SPE 164128

Factors Affecting the Stability of Scale Inhibitors Used for Capillary

Injection in High Temperature Wells
J. Rick Griffin SPE, James R. Johnstone SPE, Terry E. Cotter, and Ashleigh E. O'Brien, Kemira Chemicals Inc

Copyright 2013, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Symposium on Oilfield Chemistry held in The Woodlands, Texas, USA, 8–10 April 2013.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessar ily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohi bited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
In recent years, the percentage of oil production from more challenging environments has increased. In addition to the
numerous engineering and logistical difficulties of working at increased depth, temperature and pressure these production
zones provide a harsh environment deleterious to the performance of some critical oilfield chemicals. Scale inhibitors are one
class of oil field chemicals which are deployed through squeeze treatments into the formation and/or continuous downhole
injection for protection of production tubulars. As well depths continue to increase, the exposure time of the injected
chemicals also increases. With temperatures in the range of 180-200 °C and pressures exceeding 10,000 psi, the effect of
elevated temperature and pressure on scale inhibitor performance is a critical parameter to evaluate using chemical analytical
techniques and product performance methods.

Another trend leading to increased thermal exposure is the use of thermal enhanced recovery techniques. Scale inhibitors are
exposed to high temperatures in operations such as steam flooding and steam assisted gravity drainage (SAGD).

In this study, a range of chemicals have been evaluated for their short and medium-term thermal stability at 180 and 200 °C.
The primary application of this data is for downhole injection and squeeze treatments prior to adsorption. Inhibitor chemical
types include sulfonated polycarboxylic acid (SPCA), fluorescent tagged sulfonated polycarboxylic acid (FSPCA),
phosphorous tagged sulfonated polycarboxylic acid (PSPCA), sulfonated polyacrylocarboxylic acid (SPAC), polyacrylic acid
(PAA), polyvinyl sulfonate (PVS), polyamino polyether methylene phosphonate (PAPEMP), bis(hexamethylene)triamine
pentakis(methylene phosphonic acid) (BHTPMP) and diethylenetriamine pentakis(methylene phosphonic acid) (DTPMP). In
most cases the sodium or potassium salts of the inhibitors are used.

The chemical effect of temperature on scale inhibitors is measured through molecular weight determination,
thermogravimetric analysis (TGA), pH change, and Fourier Transform Infrared (FTIR) analysis. The performance of these
inhibitors is measured under static and dynamic conditions for inhibition of barium sulfate scale. These results help to further
the knowledge of inhibitor degradation due to thermal effects and indicate the direction for further product development of
thermally stable scale inhibitors.

Background/Introduction
World demand for oil and gas continues to increase and as easily obtained reserves become increasing depleted, production is
increasing in high temperature and pressure fields. Oilfields such as the Tiber Field in the Gulf of Mexico (Fan et al. 2010),
fields in the North Sea (Graham et al. 2002), and offshore Brazil encounter temperatures in excess of 175 °C, pressures of
12,000 to 15,000 psi, and total dissolved solids in excess of 300,000 mg/L. Formation of sulfate (barium, strontium, and
calcium), carbonate (calcium and magnesium) as well as halite has been experienced, indicating the need for scale inhibitor
deployment in these fields. In the area of steam flood operations Senthilmurugan, Ghosh et al. (2010) report serious scale
issues in the formation by calcium sulfate due to dissolution and redeposition due to the thermal front of the steam.

The objective of this study is to further the knowledge of the effect of temperature on scale inhibitors using various analytical
techniques combined with static and dynamic performance testing. The results help in selecting the best chemistry currently
2 SPE 164128

available as well as assisting in the development of more thermally stable scale inhibitors.

Jiang et al. (1998) describe the use of TGA/FTIR for the analysis of the degradation of poly(vinylsulfonic acid),
poly(vinylphosphonic acid) and their sodium salts. Based on the results of the analysis of the volatiles released during
degradation and the residues remaining after release of volatiles, a mechanism for the degradation of these polymers was
proposed. Although TGA analysis involves the dry form of the inhibitors rather than solutions found in oilfield applications,
the results indicate the relative thermal stability of the chemicals. This approach is one method used in this study for analysis
of scale inhibitor stability.

