shaw (2012) suggests this might be the case. The VS-Co synergistic IE results can
therefore be compared with the results testing PVS with the same
phosphonates. In the case of VS-Co, all the SI combinations tested
were synergistic, except DETPMPVS-Co. However, in the case
of DETPMPVS-Co, the synergistic IE was almost identical to
the individual DETPMP IE (i.e., the synergistic IE was not simply
the average of the two individual IEs). This result shows that VSCo is performing as well as DETPMP at these [SI]s. The
EDTMPAVS-Co synergistic result was clearly better than the
EDTMPAPPCA and EDTMPAPVS results (see Appendix A).
There was only limited synergy in the case of EDTMPAPPCA
and no synergy in the case of EDTMPAPVS. NTP worked well
synergistically with VS-Co; this is a noteworthy result given the
poor individual IE of NTP at [SI]s of 10, 20, and 30 ppm (see
Appendix A).
Phosphonate products DETPMP, HMTPMP, EDTMPA,
HMDP, and HEDP were tested synergistically with PFC. PFC is a
phosphorus (P)-functionalized, sulphonated copolymer. The PFC
is chemically similar to VS-Co because it contains many carboxylic acid and sulphonate functional groups; however, it also contains a quantity of phosphorus as phosphonate-type functional
groups. The chemical structure of PFC was not disclosed to us.
Indeed, the similarity between VS-Co and PFC is shown in the
synergistic IE results (see Appendix A). PFC worked well synergistically with all the phosphonate products, except DETPMP. This
was exactly the same behavior observed testing VS-Co with various phosphonates. Comparing the DETPMPPFC synergistic
result with the DETPMPVS-Co synergistic result shows that
these two results are very similar (i.e., where the synergistic IE is
almost identical to the individual DETPMP IE; see Appendix A).
As found for VS-Co, the best enhancement of IE in testing PFC
was in blends containing HMTPMP, HMDP, and HEDP. Again,
the long-carbon-chain phosphonates (HMTPMP and HMDP) and
HEDP performed markedly well in synergistic blends with a polymeric species. Figs. 5 through 7 show the results of Test 32 (i.e.,
the individual HMDP IE, individual PFC IE, and synergistic
HMDPPFC IE, respectively). This phosphonate/polymer blend
is definitely synergistic.

IE (%)

Fig. 5HMDP IE: 60:40 NSSW/FW, pH 5.5, 95 C, [SI]s of 10, 20,

and 30 ppm.

100
90
80
70
60
50
40
30
20
10
0

Synergistic 50:50 mix: PFC + HMDP

60:40 NSSW/FW pH 5.5 95C
2 hours
22 hours

5+5

10 + 10
15 + 15
[PFC] + [HMDP] / active ppm

Fig. 7Synergistic HMDP/PFC IE: 60:40 NSSW/FW, pH 5.5,

95 C, [SI]s of 515, 10110, and 15115 ppm.

Polymer/Polymer Synergistic Tests. As noted previously, only

one polymer/polymer synergistic test has been performed to date,
testing the two polymers PPCA and SPPCA. SPPCA is simply
sulphonated PPCA, although the sulphonated side chains also
contain amino functional groups because one of the SPPCA
monomers is AMPS (2-acrylamido-2-methylpropane sulphonic
acid) (i.e., the sulphonated side chains in SPPCA are not simply
sulphonate functional groups, as in VS-Co and PVS). The chemical structures for PPCA and SPPCA are shown in Shaw and

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PO169752 DOI: 10.2118/169752-PA Date: 13-February-15

PPCA 60:40 NSSW/FW pH 5.5

100
90
80
60

IE (%)

IE (%)

70
50
40
30
20
10
0
20
[PPCA] / active ppm

30

Fig. 8PPCA IE: 60:40 NSSW/FW, pH 5.5, 95 C, [SI]s of 10, 20,

and 30 ppm.

