SPE 50717
Factors Affecting the Thermal Stability of Conventional Scale Inhibitors for Application
in High Pressure/High Temperature Reservoirs
S.J. Dyer, G.M. Graham, SPE, K.S. Sorbie, SPE, Heriot-Watt University
Copyright 1999, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 1999 SPE International Symposium on
Oilfield Chemistry held in Houston, Texas, 16–19 February 1999.
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Abstract
Following an earlier paper (SPE 37274, 1997),1 we have
continued to investigate the thermal stability of scale inhibitors
for application in high pressure/high temperature (HP/HT)
reservoirs. HP/HT reservoirs are currently under development
in the North Sea and are characterised by high salinity brines
(TDS > 300,000 ppm) high temperatures (T > 175°C) and high
pressures (12,000 - 15,000 psi, ~ 800 - 1050 bar). At present
produced brines are treated with scale inhibitors to prevent
mineral scale deposition within tubulars and topside
equipment. However, the conventional polymer and
phosphonate scale inhibitors currently being used may not be
appropriate for application in the harsh HP/HT reservoirs.
In this work, results are presented from static thermal
stability tests conducted on conventional polymer and
phosphonate scale inhibitors including phosphino-
polycarboxylate (PPCA), polyvinyl sulphonate (PVS), penta-
phosphonate (DETPMP) and hexa-phosphonate (TETHMP).
The stability of the scale inhibitors has been considered at
temperatures ranging from 120°C to 200°C and other factors
which may affect thermal stability have also been investigated,
including solution pH and the presence of oxygen radicals,
iron and common cations (Na+, Ca2+, Mg2+) in the inhibitor
solution. The results from this work demonstrate how factors
such as pH and brine composition control thermal stability.
Furthermore, the controlling influence of certain factors, such
as solution pH, affect different species differently. This work
assists in the selection of scale inhibitors for use in HP/HT
applications.
Background and Introduction
With the development of a number of new HT/HP fields in the
North Sea, for example ETAP (Eastern Trough Area Project),
Elgin/Franklin and Shearwater reservoirs, a number of
important “scale” control problems are expected. These
HT/HP reservoirs are characterised by very high salinity brines
(TDS up to 300,000+ ppm), high temperatures (T > 175°C)
and pressures in the range 12,000 to 15,000 psi (~ 800 - 1,000
bar). A variety of inorganic precipitates are expected in the
new HP/HT reservoirs, which include the common oilfield
scales such as the insoluble barium/strontium/calcium
sulphates and calcium/magnesium carbonates. In addition, the
very high salinity (HS) of several of the formation brines (TDS
> 300,000 ppm) can result in halite drop-out (NaCl(s)) either
as a result of water flash-off into the gas phase as pressure
decreases during production or simply due to reduced halite
solubility as the temperature declines during production.1,2
Common Scales. In many of the new HT/HP reservoirs,
natural depletion will be used as the main recovery
mechanism. This effectively removes the possibility of
sulphate scale in producers. However, if continual injection
“wash-water” is deployed in order to dilute the produced
formation brine and prevent halite precipitation, this may lead
to a sulphate scaling problem in the production tubulars and
topside equipment. This can be resolved by incorporating an
appropriate scale inhibitor into the wash-water brine.
However, in addition to its ability to prevent scale formation in
such scenarios, the thermal stability in aqueous solution and
the brine compatibility of the scale inhibitor will be of
paramount importance.
Carbonate scales may also form during the life of these
HP/HT fields. As reservoir pressure gradually decreases, the
carbon dioxide bubble point will occur at points successively
lower down the production string. Carbonate scale formation
above the perforations can be controlled in a similar manner to
that described above by incorporation of suitable scale
inhibitors into the wash water system. Ultimately carbonate
scaling problems are expected to occur in the near-wellbore
formation, which would necessitate the use of scale squeeze
chemicals. However, since the bubble point for CO2 is
considerably less than 10,000 psi in these systems, it will by
2 S.J. DYER, G.M. GRAHAM, K.S. SORBIE
then be a HT/moderate pressure system. Note: the carbon
dioxide bubble point at Heron reservoir (in the ETAP
complex, North Sea) temperature is predicted to be ~ 4,400
psi.2,4 For squeeze inhibitor chemicals, thermal stability and