Graham, Jordan, et al. (1997) describe the degradation of polymeric inhibitors occurring by two mechanisms – scission of the
polymeric backbone and functional group degradation. Gel permeation chromatography (GPC) is used in this study to
examine the change in molecular weight distribution of the scale inhibitor polymers. Backbone scission should radically
effect the measured average molecular weight distribution and polydispersity. Fourier transform Infrared (FTIR) analysis is
used to measure the degree of functional group degradation.

Dynamic and static performance tests were conducted on the heated and unheated samples. The water chemistry chosen for
the performance testing was designed to be simple, including only the scaling ions and sodium chloride to measure the effects
of the chemical degradation of the scale inhibitors alone.

Thermal aging of the scale inhibitors was carried out primarily in a Teflon- lined Parr acid digestion bomb placed in an oven.
Some tests were also conducted by placing the scale inhibitor in 316 stainless steel capped tubes to evaluate the effect of
metal on the degradation. Dyer, Graham, et al. (1999) found that the presence of ions from seawater have a stabilizing effect
when used to dilute scale inhibitors. However, for this initial test on the chemical effect of thermal aging, no dilution was
done and the inhibitors were aged as supplied (other than pH adjustments and solids adjustment in one test).

To reduce the potential for degradation by oxygen radicals, the scale inhibitor solutions were sparged with nitrogen for 2
hours prior to testing. The oxygen content of the sample compartment headspace was also reduced in a similar manner. Dyer
and Graham (2002) reported that a low level of oxygen has a much less significant effect on thermal stability than other
factors such as solution pH. For this study therefore, no oxygen scavenger was used in the system .
SPE 164128 3

Experimental

Scale Inhibitors

Sulfonated polycarboxylic acid (SPCA), acid form and potassium salt

Fluorescent tagged sulfonated polycarboxylic acid (FSPCA), potassium salt

Phosphorous tagged sulfoanted polycarboxylic acid (PSPCA), potassium salt

Sulfonated polyacrylocarboxylic acid (SPAC), sodium salt

Polyacrylic acid (PAA), sodium salt

Polyvinyl sulfonate (PVS), sodium salt

Polyamino polyether methylene phosphonate (PAPEMP), sodium salt

Bis(hexamethylene)triamine pentakis(methylene phosphonic acid)) (BHTPMP)

Diethylenetriamine pentakis(methylene phosphonic acid) (DTPMP), sodium salt

All scale inhibitors samples were supplied by Kemira Chemicals Inc. except for PVS which was supplied by Aldrich
Chemicals; DTPMP and BHTPMP were supplied by Compass Chemicals.

The pH and percent actives of these various inhibitors are shown in Table 1. Where the effect of pH on the thermal stability
of the scale inhibitors is evaluated, pH adjustment is made by addition of 45% potassium hydroxide (RICCA Chemical,
Analytical grade) to the acid form of the inhibitor.

TGA Analysis. Samples were dried in an oven at 105 °C for one hour. Samples were run on a Mettler TGA/SDTA 851
analyzer under a 25 mL/min nitrogen purge without reactive gas. The temperature range was 50 to 400 °C with a heating
rate of 5 °C per minute.

Heat Treatment, Scale inhibitor solutions were aged either in a Parr acid digestion vessel equipped with a
polytetrafluoroethylene (PTFE) liner or in capped 316 stainless steel tubes and placed in an oven for the test period time.
Samples were removed from the oven and allowed to cool to room temperature before analysis. Oven solids were measured
before and after heat treatment and the appropriate adjustment made for percent active where necessary for the static and
dynamic performance testing. The starting and final pH of the samples was also measured.
4 SPE 164128

Molecular Weight. Samples were diluted to approximately 0.25% solids with 0.1 M sodium nitrate. The resulting
solutions were injected directly into the instrument (Waters 2690 Chromatograph with 2410 Refractive Index Detector)
GPC conditions:

Column: Waters Ultrahydrogel columns (120,250, and 500)

Detector: Refractive Index

Eluent: 0.1 M NaNO3 with 0.05% NaN3 as preservative

Flowrate: 0.65 mL/min

Processing Method: Sample chromatograms were processed relative to polyacrylic acid standard calibration curve
(Mw range from 1,930 to 495,000 dalton) using Millenium 32 Chromatography Manager

Samples were run in triplicate and results averaged.