Sorbie (2013a, Table 1). The PPCASPPCA synergistic result

did not show any enhancement in IE; indeed, the individual
PPCA IE was better. Both the PPCA 2- and 22-hour IEs were
greater than those of the synergistic blend. The PPCA 22-hour
individual IEs are most likely higher than those of the blend
because PPCA is a better crystal-growth blocker than SPPCA.
Generally, the more sulphonate functional groups present on a
polymer, the less successful it will be at crystal-growth inhibitionthis may explain the poor 22-hour synergistic IE results
(Shaw 2012; Shaw et al. 2012b; Boak 2013; Shaw and Sorbie
2013b). Further polymer/polymer combinations might be tested in
future work. Figs. 8 through 10 show the results of Test 34 (i.e.,
the individual PPCA IE, individual SPPCA IE, and synergistic
PPCASPPCA IE, respectively). This polymer/polymer blend is
definitely not synergistic.

IE (%)

Summary and Conclusions

The synergistic inhibition-efficiency (IE) test results presented in
this paper have shown that in the majority of cases, a blend of two
scale inhibitors (SIs) will behave in a synergistic manner. That is,
the IE of the blend is greater [i.e., minimum inhibitor concentration (MIC) is lower] than that of either component tested individually at the same total [SI]. In the synergistic blend, the effect on
the 2- and 22-hour IE clearly depends on the inhibition mechanisms by which the blend components operate. Phosphonate SIs
tend to operate mainly through a crystal-growth mechanism, and
this is why when these products are present in blends (particularly
in combination with polymers), the 22-hour IE is usually
enhanced. Polymers tend to operate principally through a nucleation-inhibition mechanism, although the degree to which this is
true varies from product to product. PPCA shows both nucleationinhibition and crystal-growth-inhibition qualities to some extent,

100
90
80
70
60
50
40
30
20
10
0

Synergistic 50:50 mix: PPCA + SPPCA

60:40 NSSW/FW pH 5.5 90C
2 hours
22 hours

5+5

10 + 10
15 + 15
[PPCA] + [SPPCA] / active ppm

Fig. 10Synergistic PPCA/SPPCA IE: 60:40 NSSW/FW, pH 5.5,

95 C, [SI]s of 515, 10110, and 15115 ppm.
20

Page: 20

SPPCA

95C

2 hours
22 hours

10

Stage:

100
90
80
70
60
50
40
30
20
10
0

Total Pages: 10

60:40 NSSW/FW

pH 5.5

95C

2 hours
22 hours

10

20
[SPPCA] / active ppm

30

Fig. 9SPPCA IE: 60:40 NSSW/FW, pH 5.5, 95 C, [SI]s of 10, 20,

and 30 ppm.

whereas for PVS, nucleation inhibition is the predominant mechanism. As a rule of thumb, if two SIs that operate by similar inhibition mechanisms are tested synergistically, the outcome usually
does not result in synergy [e.g., HMTPMP (Type 2) HMDP
(Type 2)]. HMTPMP and HMDP are similar chemically. Conversely, if two SIs that operate by different mechanisms are tested
together [e.g., DETPMP (Type 1) HMTPMP (Type 2)], the outcome usually does result in positive synergy. Therefore, the optimum synergistic blends are those that contain chemicals that
operate by different scale-inhibition mechanisms.
The use of synergistic SIs clearly enables multiple inhibition
mechanisms to operate effectively simultaneously. The mechanistic benefits of both inhibitors are exploited in the synergistic tests.
For example, earlier basic IE tests have shown that DETPMP is
more efficient than HMTPMP at 22 hours (Shaw et al. 2012a)
because DETPMP is probably a better crystal-growth blocker
(Yuan et al. 1998; Sorbie et al. 2000; Sorbie and Laing 2004). In
some cases, HMTPMP has been shown to be more efficient than
DETPMP at 2 hours, particularly in higher [Ca2] brine mixes
(Shaw 2012; Shaw et al. 2012a), and hence, HMTPMP may be a
better nucleation inhibitor than DETPMP, which may be related
to the HMTPMP chemical structure. Similar arguments could be
put forward for other combinations of SIs tested in this work. It
would also be possible to test blends of three SIsthis is even
more likely to yield better IE results. All synergistic tests conducted in this paper were conducted under static conditions. It
would also be beneficial to test selected synergistic SI combinations in the future under dynamic conditions (tube-blocking tests)
to see if there is still positive or negative synergy.
The use of certain combinations of SIs could yield benefits if
incorporated as part of a squeeze treatmenteach SI product will
have different adsorption and precipitation characteristics. This
may result in a more-effective squeeze treatment and in extended
squeeze lifetimes.
To quantify the synergistic enhancement numerically, we may
define the 2- and 22-hour %Synergy in two ways, as follows:


100  MinW1 ; W2  W3 
. . . . . . . . . 3
%Synergy
MinW1 ; W2


100  AvgW1 ; W2  W3 
%Synergy
; . . . . . . . . . 4
AvgW1 ; W2
where W1, W2, and W3 are the measured (or estimated) MIC levels
of SI1 alone, SI2 alone, and the SI blend, respectively (in ppm).
To obtain a positive %Synergy in Eq. 3, the blend MIC (W3) must
be lower than the minimum MIC of the two components in the
blend (W1 for SI1 and W2 for SI2). To obtain a positive %Synergy
in Eq. 4, the blend MIC (W3) must be lower than the average MIC
of the two components in the blend. Some degree of improved
performance is required for both Eqs. 3 and 4 to obtain a positive
%Synergy, but Eq. 3 is clearly a more-pessimistic or -strict performance measure.
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% SYNERGY Calculated With Minimum MIC

100
%Synergy =

2 hours

100.[Min(1; 2) 3]
Min(1; 2)

22 hours

50

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34

50
PHOSPHONATE/PHOSPHONATE TESTS

100

PHOSPHONATE/POLYMER TESTS
POLYMER/POLYMER TEST

150

Test Number

Fig. 112- and 22-hour %Synergy for all 34 SI blends tested in this work, calculated by Eq. 3; W1, W2, and W3 are the measured (or
estimated) MIC levels of SI1 alone, SI2 alone, and the SI blend, respectively.

Figs 11 and 12 show the 2- and 22-hour %Synergy for each of

the synergistic combinations of SIs shown in Fig. 1, calculated
from Eqs. 3 and 4, respectively. As expected, the more-strict
%Synergy calculation (Eq. 3) shows that fewer of the SI blends
show a positive effect. However, even for the stricter Eq. 3 criterion, 20 out of the 34 pairs (Tests 1, 2, 3, 4, 5, 7, 8, 9, 10, 19, 24,
25, 26, 27, 28, 29, 30, 31, 32, and 33) of SIs show a positive effect
at both 2 and 22 hours, and just 5 pairs (tests 11, 12, 14, 18, and
34) show a negative %Synergy effect at both times. For the lessstrict definition of %Synergy in Eq. 4, nearly all SI combinations
show some synergistic benefit in terms of IE performance. In
Figs. 11 and 12, it is clearly shown which SI combinations are
phosphonate/phosphonate, phosphonate/polymer, and polymer/
polymer (see color coding). Refer to Fig. 1 for the actual SIs
tested. The numerical data (i.e., %Synergy values) behind Fig. 11
are given in Fig. 13 (2-hour data) and Fig. 14 (22-hour data). The
numerical data (i.e., %Synergy values) behind Fig. 12 are given in
Fig. 15 (2-hour data) and Fig. 16 (22-hour data). Figs. 13 through
16 are in the same format as Fig. 1, such that the experiment to
which the %Synergy values relate can be found easily.

Future Work: Synergistic Static Barium Sulfate IE Tests

Varying Ca21/Mg21. Numerous static synergistic tests have
been performed testing several of the SI combinations examined
in this paper, varying the produced-water molar ratio of Ca2/
Mg2. Under base-case conditions (i.e., in all 60:40 North Sea
seawater/formation water tests described in this paper), the produced-water molar ratio of Ca2/Mg2 was equal to 0.57. In the
future tests, produced water Ca2/Mg2 molar ratios of 0.1, 1,
and 10 will be tested. The ionic strength will be kept at the same
level as that used in the tests described in this paper.
Nomenclature
C0 control barium concentration at time t0, ppm
C(t) test-sample barium concentration at time t, ppm
Cb(t) barium concentration in the blank solution (no SI) at time
t, ppm
Ksp solubility product of barium sulfate
W1 measured (or estimated) MIC for SI1, ppm
W2 measured (or estimated) MIC for SI2, ppm
W3 measured (or estimated) MIC for SI blend, ppm