brine compatibility become even more important issues than
for “wash water” chemicals. This is because (i) the inhibitor
species would be expected to survive in the formation for
extended periods of time (squeeze lifetime); and (ii) for natural
depletion production scenarios, high concentrations of the
inhibitor species would have to be compatible in the very high
salinity formation brines.
Current Scale Inhibitor Technology. It is important to
determine whether scale inhibitor species currently applied in
more conventional reservoirs will have any application in these
more severe HP/HT conditions. In particular, thermal stability
and brine compatibility issues are likely to be controlling
factors in the selection and application of inhibitor chemicals
in these harsh conditions.1-7 Previous work has shown that
phosphonate based inhibitor species may not be applicable due
to poor thermal stability,1,3,6 although some studies have
indicated less dramatic results for certain phosphonates.7,8
Furthermore, the thermal stability of polycarboxylate species
at 175°C are controlled by test solution pH and brine
salinity.1,3 More recent work has examined the thermal
stability of selected poly vinyl sulphonate (PVS) and
sulphonated co-polymer (VS-Co)4,5,9 inhibitor species at
temperatures up to 200°C. The results indicate that improved
thermal stability is observed for the sulphonated polymer
chemistries. Furthermore, their thermal stability at these
elevated temperatures is still somewhat controlled by solution
pH and brine salinity, in an analogous manner to that reported
for polycarboxylate species.1,3,9 In addition, certain PVS and
VS-Co inhibitor species have been shown to exhibit
significantly better compatibility in the very high salinity
formation brines than other polycarboxylate species.3,4,9 It is
therefore considered that sulphonated species, including
selected PVS and VS-Co inhibitors, may be the most
appropriate species, for scale control under HP/HT field
conditions.3,4,9
Outline of the Current Study
Previous work has examined the effect of thermal ageing at
175°C and 200°C on the barium sulphate inhibition efficiency
of phosphino-polycarboxylate (PPCA), polyvinyl sulphonate
(PVS), sulphonated co-polymer (VS-Co), penta-phosphonate
(DETPMP) and hexa-phosphonate (TETHMP) inhibitor
species.1 This thermal ageing was conducted on both solid
inhibitor species and in aqueous solutions of the scale
inhibitors. The pH of the samples in solution was both the
“supplied” pH and at adjusted values in the range pH 2 - 6.1,9
In this paper we consider the thermal stability of the generic
scale inhibitors PPCA, PVS and DETPMP at temperatures
ranging from 120°C to 200°C with the inhibitor solution
initially adjusted to pH 2 - 6. We also consider the effect of
SPE 50717
other factors on thermal stability, including the presence of
oxygen radicals, iron and common cations (Na+, Ca2+, Mg2+) in
the inhibitor solution.
Hexa-phosphonate (TETHMP) was not included in the
testing as previous work has suggested that its thermal stability
was similar to DETPMP.1 This work was undertaken to
determine which generic scale inhibitors are most suited for
application in high temperature reservoirs and under what
conditions their scale inhibition efficiency will be reduced.
Experimental Procedure
In this study three generically different scale inhibitors, PPCA,
PVS and DETPMP, were thermally aged in hydrothermal
bombs at various temperatures between 120°C and 200°C.
Different additives, such as hydrogen peroxide, iron containing
crushed core and swarf and various cations were incorporated
into the inhibitor solutions to determine their effect on the
thermal stability of the inhibitors.
Thermal Stability Tests. Thermal ageing of the inhibitor
species was performed in Teflon lined stainless steel
hydrothermal bombs, as described previously.1,3 The relevant
inhibitor was dissolved in either sea water (SW), distilled
water (DW) or a solution containing specific cations (10,000
ppm sodium, 500 ppm calcium or 2,000 ppm magnesium), to
give a solution of 1,000 ppm active. Lithium chloride (50
ppm) was also added to this solution to act as a tracer. The
solutions were split into 150 ml aliquots and the pH adjusted
with HCl and NaOH to that required (between pH 2 and 6).
In certain tests, hydrogen peroxide (1 ml/L, 30% solution)
was added to the solution and in other experiments, crushed
Upper Skagerrak core material (0.5 g/bomb) and stainless steel
swarf (0.5 g/bomb) were added. These substances were added
in order to induce more severe catalysed oxidative degradation
conditions.10
The Teflon cups were weighed, 30 ml of each test solution