Dynamic Scale Testing. Table 2 shows the composition of the cationic and anionic solutions used in the dynamic scale
testing. The cationic and anionic solutions are pumped separately through preheating coils in a 70 °C oven then after
flowing through a mixing tee into a scaling coil equipped with inlet and outlet pressure transducers. Flow continues until
the pressure differential reaches 6 psi, indicating scale formation in the coil. The time to form scale without inhibitor is
determined and then performance at each level of inhibitor is measured for twice the scaling time in the absence of
inhibitor. The minimum inhibitory concentration (MIC) is defined as the lowest concentration which prevents scaling of the
coil. The scaling index for barium sulfate in this system was calculated to be 2.97 using ScaleSoft Pitzer™ SSP2012,
indicating a moderately high scaling tendency.

Static Scale Testing. The cationic and anionic solutions are placed in 8 ounce jars. Scale inhibitor is added to the
anionic solution. The jars are placed in a 70 °C water bath for one hour to allow temperature equilibrium and then mixed.
The solutions are allowed to sit for 16 hours and then removed from the water bath. The solutions are filtered and the
amount of barium remaining in the solution is measured using Hach DR 5000 Spectrophotometer using Hach method 20
(turbidimetric). Two measurements were made at each inhibitor level and averaged.

Infrared Analysis of Heated and Unheated Samples. Scale inhibitor solutions were first dried in a 110 °C oven,
cooled to room temperature and ground with a mortar and pestle. Samples were analyzed on a Perkin-Elmer Spectrum 100
FTIR with Spectrum Software.
SPE 164128 5

Results and Discussion

TGA Analysis. Results of TGA analysis for the polymeric inhibitors are shown in Fig. 1 and for phosphonate inhibitors
in Fig. 2. Rate loss curves are shown in Fig. 3 for polymeric inhibitors and in Fig. 4 for phosphonates. PVS and the various
sulfonated polycarboxylic copolymers have very similar curves with slightly lower values for the phosphorous and
fluorescent tagged polymers. Onset of the largest degradation rate is around 325 °C with maximum degradation at 350 °C.
Following the analysis of Jiang et al. (1999) the slight loss in weight before 325 °C is mainly due to hydration water in the
sample. The degradation between 325 and 400 °C is primarily loss of sulfate.

Lower temperature degradation occurs in the curve for PAA and SPAC. For PAA, the only side group in the polymer is a
carboxylate functionality. McGaugh and Kottle (1967) analyzed the degradation of polyacrylic acid and found loss of water
due to anhydride formation in this same temperature range. Although SPAC is a sulfonated polymer, the amount of
sulfonation is much less than in the other sulfoanted polymers and does not have the same thermal stablity. Two regions of
weight loss occur in the curve for SPAC. This may be due to the two types of carboxylic acids found in the backbone of
this polymer. A similar weight loss might have been expected in the curves for the SPCA inhibitors. The absence of
anhydride formation could be due to stearic hindrance from the bulkier sulfonate group.

The TGA curves for the phosphonates have weight loss onset at 250 °C for PAPEMP and 300 °C for DTPMP. The onset
temperature for BHTPMP was 350 °C, though there are some minor losses at 150 and 275 °C.

Although the TGA analysis is run on dry polymer and reactions in solution are likely to be different, the general stability
trend found in this analysis matches well with the other analyses and previously reported experimental results. In general,
the results show a lower degradation temperature for phosphonates compared to sulfonated polymers.

Molecular Weight. The change in molecular weight with time and temperature is listed in Table 3 and shown for SPCA
in Fig. 5. In most cases, the molecular weight decreased slightly at 180 °C for exposure times up to 7 days. The effect on
molecular weight is much more severe at 200 °C.The effects for each inhibitor are discussed below.

PVS – the average molecular weight was unchanged after exposure to 200 °C for 7 days, however the amount of low
molecular weight fragments was increased (See Fig 6.)