% SYNERGY Calculated With Average MIC

120
PHOSPHONATE/PHOSPHONATE TESTS

100

PHOSPHONATE/POLYMER TESTS

%Synergy =

100.[Avg(1; 2) 3]
Avg(1; 2)

2 hours
22 hours

POLYMER/POLYMER TEST

80

60
40
20
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34

20
40
Test Number

Fig. 122- and 22-hour %Synergy for all 34 SI blends tested in this work, calculated by Eq. 4; W1, W2, and W3 are the measured (or
estimated) MIC levels of SI1 alone, SI2 alone, and the SI blend, respectively.
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21

PO169752 DOI: 10.2118/169752-PA Date: 13-February-15

Polymer

Phosphonate

EDTMPA
HMDP
HEDP
NTP
HPAA
OMTHP
DETPMP
HMTPMP
PPCA
PVS
VS-Co
PCF
SPPCA

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33%
33%
25%
50%
20%
33%
0%
33%
33%
17%

20%
0%
0%
33%
33%
33%

25%
33%
17%

EDTMPA

HMDP

HEDP

29%

20%

13%
0%

33%

NTP HPAA OMTHP

Phosphonate

20%
50%
20%
20%
20%

0%
33%
33%

DETPMP

HMTPMP

50%
PPCA

PVS

VS-Co
Polymer

PFC

SPPCA

Polymer

Phosphonate

Fig. 132-hour %Synergy values, calculated by Eq. 3.

EDTMPA
HMDP
HEDP
NTP
HPAA
OMTHP
DETPMP
HMTPMP
PPCA
PVS
VS-Co
PCF
SPPCA

50%
38%
20%
60%
43%
50%
0%
133%
25%
13%

33%

43%
0%
20%
20%
60%
50%

43%

11%
11%

40%
40%
40%

EDTMPA HMDP

HEDP

42%

43%
14%
71%
0%
14%

20%
10%
60%
60%
25%

NTP
HPAA OMTHP DETPMP HMTPMP
Phosphonate

PPCA

PVS

VS-Co
Polymer

PFC

SPPCA

Fig. 1422-hour %Synergy values, calculated by Eq. 3.

Polymer

Phosphonate

EDTMPA
HMDP
HEDP
NTP
HPAA
OMTHP
DETPMP
HMTPMP
PPCA
PVS
VS-Co
PCF
SPPCA

33%
43%
46%
0%
28%
33%
20%
0%
33%
17%

28%
0%
20%
43%
33%
33%

25%
43%
29%

EDTMPA

HMDP

HEDP

33%

39%

46%
58%

60%

NTP HPAA OMTHP

Phosphonate

28%
33%
8%
27%
27%

20%
43%
33%
33%

DETPMP

HMTPMP

9%
PPCA

PVS

VS-Co
Polymer

PFC

SPPCA

Polymer

Phosphonate

Fig. 152-hour %Synergy values, calculated by Eq. 4.

EDTMPA
HMDP
HEDP
NTP
HPAA
OMTHP
DETPMP
HMTPMP
PPCA
PVS
VS-Co
PCF
SPPCA

56%
44%
47%
14%
47%
56%
67%
97%
40%
22%

53%
0%
68%
98%
64%
50%

37%

53%

97%
46%
40%

55%
73%

56%

53%
66%
98%
26%
29%

68%
98%
64%
60%
11%

EDTMPA HMDP

HEDP

NTP
HPAA
Phosphonate

OMTHP DETPMP HMTPMP

PPCA

PVS

VS-Co
Polymer

PFC

SPPCA

Fig. 1622-hour %Synergy values, calculated by Eq. 4.

Acknowledgement
The authors would like to thank the following sponsors of the
Flow Assurance and Scale Team Joint-Industry Project at HeriotWatt University for their support: Baker Hughes, BG Group, BP,
BWA Water Additives, Chevron, Clariant, ConocoPhillips,
Equion, Foundation CMG, GALP, MI Swaco, Multi-Chem,
MWV, Nalco-Champion, Nexen, Petrobras, Petronas, PTT, REP,
Shell, Statoil, Talisman Energy, ThermPhos, and Total. We would
22

also like to thank the anonymous reviewer who tabulated our

results in Figs. 1, 13, 14, 15, and 16, and kindly supplied us with
the spreadsheet.
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Appendix A
See Tables A-1 and A-2.