was placed in the cups and the cups were re-weighed. The
cups were also re-weighed following the addition of the
crushed core and swarf. The solutions were blanketed (not
sparged) with nitrogen and the cups were sealed. The Teflon
cups were then placed in the hydrothermal bombs and sealed
tightly. The bombs were placed in an oven for 5 days at the
appropriate temperature. Following this thermal ageing
process, the “bombs” were allowed to cool to room
temperature and evaluated as described below.
Thermal Stability Evaluation - Comparative Inhibition
Performance. Following thermal ageing, the samples were
made up to the starting volume of ~ 30 ml. Note: slight
evaporation may have caused a small reduction in volume.
However, if significant evaporation (> 25% of volume) had
occurred, the sample was discarded. The samples and original
stocks (non-thermally aged) were then analysed for the
presence of lithium tracer by ICP (Inductively Coupled
Plasma) Spectroscopy. This process allows for any slight
SPE 50717 FACTORS AFFECTING THE THERMAL STABILITY OF CONVENTIONAL SCALE INHIBITORS FOR APPLICATION IN HIGH
PRESSURE/HIGH TEMPERATURE RESERVOIRS
evaporation effects to be accounted for accurately. Any
difference in [Li] can then be adjusted during the dilution step
prior to comparative barium sulphate inhibition efficiency
testing.
Comparative inhibition efficiency tests were then
conducted, as described elsewhere,1,9,11 in order to compare the
barium sulphate inhibition efficiency of the thermally aged
inhibitor samples with that of their respective stock samples
(non-thermally aged). The inhibition efficiency tests were
performed in the moderate/severe barium sulphate scaling
brine mix of 50:50 sea water (SW) and Forties type formation
water (FW) at 95°C, with the solutions buffered to pH 5.5. The
calcium level of Forties brine was reduced from 5,000 ppm to
2,000 ppm due to inhibitor/brine compatibility issues.1
Inhibitor concentrations in the range 8 - 10 ppm (active) were
examined in this brine mixture in order to give a reasonable
level of performance (40 - 80% efficiency at 2 hours residence
time). A summary of the tests conducted in this study is
presented in Table 1 and the compositions of the brines used
are shown in Table 2. Note: as described previously,1,6,9 in
these studies it is not the absolute inhibitor performance with
which we are primarily concerned, but rather the change in
performance of the thermally aged sample when compared
with its respective stock (non-thermally aged) sample.
Thermal Stability Results
PPCA.
Effect of pH at 180°C and 200°C. Figure 1 presents the
comparative thermally aged (180°C and 200°C) vs. non-
thermally aged (stock) barium sulphate inhibition efficiencies
for PPCA in sea water at pH 2 - 6. From Figure 1 it is evident
that thermally ageing the PPCA at 180°C at pH 5 and 6 did not
alter its inhibition efficiency. However, thermal ageing at
180°C at pH 3 and 4 led to complete loss of performance and
at pH 2 led to a partial reduction in performance. When
thermal ageing was carried out at 200°C the inhibition
performance of the PPCA was further reduced at pH 5 and 6.
This led to a partial reduction in performance and at pH 2 - 4 it
led to complete loss of inhibition efficiency. At both
temperatures the inhibition performance of the PPCA after
thermal ageing was strongly dependent on initial pH.
Effect of Oxygen Radicals (Hydrogen Peroxide). Figure 2
presents the comparative thermally aged (180°C) vs. non-
thermally aged (stock) barium sulphate inhibition efficiencies
for PPCA in sea water at pH 2 - 6 with hydrogen peroxide
added (to act as a source of oxygen radicals to initiate
oxidative degradation). From Figure 2 it can be seen that
thermally ageing PPCA with hydrogen peroxide led to the
complete loss of inhibition efficiency at pH 2 - 4 and to the
partial loss of inhibition efficiency at pH 5 and 6. As with the
thermal stability tests at different temperatures, the effect of
hydrogen peroxide was strongly dependent on the initial
solution pH.
3
Effect of Iron (Core and Swarf). Figure 3 presents the
comparative thermally aged (180°C) vs. non-thermally aged
barium sulphate inhibition efficiencies for PPCA in sea water
at pH 2, 4 and 6 with iron added (from crushed core and
swarf), to act as a catalyst for oxidative degradation. From
Figure 3 it can be seen that thermally ageing PPCA with iron
at an initial pH of 6, did not reduce the inhibition performance
and, as expected from previous results (Figure 1) complete
loss of inhibition efficiency was observed for the PPCA with
an initial pH of 4. However, at an initial pH of 2, thermal