SPCA – overall molecular weight loss of 7% after 3 days and 11% after 7 days, The loss was more severe (51%) after 7
days at 200 °C. pH had no effect at 180 °C on the molecular weight loss. Aging was also conducted in metal tubes and
PTFE at 200 °C. This had no effect on the loss of molecular weight.

PAA – the average molecular weight increased 7-10% after 3 and 7 days at 180 °C. This could indicate some crosslinking
of polymer which was also indicated by an increase in polydispersity. Further analysis is required to determine the exact
cause of this apparent increase in molecular weight.

Overall, exposure of all polymeric inhibitors at 180 °C had little effect on molecular weight. The molecular weight of both
6 SPE 164128

inhibitors tested was affected by exposure to 200 °C, though in different ways.

Dynamic Scale Inhibition. The results of dynamic scale testing are shown in Table 4 (180 °C) and Table 5 (200 °C).

After exposure at 180 °C, there is little change in performance of the inhibitors. The MIC for SPCA was the same over the
pH range of 5 to 10. The attachment of the phosphorous or fluorescent tag also had no effect on stability or performance.
There was a slight decrease in performance of PAA.

At 200 °C, neutralized sulfonated polymers showed little effect, however the acid form lost effectiveness, PAPEMP
completely lost effectiveness. The performance of PVS was completely unaffected by exposure to 200 °C for 7 days (Fig.
7).

Static Scale Inhibition. The results of static inhibitions tests after 180 °C exposure are shown in Figs. 8 and 9.

There was a significant drop in performance of pH 5 and 6 of SPCA at 180 °C compared to higher pH values, indicating
that the degradation pathway could be acid catalyzed. Performance of PAA also decreased significantly at pH 5 and 7.

The more significant drops in performance of scale inhibitors in the static test compared to the lack of performance drop in
dynamic testing indicates the more severe conditions found in the static test. In addition to the longer scaling times (16
hours in the static test compared to a few seconds in the dynamic test), the static test requires inhibition of nucleation for
successful results. Dynamic testing can be successful through crystal distortion and dispersion mechanisms as well.

The results for exposure to 200 °C are shown in Fig. 10 and 11, SPCA was aged in a PTFE liner as well as in 316 stainless
steel tubes. Results show that performance was lower for the polymer aged in stainless steel. The polymer was also diluted
to 50% and 15% of the original activity with DI water. There was also a similar drop in performance upon dilution,
consistent with previously reported results.

Sorbie and Laing (2004) report that the presence of calcium is necessary for the functioning of phosphonate type inhibitors.
Since this system contains no calcium, the performance of the phosphonates should only be compared before and after
treatment and not with other chemistry types.

FTIR Analysis. FTIR analysis was conducted to measure the amount of functional group degradation. Frequencies for the
carboxylate functionality are generally found in 1670-1820 cm-1 range, sulfonate in the 1055 and 1175 cm-1 region, and
phosphonate around 910 cm-1. Assignment of the absorbance frequencies in this study is based on reference to standard IR
absorption frequency tables as well as knowledge of the chemical structures of the inhibitors and the raw materials used to
manufacture them.

The results of the analysis show that for short term (< 24 hour) exposure at 180 °C, very little change occurs in the IR
spectra. Figure 12 shows no change in the IR spectra of PAA at various times of thermal exposure times up to 24 hours.
Significant reduction in carbonyl absorption is observed between 24 hours and 3 days of exposure.
SPE 164128 7

For heat treatment at 200 °C, more significant changes are observed in the IR spectra. Figure 13 shows the spectra of
SPCA at 200 °C for 2 and 4 hours. The carbonyl absorption band has shifted slightly following thermal exposure,
indicating an isomerization. Figure 14 shows the spectra of PVS after 7 days of exposure to 200 °C and is identical to the
untreated sample. In general, the sulfonate absorption bands of all sulfonated polymers tested were less affected by heat
treatment than the carbonyl absorption. All phosphonate functional groups were severely diminished in intensity after
exposure to 200 °C for 7 days.