SI

SI Type

[SI]s (ppm)

2-hour IEs (%)

22-hour IEs (%)

OMTHP

Phosphonate

2, 4, 6, 8

22, 48, 81, 94

25, 46, 69, 82

DETPMP

Phosphonate

2, 4, 6, 8, 10, 20, 30

4, 18, 39, 56, 64, 93, 96

3, 19, 36, 48, 44, 73, 84

HMTPMP

Phosphonate

4, 6, 8, 10, 12, 20, 30

6, 7, 10, 19, 21, 90, 95

0, 0, 0, 0, 2, 23, 50

HMDP

Phosphonate

10, 20, 30

6, 23, 93

0, 4, 12

EDTMPA

Phosphonate

10, 20, 30

56, 81, 91

26, 56, 80
0, 3, 8, 12, 20, 25

NTP

Phosphonate

10, 20, 30, 40, 50, 60

9, 18, 24, 33, 53, 73

HEDP

Phosphonate

10, 20, 30

6, 8, 96

1, 7, 21

HPAA

Phosphonate

10, 20, 30, 40, 50, 60

2, 6, 10, 19, 21, 23

0, 1, 5, 7, 9, 11

PPCA

Polymer

10, 20, 30

75, 92, 94

17, 28, 34

SPPCA

Polymer

10, 20, 30

54, 79, 86

12, 14, 13

VS-Co

Polymer

10, 20, 30

58, 80, 92

26, 40, 58

PFC

Polymer

10, 20, 30

52, 75, 93

20, 22, 37

PVS

Polymer

10, 20, 30

47, 62, 70

15, 19, 21

Table A-1Individual scale-inhibitor (SI) barite-inhibition efficiencies (IEs).

Test
Number

SI Blend

SI Blend Combination

[SI]s (ppm)

2-hour IEs (%)

22-hour IEs (%)