ageing of PPCA in the presence of iron, led to a complete loss
of inhibition efficiency, whereas only a partial reduction in
inhibition efficiency had been observed after thermal ageing
without iron present (see Figure 1). The concentration of iron
in solution after thermal ageing is given in Table 3 and from
this it can be seen that as pH decreased, so the iron
concentration in solution increased. Hence, the loss of
inhibition efficiency observed for the pH 2 sample
corresponded to an increase in solution iron concentration.
Related work at this laboratory indicates that the presence of
iron in this brine system would reduce the performance of
PPCA.
Effect of Solution Cations. Figure 4 presents the
comparative thermally aged (180°C) vs. non-thermally aged
barium sulphate inhibition efficiencies for PPCA in distilled
water and in a 10,000 ppm sodium solution (similar to sea
water concentration) at pH 2 - 6. From Figure 4 it is evident
that thermally ageing PPCA in distilled water led to an almost
complete loss of inhibition efficiency at all pH values.
However, when the PPCA was thermally aged in the 10,000
ppm sodium solution, the inhibition performance was similar
to that observed after thermal ageing in sea water (Figure 1).
Figure 5 presents the comparative thermally aged (180°C)
vs. non-thermally aged barium sulphate inhibition efficiencies
for PPCA in a 500 ppm calcium solution (similar to
concentration in sea water) and a 2,000 ppm magnesium
solution. From this figure it can be seen that thermally ageing
PPCA in these solutions led to a similar inhibition efficiency
as that observed for the thermal ageing of PPCA in sea water
and a 10,000 ppm sodium solution.
PVS.
Effect of pH at 180°C and 200°C. Figure 6 presents the
comparative thermally aged (180°C and 200°C) vs. non-
thermally aged (stock) barium sulphate inhibition efficiencies
for PVS in sea water at pH 2 - 6. From Figure 6 it can be seen
that the inhibition efficiency of PVS was not significantly
reduced by thermal ageing at either 180°C or 200°C at any pH
examined.
Effect of Oxygen Radicals (Hydrogen Peroxide). Figure 7
presents the comparative thermally aged (180°C) vs. non-
thermally aged barium sulphate inhibition efficiencies for PVS
in sea water at pH 2 - 6 with hydrogen peroxide added (to act
as a source of oxygen radicals). From Figure 7 it can be seen
4 S.J. DYER, G.M. GRAHAM, K.S. SORBIE
that the inhibition efficiency of PVS was partially reduced by
thermal ageing at all pH values examined.
Effect of Iron (Core and Swarf). Figure 8 presents the
comparative thermally aged (180°C) vs. non-thermally aged
barium sulphate inhibition efficiencies for PVS in sea water at
pH 2, 4 and 6 with iron added (from crushed core and swarf),
to act as a catalyst for oxidative degradation. From Figure 8 it
can be seen that thermally ageing PVS with iron, at any of the
initial pH values, did not significantly reduce the inhibition
efficiency. The concentration of iron in solution after thermal
ageing is given in Table 3 and from this it can be seen that, as
for PPCA, decreasing the pH increased the iron concentration
in solution. However, related work at this laboratory has
shown that the presence of iron in this brine system does not
influence the performance of PVS.
Effect of Solution Cations. Figure 9 presents the
comparative thermally aged (200°C) vs. non-thermally aged
barium sulphate inhibition efficiencies for PVS in distilled
water and a 10,000 ppm sodium solution (similar to sea water
concentration) at pH 2 - 6. From Figure 9 it can be seen that
decreasing the initial pH form 5 to 2 reduced the inhibition
efficiency of the PVS when thermally aged in distilled water.
However, when the PVS was thermally aged in a 10,000 ppm
sodium solution the inhibition efficiencies at all initial pH
values were similar to those of the stock solutions. Hence, in
the sodium solution, the inhibition efficiency of PVS was
similar to that observed when the PVS was thermally aged in
sea water (Figure 6).
Figure 10 presents the comparative thermally aged (180°C)
vs. non-thermally aged barium sulphate inhibition efficiencies
for PVS in a 500 ppm calcium solution (similar concentration
to sea water) and a 2,000 ppm magnesium solution. From this
figure it can be seen that thermally ageing PVS in these
solutions led to a similar reduction in performance as that
observed for the thermal ageing of PVS in distilled water and
not sea water.
DETPMP.
Effect of pH at 120°C, 130°C and 150°C. Figure 11
presents the comparative thermally aged (120°C, 130°C and
150°C) vs. non-thermally aged (stock) barium sulphate
inhibition efficiencies for DETPMP in sea water at pH 2 - 6.