Change in pH. The change in pH of various inhibitors before and after thermal exposure is given in Table 6. Clearly
thermal exposure leads to higher pH in the sulfonated copolymers but not in PAA, PVS, or PAPEMP. There seems to be a
reaction in these copolymers involving the acid and sulfonic functionality which needs to be further defined.

Summary and Conclusion

The thermal stability of scale inhibitors is an increasingly important topic in oil and gas production. A variety of methods
are available to analyze the effect of thermal exposure on scale inhibitors including chemical analysis as well as product
performance testing. The effects on chemical structure such as molecular weight distribution of polymers need to be
evaluated in combination with performance testing since performance is not always changed due to chemical change.
However, a better understanding of these chemical changes can help guide the development of more thermally stable scale
inhibitors. The conditions under which the scale inhibitors are thermally aged, such as pH dilution, and materials of
construction of the aging cell all appear to be significan factors. The chemical analysis and performance testing shows a
clear advantage to sulfonation for improving thermal stability.

Future study will evlaute the effects of ions commonly found in foramtiona nd produced waters as well as temperatures
above 200 °C.
8 SPE 164128

References

Dyer S.J., Graham G.M., and Sorbie K.S.: “Factors Affecting the Thermal Stability of Conventional Scale Inhibitors for Application in
High Pressure/High Pressure Temperature Reservoirs”, SPE 50717, presented at the 1999 SPE International Symposium on Oilfield
Chemistry, Houston, Texas, 16-19 February. http://dx.doi.org/10.2118/50717-MS

Dyer S.J. and Graham G.M.:”Thermal Stability of Generic Barium Sulphate Scale Inhibitor Species Under Static and Dynamic
Conditions”, Journal of Petroleum Science & Engineering” 37 (2003) 171-181. http://dx.doi.org/10.1016/S0920-4105(02)00351-0

Fan C., Kan A.T., Zhang P. et al:”Scale Prediction and Inhibition for Oil and Gas Production at High Temperature/High Pressure”, SPE
130690, presented at the SPE International Conference on Oilfield Scale, Aberdeen, 26-27 May 2010. http://dx.doi.org/10.2118/130690-
MS

Graham G.M., Jordan M.M.,. Graham G.C, et al.: “The Implication of HP/HT Reservoir Conditions on the Selection and Application of
Conventional Scale Inhibitors: Thermal Stability Studies”, SPE 37274, Presented at the 1997 SPE International Symposium on Oilfield
Chemistry, Houston, TX, 18-21 February. http://dx.doi.org/10.2118/37274-MS

Graham G.M., Dyer S.J., Sorbie K.S., et al..: “Scale Inhibitor Selection for Continuous and Downhole Squeeze Application in HP/HT
Conditions”, SPE 49197, Presented at the 1998 SPE Annual Technical Conference and Exhibiton, New Orleans, Louisiana, 27-30
September. http://dx.doi.org/10.2118/49197-MS

Graham G.M., Dyer S.J., and P.Shone:”Potential Application of Amine Methylene Phosphonate-Based Inhibitor Species in HP/HT
Environments for Improved Carbonate Scale Inhibitor Performance”, SPE 80284, 2002 ,revised for publication from Paper SPE 60217
presented at the 2000 SPE International Symposium on Oilfield Scale, Aberdeen,UK 26-27 January. http://dx.doi.org/10.2118/60217-MS

Jiang D.D., Yao Q. McKinney M.A. et al..: “TGA/FTIR Studies on the Thermal Degradation of Some Polymeric Sulfonic and
Phosphonic Acids and their Sodium Salts”, Polymer Degradation and Stability 63 (1999) 423-434. http://dx.doi.org/10.1016/S0141-
3910(98)00123-2

McGaugh M.C. and Kottle S.: “The Thermal Degradation of Acrylic acid-Ethylene Polymers”, Journal of Polymer Science: Part A-1,
6:1243-1248 (1968). http://dx.doi.org/ 10.1002/pol.1968.150060515