DETPMP + HMTPMP

Phosphonate/Phosphonate

5+5, 10+10, 15+15

87, 96, 97

84, 96, 96

DETPMP + EDTMPA

Phosphonate/Phosphonate

5+5, 10+10, 15+15

69, 95, 100

56, 92, 94

DETPMP + HMDP

Phosphonate/Phosphonate

5+5, 10+10, 15+15

61, 95, 94

57, 92, 96

DETPMP + HEDP

Phosphonate/Phosphonate

5+5, 10+10, 15+15

44, 94, 95

45, 92, 93

HMTPMP + EDTMPA

Phosphonate/Phosphonate

5+5, 10+10, 15+15

56, 96, 96

22, 93, 96

HMTPMP + HMDP

Phosphonate/Phosphonate

5+5, 10+10, 15+15

7, 82, 94

0, 9, 15

EDTMPA + HMDP

Phosphonate/Phosphonate

5+5, 10+10, 15+15

37, 95, 94

14, 90, 98

EDTMPA + HEDP

Phosphonate/Phosphonate

5+5, 10+10, 15+15

43, 90, 94

45, 84, 94

NTP + HEDP

Phosphonate/Phosphonate

5+5, 10+10, 15+15

2, 14, 98

0, 4, 61

10

NTP + HPAA

Phosphonate/Phosphonate

20+20, 25+25, 30+30

25, 89, 94

8, 51, 95

11

HEDP + HPAA

Phosphonate/Phosphonate

5+5, 10+10, 15+15

3, 7, 15

1, 6, 13

12

OMTHP + DETPMP

Phosphonate/Phosphonate

1+1, 2+2, 3+3, 4+4

11, 42, 57, 86

12, 42, 52, 74

13

OMTHP + HMTPMP

Phosphonate/Phosphonate

2+2, 3+3, 4+4, 5+5, 6+6

37, 67, 92, 97, 99

40, 54, 89, 93, 89

14

DETPMP + PPCA

Phosphonate/Polymer

5+5, 10+10, 15+15

66, 86, 93

40, 61, 81

15

HMTPMP + PPCA

Phosphonate/Polymer

5+5, 10+10, 15+15

81, 97, 96

30, 49, 85

16

EDTMPA + PPCA

Phosphonate/Polymer

5+5, 10+10, 15+15

70, 92, 94

30, 46, 73

17

HMDP + PPCA

Phosphonate/Polymer

5+5, 10+10, 15+15

59, 94, 93

18, 44, 67

18

DETPMP + PVS

Phosphonate/Polymer

5+5, 10+10, 15+15

48, 85, 97

19, 40, 51

19

HMTPMP + PVS

Phosphonate/Polymer

5+5, 10+10, 15+15

76, 95, 95

33, 61, 71

20

EDTMPA + PVS

Phosphonate/Polymer

5+5, 10+10, 15+15

64, 90, 93

26, 54, 55

21

HMDP + PVS

Phosphonate/Polymer

5+5, 10+10, 15+15

57, 92, 98

19, 24, 31

22

HEDP + PVS

Phosphonate/Polymer

5+5, 10+10, 15+15

44, 77, 96

16, 21, 30

23

DETPMP + VS-CO

Phosphonate/Polymer

5+5, 10+10, 15+15

59, 92, 94

45, 76, 83

24

HMTPMP + VS-CO

Phosphonate/Polymer

5+5, 10+10, 15+15

81, 94, 94

64, 93, 94

25

EDTMPA + VS-CO

Phosphonate/Polymer

5+5, 10+10, 15+15

66, 91, 97

48, 79, 91

26

HMDP + VS-CO

Phosphonate/Polymer

5+5, 10+10, 15+15

71, 97, 95

36, 91, 96

27

NTP + VS-CO

Phosphonate/Polymer

5+5, 10+10, 15+15

52, 88, 90

37, 53, 82
32, 76, 91

28

HEDP + VS-CO

Phosphonate/Polymer

5+5, 10+10, 15+15

45, 94, 98

29

DETPMP + PFC

Phosphonate/Polymer

5+5, 10+10, 15+15

54, 92, 95

39, 75, 89

30

HMTPMP + PFC

Phosphonate/Polymer

5+5, 10+10, 15+15

71, 93, 94

66, 96, 100

31

EDTMPA + PFC

Phosphonate/Polymer

5+5, 10+10, 15+15

62, 85, 96

47, 67, 86

32

HMDP + PFC

Phosphonate/Polymer

5+5, 10+10, 15+15

62, 95, 93

46, 88, 96

33

HEDP + PFC

Phosphonate/Polymer

5+5, 10+10, 15+15

37, 87, 96

31, 65, 93

34

PPCA + SPPCA

Polymer/Polymer

5+5, 10+10, 15+15

59, 76, 92

13, 14, 15

Table A-2SI-blend barite IEs.

24

February 2015 SPE Production & Operations

ID: jaganm Time: 16:20 I Path: S:/3B2/PO##/Vol00000/140028/APPFile/SA-PO##140028

PO169752 DOI: 10.2118/169752-PA Date: 13-February-15

Scott Shaw is a research associate within the Flow Assurance

and Scale Team (FAST) at the Institute of Petroleum Engineering at Heriot-Watt University, Edinburgh. His research interests
include oilfield scale control, barium sulfate inhibition efficiency, metal/scale-inhibitor interactions, and chemicalanalysis techniques. Shaw has authored 15 technical papers
to datefour of which were peer reviewed. He holds a BSc
degree in applied chemistry from Edinburgh Napier University
and a PhD degree in petroleum engineering from HeriotWatt University. Shaw is a member of SPE and the National

Stage:

Page: 25

Total Pages: 10

Association of Corrosion Engineers. email: Scott.Shaw@pet.

hw.ac.uk.
Ken Sorbie is the principal investigator within FAST at the Institute of Petroleum Engineering at Heriot-Watt University. His
research interests include oilfield chemistry, reservoir characterization, and fundamentals of multiphase-fluid flow in porous
media. Sorbie holds a degree in chemistry from Strathclyde
University and a PhD degree in theoretical chemistry and
applied mathematics from Sussex University. He has served on
several SPE committees. email: Ken.Sorbie@pet.hw.ac.uk.

February 2015 SPE Production & Operations

ID: jaganm Time: 16:20 I Path: S:/3B2/PO##/Vol00000/140028/APPFile/SA-PO##140028

25