From Figure 11 it can be seen that when DETPMP was
thermally aged at 120°C, the inhibition efficiency at pH 2 - 5
was similar to that of the stock solutions. However, at pH 6
the inhibition efficiency was partially reduced. Increasing the
temperature to 130°C resulted in partially reduced inhibition
efficiencies at all initial pH values, with the inhibition
performance decreasing as the pH increased. Thermal ageing
DETPMP at 150°C led to a complete loss of inhibition
efficiency at all pH values tested.
Effect of Distilled Water. Figure 12 presents the
comparative thermally aged (120°C) vs. non-thermally aged
barium sulphate inhibition efficiencies for DETPMP in
distilled water at pH 2 - 6. From Figure 12 it can be seen that
SPE 50717
thermally ageing DETPMP under these conditions resulted in
a complete loss of inhibition efficiency at all pH values tested.
Discussion
Temperature and pH. The results presented above indicate
that as the temperature is increased from 180°C to 200°C, so
the inhibition performance of thermally aged PPCA decreases.
That is, the PPCA degrades more as the temperature increases,
as has been suggested previously.1 However, the inhibition
efficiency of the PPCA after thermal ageing at both
temperatures, is strongly influenced by the initial solution pH,
with the greatest reduction in inhibition efficiency occurring in
the intermediate pH range of 3 - 4. Previous work has
indicated that PVS is thermally stable up to 200°C1 and the
results for PVS also show that the inhibition efficiency at all
pH values tested, is not reduced when the temperature is
increased from 180°C to 200°C.9 Hence, PVS is more suited
for application in high temperature reservoirs (180°C to
200°C) than PPCA, particularly as the pH does not have to be
carefully controlled. However, tests in lower salinity brines
(distilled water) do indicate a relationship between thermal
stability and ageing pH (see below).
As with PPCA, the inhibition performance of DETPMP
decreases as the temperature of thermal ageing is increased
from 120°C to 130°C and 150°C. Also the inhibition
efficiency of the DETPMP is strongly dependent on the pH of
the initial solution. However, with DETPMP the inhibition
efficiency decreases as the pH increases from pH 2 to 6. The
complete loss of inhibition efficiency for DETPMP after
thermal ageing at 150°C indicates that, as previously
observed,1,4,7 it is less thermally stable than either PPCA or
PVS and is therefore less suited for application in high
temperature fields.
Oxidative Degradation. The addition of hydrogen peroxide, to
induce oxidative degradation10 in the thermal ageing solution,
decreases the inhibition efficiency of PPCA. As with the effect
of temperature, this reduction in performance is strongly
dependent on initial solution pH. However, when PVS is
thermally aged in the presence of hydrogen peroxide, the
inhibition efficiency of the PVS at all pH values is partially
reduced.9 Therefore, although the effect of oxidative degradation
on PPCA is strongly dependent on pH, for PVS it is independent
of solution pH. It is thought that oxidative degradation by
oxygen radicals is one of the potential mechanisms for the
degradation of both PVS and PPCA inhibitor species. Note: the
hydrogen peroxide concentration used in these tests was
considerably higher than would be expected in the field, where
oxygen levels would be minimised (reducing environment),
although other free radicals may be of more importance.
Iron Catalysed Inhibitor Degradation. The addition of iron
to the thermal ageing solution, from either crushed core or
swarf, leads to a reduction in the inhibition efficiency of PPCA
with an initial pH of 2. This reduction in inhibition efficiency
SPE 50717 FACTORS AFFECTING THE THERMAL STABILITY OF CONVENTIONAL SCALE INHIBITORS FOR APPLICATION IN HIGH
PRESSURE/HIGH TEMPERATURE RESERVOIRS
corresponds to a significant increase in solution iron
concentration (∼ 20 ppm). However, a similar increase in
solution iron concentration did not effect the inhibition
efficiency of PVS when thermally aged at pH 2. No reduction
in inhibition efficiency is observed after thermal ageing at pH
6 for either PVS or PPCA or pH 4 for PVS, but at these pH
values only a very small amount of iron was released into
solution (< 4 ppm). The results at pH 2 indicate that at 180°C
the inhibition efficiency of PPCA is reduced due to the effect
of iron affecting its performance.
Thermal Stability from Solution Cations. The thermal
ageing tests indicated that for all three inhibitor species,
inhibition efficiency is reduced when the inhibitor is dissolved
in distilled water rather than sea water. This suggests that the