Sorbie K.S. and Laing N.: “How Scale Inhibitors Work: Mechanism of Selected Barium Sulfate Scale Inhibitors Across a Wide
Temperature Range”, SPE 87470, Presented at the 6th International Symposium on Oilfield Scale, Aberdeen, UK, 26-27 May 2004.
http://dx.doi.org/10.2118/87470-MS

Senthilmurugan B., Ghosh B., Kundu S.S., et al..: “Maleic Acid Based Scale Inhibitors for Calcium Sulfate Scale Inhibition in High
Temperature Application”, Journal of Petroleum Science and Engineering 75 (2010) 189-195.
http://dx.doi.org/10.1016/j.petrol.2010.11.002
SPE 164128 9

Tables

TABLE 1- SCALE INHIBITORS USED IN THIS STUDY

Scale Inhibitor % Actives pH

Sulfonated polycarboxylic acid (SPCA) Variable Variable

Fluorescent tagged sulfonated polycarboxylic acid (FSPCA) 39 6.0

Phosphorous tagged sulfonated polycarboxylic acid (PSPCA) 36 6.0

Sulfonated polyacrylocarboxylic acid (SPAC) 43 5.0

Polyacrylic acid (PAA) 54 4.8

Polyvinyl Sulfonate (PVS) 25 8.2

Polyamino polyether methylene phosphonate (PAPEMP) 50 4.5

Bis(hexamethylene)triamine pentakis(methylene phosphonic acid) (BHTPMP) 50 0.5

Diethylenetriamine pentakis(methylene phosphonic acid) (DTPMP) 32 1.6

TABLE 2- CATIONIC AND ANIONIC SOLUTIONS FOR STATIC AND DYNAMIC SCALING TESTS (MG/L)

Ion Cationic Solution Anionic Solution

Sodium 2950 3210

Barium 370 0

Chloride 4740 4550

Sulfate 0 540
10 SPE 164128

TABLE 3- MOLECULAR WEIGHT AND POLYDISPERSITY OF SCALE INHIBITORS BEFORE AND

AFTER HEAT TREATMENT

Chemistry pH Temperature (°C) Days Mw Polydispersity

SPCA 5 25 0 2471 1.65
SPCA 5 180 3 2183 1.68
SPCA 6 25 0 2410 1.65
SPCA 6 180 7 2267 1.80
SPCA 7 25 0 2398 1.64
SPCA 7 180 3 2219 1.63
SPCA 7 180 7 2161 1.62
SPCA 8 25 0 2404 1.64
SPCA 8 180 3 2296 1.65
SPCA 8 180 7 2256 1.65
SPCA 10 25 0 2415 1.65
SPCA 10 180 7 2296 1.65
SPCA 15% -
7 200 7 1050 1.32
PTFE
SPCA 15% - SS 7 200 7 1102 1.35
SPCA 50% -
7 200 7 1397 1.44
PTFE
SPCA 50%- SS 7 200 7 1171 1.36
PAA 4.8 25 0 1747 1.55
PAA 4.8 180 3 1872 1.67
PAA 4.8 180 7 2065 1.82
PVS 7 25 0 1891 1.63
PVS 7 200 7 1941 1.66
SPE 164128 11

TABLE 4 – DYNAMIC SCALE PERFORMANCE RESULTS, 180 °C

Inhibitor pH Day MIC
SPCA 5 0 15
SPCA 5 3 15
SPCA 5 7 15
SPCA 6 0 15
SPCA 6 3 15
SPCA 6 7 25
SPCA 7 0 15
SPCA 7 3 15
SPCA 7 7 15
SPCA 8 0 15
SPCA 8 3 15
SPCA 8 7 15
SPCA 10 0 15
SPCA 10 3 15
SPCA 10 7 15
FSPCA 6 0 15
FSPCA 6 3 15
FSPCA 6 7 15
PSPCA 6 0 15
PSPCA 6 3 15
PSPCA 6 7 15
PAA 5 0 5
PAA 5 3 10
PAA 5 7 15

TABLE 5 – DYNAMIC SCALE PERFORMANCE RESULTS, 200 °C

Inhibitor pH Day MIC
SPCA 1 0 15
SPCA 1 7 >50
PAPEMP 5 0 15
PAPEMP 5 7 >50
PVS 8 0 15
PVS 8 7 15
SPAC 5 0 5
SPAC 5 7 15
SPCA 7 0 15
SPCA 7 7 15
12 SPE 164128