ions in sea water are stabilising the inhibitor species and
reducing thermal degradation.9 It is postulated that the
functional groups in the inhibitor molecules are complexing
with the brine cations present in sea water and this stabilises
the inhibitor molecules in such a way as to render them less
susceptible to thermal degradation, by preventing hydrolysis
reactions from occurring. The thermal ageing tests conducted
with PVS and PPCA dissolved in solutions of 10,000 ppm
sodium (similar concentration to sea water) indicate that the
stability and hence inhibition efficiency, of the inhibitors after
thermal ageing in sea water, is due to the presence of the
sodium ions in solution. Further tests also indicate that
solutions of 500 ppm calcium and 2,000 ppm magnesium
stabilise the PPCA inhibitor species, but they do not increase
the stability of PVS above that observed in distilled water.
Conclusions
The results from this study can be summarised as follows:
1. The inhibition efficiencies of thermally aged PPCA and
DETPMP are strongly dependent on pH, as well as temperature.
2. The inhibition efficiency of PPCA is further reduced
when it is thermally aged at 180°C, in the presence of
hydrogen peroxide, which act as catalysts for oxidative
degradation and iron.
3. PVS is thermally stable up to 200°C at pH 2 - 6. This
inhibition efficiency is reduced when PVS is thermally aged in
the presence of hydrogen peroxide at 180°C, but not in the
presence of iron.
4. The inhibition efficiencies of PVS and PPCA are reduced
when they are thermally aged in distilled water, rather than sea
water. The improved stability observed in sea water is due to
sodium ions stabilising the inhibitor species. Calcium and
magnesium also stabilise PPCA, but not PVS at the
concentrations tested here.
5. When applying inhibitor species in HP/HT environments,
care must be taken to ensure that the application conditions,
such as temperature, pH, cation composition of solution
(including iron) and presence of oxygen radicals, will not
reduce the inhibition efficiency of the selected scale inhibitor.
5
Nomenclature
DETPMP = Diethylene triamine pentamethylene phosphonate
PPCA = Poly phosphino carboxylic acid
PVS = Poly vinyl sulphonate
HP/HT = High Pressure/High Temperature
HS = High Salinity
TDS = Total Dissolved Solids
Acknowledgments
We would like to thank the Production Chemistry Department,
Technical Services Division of Shell UK. Exploration and
Production and the CMPT (EPSRC Ref: GR/K69509, CMPT
Ref: RES045) for funding this study. We would like to thank
Gordon C. Graham, formally of Shell UK. Exploration and
Production (currently Nalco Exxon Energy Chemicals) and
Willem Sablerolle of Shell International for their support and
helpful discussions.
References
1. Graham, G.M., Jordan, M.M., Graham, G.C., Sablerolle, W.,
Sorbie, K.S., Hill, P. and Bunney, J.: “The Implication of
HP/HT Reservoir Conditions on the Selection and Application
of Conventional Scale Inhibitors: Thermal Stability Studies,”
paper SPE 37274, presented at the 1997 SPE International
Symposium on Oilfield Chemicals, held in Houston, TX, Feb.
18-21.
2. Jasinski, R., Sablerolle, W., Amory, M.: “ETAP: Scale
Prediction and Control for the Heron Cluster,” paper SPE
38767 presented at the 1997 SPE Annual Technical Conference
and Exhibition, San Antonio, TX, Oct. 5-8.
3. Graham, G.M., Graham, G.C., Jordan, M.M., Sorbie, K.S., Hill,
P., Dyer, S.J., and Littlehales, I.: “The Influence of High
Temperature and High Salinity Conditions on the Testing and
Potential Application of Scale Inhibitors Under Harsh HP/HT
Reservoir Conditions”, presented at the 1997 NIF 8th
International Oil Field Chemical Symposium, Geilo, Mar. 2-5.
4. Graham, G.M., Dyer S.J., Sorbie, K.S., Sablerolle, W.R., Shone,
P. and Frigo, D.: “Scale Inhibitor Selection for Continuous and
Downhole Squeeze Application in HP/HT Conditions”, paper
SPE 49197 prepared for the 1998 SPE Annual Technical
Conference and Exhibition, New Orleans, LA, Sept. 27-30.
5. Collins, I..: “Scale Inhibition at High Reservoir Temperature”,
presented at the 1995 Advances in Solving Oilfield Scaling,
Aberdeen, Nov.
6. Jordan, M.M., Sorbie, K.S., Graham, G.M., Taylor, K. and
Hennessey, S.: “The Implications of HP/HT Reservoir
Conditions on the Selection and Application of Scale Inhibitors
- Some Preliminary Results,” presented at the 1996 NIF 7th
International Oil Field Chemicals Symposium, Geilo, Mar. 17-
20.
7. Grüner H.P.: “Downhole Scale Control in a High Temperature
and High Calcium Environment,” presented at the 1996 NIF 7th
International Oil Field Chemicals Symposium, Geilo, Mar. 17-
20.
6 S.J. DYER, G.M. GRAHAM, K.S. SORBIE SPE 50717

8. Brockmann, R., Bache, O., Asheim, T.I., Feasey, N.D. and
Jordan, M. “CaCO3 Inhibition Efficiency and Thermal Stability
of Generically Different Scale Inhibitors for High Temperature
Conditions,” presented at the 1998 NIF 9th International Oil
Field Chemicals Symposium, Geilo, Mar. 22-25.
9. Graham G.M., Dyer S.J., Sablerolle W., Graham G.C., and
Sorbie K.S.: (1998) “Practical Solutions to Scaling in HP/HT
and High Salinity Reservoirs,” presented at the 1998 Advances
in Solving Oilfield Scaling Problems, Aberdeen, Jan. 28-29.
10. Wellington, S.L.: “Biopolymer Solution Viscosity Stabilisation
- Polymer Degradation and Antioxidant Use,” SPEJ, (December
1983) 901.
11. Graham G.M. (Editor): OSRG Laboratory Procedures Manual,
Version 2.0, Dept. of Petroleum Engineering, Heriot-Watt U.,
Edinburgh (Sept. 1995).

TABLE 1-SUMMARY OF TESTS UNDERTAKEN IN THIS STUDY

Inhibitor Temperature (°C) Solvent Additive pH
PPCA 180 Sea water .... 2, 3, 4, 5, 6
PPCA 200 Sea water .... 2, 3, 4, 5, 6
PPCA 180 Sea water Hydrogen peroxide 2, 3, 4, 5, 6
PPCA 180 Sea water Crushed core 2, 3, 4, 5, 6
PPCA 180 Sea water Swarf 2, 3, 4, 5, 6
PPCA 180 Distilled water .... 2, 3, 4, 5, 6
PPCA 180 Distilled water 10,000 ppm sodium 2, 3, 4, 5, 6
PPCA 180 Distilled water 500 ppm calcium 2, 3, 4, 5, 6
PPCA 180 Distilled water 2,000 ppm magnesium 2, 3, 4, 6
PVS 180 Sea water .... 2, 3, 4, 5, 6
PVS 200 Sea water .... 2, 3, 4, 5, 6
PVS 180 Sea water Hydrogen peroxide 2, 3, 4, 5, 6
PVS 180 Sea water Crushed core 2, 3, 4, 5, 6
PVS 180 Sea water Swarf 2, 3, 4, 5, 6
PVS 200 Distilled water .... 2, 3, 4, 5
PVS 200 Distilled water 10,000 ppm sodium 2, 3, 4, 5, 6
PVS 200 Distilled water 500 ppm calcium 2, 3, 4, 5, 6
PVS 200 Distilled water 2,000 ppm magnesium 2, 3, 4, 5, 6
DETPMP 120 Sea water .... 2, 4, 5, 6
DETPMP 130 Sea water .... 2, 3, 5, 6
DETPMP 150 Sea water .... 2, 3, 4, 5, 6
DETPMP 120 Distilled water .... 2, 3, 4, 5, 6
SPE 50717 FACTORS AFFECTING THE THERMAL STABILITY OF CONVENTIONAL SCALE INHIBITORS FOR APPLICATION IN HIGH
PRESSURE/HIGH TEMPERATURE RESERVOIRS 7

TABLE 2-BRINE COMPOSTITIONS USED IN

THIS STUDY
Ion Sea Water (ppm) Forties FW (ppm)
Sodium 10,890 31,275
Calcium 428 2,000
Potassium 460 654
Magnesium 1,368 739
Barium 0 269
Strontium 0 771
Sulphate 2,960 0
Chloride 19,766 60,848

TABLE 3-[IRON] RELEASED FROM CORE AND SWARF DURING THERMAL

AGEING
Inhibitor Sample Initial pH Initial [iron] (ppm) Final [iron] (ppm)
PPCA Thermally aged 2 0 0
PPCA Thermally aged with core 2 0 21.4
PPCA Thermally aged with swarf 2 0 8.7
PPCA Thermally aged 4 0 0
PPCA Thermally aged with core 4 0 1.9
PPCA Thermally aged with swarf 4 0 2.6
PPCA Thermally aged 6 0 0
PPCA Thermally aged with core 6 0 0.2
PPCA Thermally aged with swarf 6 0 0
PVS Thermally aged 2 0 0
PVS Thermally aged with core 2 0 25.2
PVS Thermally aged with swarf 2 0 15.2
PVS Thermally aged 4 0 0
PVS Thermally aged with core 4 0 0
PVS Thermally aged with swarf 4 0 3.6
PVS Thermally aged 6 0 0
PVS Thermally aged with core 6 0 2
PVS Thermally aged with swarf 6 0 1.9
 100

80

% Barium Sulphate Inhibition Efficiency

60

Stock for 180ûC

40
Thermally aged 180ûC
Stock for 200ûC
Thermally aged 200ûC

20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 1 Barium sulphate inhibition efficiency of stock and thermally aged (180ûC or 200ûC,
SW, 5 days, [SI] = 1,000ppm, various pH) PPCA. Comparative inhibition efficiency conditions:
50:50 Forties FW:SW, 95ûC, 2 hours residence time.

100

80
% Barium Sulphate Inhibition Efficiency

60

40
Stock
Thermally aged

20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 2 Barium sulphate inhibition efficiency of stock and thermally aged (180ûC, SW, 5 days,
[SI] = 1,000ppm, various pH) PPCA with added hydrogen peroxide. Comparative inhibition
efficiency conditions: 50:50 Forties FW:SW, 95ûC, 2 hours.