TABLE 6 - pH CHANGE UPON THERMAL TREATMENT

pH
Inhibitor Chemistry Initial pH Temperature (°C) Days Final pH
Change
SPCA 0.8 200 7 8.0 7.2
SPCA 5.0 180 3 8.3 3.3
SPCA 6.0 180 7 8.2 2.2
SPCA 7.0 180 7 8.7 1.7
SPCA 8.0 180 7 9.0 1.0
SPCA 10.0 180 7 9.2 -0.8
SPCA - PTFE 7.0 200 7 9.0 2.0
SPCA - SS 7.0 200 7 9.3 2.3
PAA 4.8 180 3 5.0 0.2
PAA 4.8 180 7 5.1 0.3
PAPEMP 3.8 200 7 3.8 0.0
FSPCA 7.0 200 3 9.2 2.2
FSPCA 7.0 200 7 9.4 2.4
PSPCA 7.0 180 3 7.4 0.4
PSPCA 7.0 180 7 7.8 0.8
PSPCA 7.0 200 7 8.4 1.4
PVS 8.2 200 7 7.9 -0.3
SPE 164128 13

Figures

TGA Analysis of Polymeric Scale Inhibitors

100%

SPCA
90%
FSPCA
Weight (% of original)

80% PSPCA
SPAC
70% PAA
PVS
60%

50%

40%
50 100 150 200 250 300 350 400
Temperature (°C)

Fig. 1. Plots of percent weight loss of polymeric scale inhibitors with temperature.

TGA Analysis of Phosphonate Scale Inhibitors

100%

90%
PVS
Weight (% of original)

80% PAPEMP

BHTPMP
70%
DTPMP
60%

50%

40%
50 100 150 200 250 300 350 400
Temperature (°C)

Fig. 2- Plots of percent weight loss of phosphonate scale inhibitors versus temperature. PVS is plotted for reference.
14 SPE 164128

TGA Analysis of Polymeric Scale Inhibitors

Rate of Weight Loss

Temperature (°C)
50 100 150 200 250 300 350 400
0.001

-0.009

-0.019 SPCA
FSPCA
-0.029
Weight loss (mg/°C)

PSPCA
-0.039
SPAC
-0.049 PAA
-0.059 PVS

-0.069

-0.079

-0.089
Fig. 3 - Rate of mass loss versus temperature for polymeric scale inhibitors.

TGA Analysis of Phosphonate Scale Inhibitors

Rate of Weight Loss

Temperature (°C)
50 100 150 200 250 300 350 400
0.01
PVS
0 (Reference)
-0.01
PAPEMP
-0.02
Weight loss (mg/°C)

-0.03
BHTPMP
-0.04
-0.05
DTPMP
-0.06
-0.07
-0.08
-0.09
Fig.4- Rate of mass loss versus temperature for phosphonate scale inhibitors. PVS is plotted for reference.
SPE 164128 15

Molecular Weight of SPCA 7 day 180 and 200°C

2600

2400

2200
Molecular Weight (daltons)

2000 pH 5
pH 6
1800
pH 7
1600 pH 8
pH 10
1400
pH 7 200C
1200

1000
0 1 2 3 4 5 6 7 8
Exposure time (days)

Fig. 5. Molecular weight change of SPCA at various pH values at 180 °C and at pH 7 at 200 °C
16 SPE 164128

Fig. 6. Molecular weight distribution of PVS before (left) and after (right) exposure to 200 °C for 7 days. The higher level of lower
molecular weight fractions relative to the main polymer peak is shown.
SPE 164128 17

Polyvinyl Sulfonate Barium Sulfate Inhibition

Heated for 7 days 200°C

5
Differential Pressure (psi)

PVS unheated
3
PVS 200°C 7 days

1
15
50 30 20
0
0 20 40 60 80 100 120
Time (min)

Fig 7- Dynamic performance testing of PVS before and after heat treatment at 200 °C for 7 days. Numbers underneath the curve
indicate the mg/L of active scale inhibitor in the time range.

PERFORMANCE OF SPCA HEAT TREATED 180C

100
90
80
70
% Inhibition

60
50
40
30
20
10
0
SPCA SPCA SPCA SPCA SPCA SPCA SPCA SPCA SPCA SPCA SPCA SPCA SPCA
pH5 pH6 pH7 pH8 pH10 pH5 pH5 pH6 pH7 pH7 pH8 pH8 pH10
3day 7day 7day 3day 7day 3day 7day 7day
Fig. 8 – Static inhibition performance of unheated and heated SPCA at various pH and exposure times. All scale inhibitors are used
at 30 mg/L.
18 SPE 164128

PAA Static Performance Before and After Heat Exposure at 180°C

45.00

40.00

35.00

30.00
% Inhibition

25.00

20.00

15.00

10.00

5.00

0.00
PAA pH 7 PAA ph7/7 days PAA pH 5/3 days PAA pH 5/days
Fig. 9 – Static inhibition performance of unheated and heated PAA at various pH and exposure times. All scale inhibitors are used at
30 mg/L.

SPCA Performance Stainless/PTFE and Concentration

pH 7 Heat Treated 200°C
70

60

50
% Inhibition

40

30

20

10

0
SPCA PTFE SPCA 316SS 50% SPCA 50% SPCA 15% SPCA 15% SPCA
PTFE 316SS PTFE 316SS

Fig. 10 – SPCA static performance after exposure to 200°C in PTFE and 316SS and at different dilutions with DI water, all tests run at
30 mg/L active inhibitor
SPE 164128 19

Phosphonate and PVS Static Performance Before and After Heat Exposure at 200°C
100.00

90.00

80.00

70.00

60.00
% Inhibition

50.00

40.00

30.00

20.00

10.00

0.00
PAPEMP PAPEMP 7 Days PVS PVS 7 day BHTPMP BHTPMP 7 day DTPMP DTPMP 7 day

Fig. 11 – Phosphonate and PVS static performance before and after exposure to 200 °C, all tests run at 30 mg/L active inhibitor

870.16
2767.47 1629.54 1280.52
2343.02
715.41
3 Days 1157.49
1137.21 1047.62
1567.07 784.18
1702.96 1403.10

1446.99
2935.52 1931.63

2533.14 2161.63 1981.72 1138.00 1047.68

24 Hours 1566.88 785.96

1703.66 1402.97
2020.05
2941.20 2519.91 2038.07

2160.97 1984.04 1137.47 1047.65

6 Hours
1566.50 797.30
1703.88 1402.40
A 2049.97
2938.82
2534.85 2322.372161.33 1979.70
1137.44 1047.48

4 Hours 790.16
1568.15
2049.55 1702.84 1403.20

2939.94 2162.06
2527.24 2186.11 1983.25
1176.10 1046.73
2 Hours
785.30
1702.59 1565.91 1401.68

1448.74
2941.99 1949.07
2530.82 1981.84

PAA
PCA

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0
cm-1
Fig 12. PAA infrared scan up to 3 days exposure at 180 °C
20 SPE 164128

1570.74 1043.30

1183.15

1399.84

777.80
4 Hours 200°C 2049.87
2183.95 1676.55
3421.67
2929.76 2324.85 2161.77
1043.11

1182.89
1570.32

1399.61

777.25
A
1676.57
3394.86 2929.20 2036.98
2 Hours 200°C 2183.77 1039.57

1151.02

1712.99

935.97 779.85

1773.89
2941.76 1415.84
2050.98 1850.75
SPCA
2180.00

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0
cm-1
Fig. 13- Infrared Scan of SPCA before and after heat treatment at 200 °C for 2 and 4 hours hours.

1035.93
1168.23

712.91

200°C 7 days
3436.72
2049.56 1645.56
2941.50 2180.89 1980.07 1424.51 1035.88
1162.93

712.02

743.64

UNHEATED

3455.36
2945.56 2049.93 1644.57 1448.03
2180.07 1981.74

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0
cm-1
Fig. 14 - Infrared scan of PVS before and after heat treatment at 200 °C for 7 days.