100

80
% Barium Sulphate Inhibition Efficiency

60

Stock
40
Thermally aged
Thermally aged + core
Thermally aged + swarf

20

0
pH 2 pH 4 pH 6
Thermal Ageing Solution pH
Figure 3 Barium sulphate inhibition efficiency of stock and thermally aged (180ûC, SW, 5 days,
[SI] = 1,000ppm, various pH) PPCA with added iron from core and swarf. Comparative
inhibition efficiency conditions: 50:50 Forties FW:SW, 95ûC, 2 hours.
 100

80

% Barium Sulphate Inhibition Efficiency

60

DW stock
40
DW thermally aged
Na stock
Na thermally aged

20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 4 Barium sulphate inhibition efficiency of stock and thermally aged (180ûC, DW or
10,000ppm Na, 5 days, [SI] = 1,000ppm, various pH) PPCA. Comparative inhibition efficiency
conditions: 50:50 Forties FW:SW, 95ûC, 2 hours residence time.

100

80
% Barium Sulphate Inhibition Efficiency

60

Excessive evaporation from

Ca stock
hydrothermal bomb

40
Ca thermally aged
Mg stock
Mg thermally aged

20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 5 Barium sulphate inhibition efficiency of stock and thermally aged (180ûC, 500ppm Ca
or 2,000ppm Mg, 5 days, [SI] = 1,000ppm, various pH) PPCA. Comparative inhibition
efficiency conditions: 50:50 Forties FW:SW, 95ûC, 2 hours residence time.

100

80
% Barium Sulphate Inhibition Efficiency

60

Stock for 180ûC

40
Thermally aged 180ûC
Stock for 200ûC
Thermally aged 200ûC

20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 6 Barium sulphate inhibition efficiency of stock and thermally aged (180ûC or 200ûC,
SW, 5 days, [SI] = 1,000ppm, various pH) PVS. Comparative inhibition efficiency conditions:
50:50 Forties FW:SW, 95ûC, 2 hours residence time.
 100

80

% Barium Sulphate Inhibition Efficiency

60

40 Stock
Thermally aged

20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 7 Barium sulphate inhibition efficiency of stock and thermally aged (180ûC, SW, 5 days,
[SI] = 1,000ppm, various pH) PVS with added hydrogen peroxide. Comparative inhibition
efficiency conditions: 50:50 Forties FW:SW, 95ûC, 2 hours.

100

80
% Barium Sulphate Inhibition Efficiency

60

Stock
40
Thermally aged
Thermally aged + core
Thermally aged + swarf

20

0
pH 2 pH 4 pH 6
Thermal Ageing Solution pH
Figure 8 Barium sulphate inhibition efficiency of stock and thermally aged (180ûC, SW, 5 days,
[SI] = 1,000ppm, various pH) PVS with added iron from core and swarf. Comparative
inhibition efficiency conditions: 50:50 Forties FW:SW, 95ûC, 2 hours.

100

80
% Barium Sulphate Inhibition Efficiency

60
Excessive evaporation from

DW stock
40
hydrothermal bomb

DW thermally aged
Na stock
Na thermally aged

20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 9 Barium sulphate inhibition efficiency of stock and thermally aged (200ûC, DW or
10,000ppm Na, 5 days, [SI] = 1,000ppm, various pH) PVS. Comparative inhibition efficiency
conditions: 50:50 Forties FW:SW, 95ûC, 2 hours residence time.
 100

80

% Barium Sulphate Inhibition Efficiency

60

Ca stock
40
Ca thermally aged
Mg stock
Mg thermally aged

20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 10 Barium sulphate inhibition efficiency of stock and thermally aged (200ûC, 500ppm Ca
or 2,000ppm Mg, 5 days, [SI] = 1,000ppm, various pH) PVS. Comparative inhibition efficiency
conditions: 50:50 Forties FW:SW, 95ûC, 2 hours residence time.

100

80
% Barium Sulphate Inhibition Efficiency

60

Stock for 120ûC

Excessive evaporation from

Excessive evaporation from

Thermally aged 120ûC

hydrothermal bomb

hydrothermal bomb

40
Stock for 130ûC
Thermally aged 130ûC
Stock for 150ûC
Thermally aged 150ûC
20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 11 Barium sulphate inhibition efficiency of stock and thermally aged (120ûC, 130ûC or
150ûC, SW, 5 days, [SI] = 1,000ppm, various pH) DETPMP. Comparative inhibition efficiency
conditions: 50:50 Forties FW:SW, 95ûC, 2 hours residence time.

100

80
% Barium Sulphate Inhibition Efficiency

60

40 Stock
Thermally aged

20

0
pH 2 pH 3 pH 4 pH 5 pH 6
Thermal Ageing Solution pH
Figure 12 Barium sulphate inhibition efficiency of stock and thermally aged (120ûC, DW, 5 days,
[SI] = 1,000ppm, various pH) DETPMP. Comparative inhibition efficiency conditions: 50:50
Forties FW:SW, 95ûC, 2 hours residence time.