Paper No.

CORROS1ON97
169

HIGH PERFORMANCE OILFIELD SCALE INHIBITORS

Y. Duccini and A. Dufour

NorsoHaas S.A.
Pare Technologique Afata -60550
Vemeuil En Haflatte, France

W.M. Harm, T.W. Sanders and B. Weinstein

Rohm and Haas Company
Spring House, PA 19477-0904

ABSTRACT

Sea water often reacts with the formation water in offshore fields to produce barium, calcium and
strontium sulfate deposits that hinder oil production. Newer fields often have more difficult to control
scafe problems than older ones, and current technology scafe inhibitors are not able to control the
deposits as well as needed. In addition, ever more stringent regulations designed to minimize the
impact of inhibhorx on the environment are being enacted. Three new inhibhors are presented that
overcome many of the problems of older technology scrde inhibitors.

Keywords: scale inhibitors, squeeze treatment, oil production, polymers, bwium sulfate, adsorption,
biodegradabilky

Copyright
al 997 by NACE International.Requestsfor permission to publishthismanuscriptin any fOrm, in part or in whole must be made in writing to NACE
International, Conferences revision, P.O. Box 218340, Houston, Texas 7721 S-8340. The material presented and the views expressed in this
paper are solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.
 INTRODUCTION.

Water flooding is the most commonly used technique to maintain oil production on offshore
platforms. In this process, sea water is injected under pressure into the reservoir via injection wells,
which drives the oil through the formation into nearby production wells.

Since sea water contains high concentrations of dissolved salts such as sulfate, chemical reactions
with the formation water can give rise to unwanted inorganic deposits that can block the formation,
tubing, valves and pumps. These deposits are primarily composed of BaS04, CaSO~, and SrSOq. In
some fields, CaCO~ is a major problem.

In the North Sea area, formation water chemistry can vary enormously . In the Central North Sea
Province, Ba+ levels can vary from a few mg/L to over 1000 mg/L and pH varies from about 4.4 (otlen
due to high partird pressures of CO,, such as in the Ula and Gyda fields) to over 7.5. In the Northern
North Sea province, pHs as high as 11.7 have been measured. In the Southern North Sea, the waters
are high salinity, sulfate rich and acidic.

Recently, there has been a push for low toxicity chemicals to handle scrde and corrosion problems 27.
New inhibitors must now conform to guidelines s~ci~ing maximum usage for materials having an
impact on the environment.

Since the conditions vary widely and the regulations governing the use of scafe and corrosion
inhibitors arc becoming ever more stringent, it is impossible today for a single inhibitor to meet afl the
requirements at a commercially feasible cost. The ideal inhibitor that could be used in both downhole
squeeze treatments and topside application would require the foflowing properties:

effective scale control at low inhibitor concentration.

compatibility with sea and formation water.
brdanced adsorption - resorption properties aflowing the chemicals to be slowly and
homogeneously released into production water at concentrations that provide effective
scale control.
high thermal stability.
low toxicity and high bbdegradability.
low cost.

Currently there are a variety of scale inhibitors available such as polyaerylic acid,
phosphinocaboxylic acid, sulfonated polymers and phosphonates. None of these are fully satisfactory
for the demanding conditions currently encountered in the North Sea.

To meet these requirements, we have developed three new scale control chemistries that we believe
come closer to fulfilling the requirements of an ideal scrde inhibitoc

1. An improved general purpose scale inhibitor for moderate condhions.

2. A high performance scale inhibitor for hamh conditions.
3. A low toxicity, biodegradable inhibitor for environmentally sensitive areas.

169/2
 In an emlier paper 8, we f~st introduced these chemistries to the North Sea oil production industry.
Since then, we have made modifications to further improve their performance attributes and conducted
additional studies to more fully evaluate them.

In this paper, these tbrw inhibitors arc compared to widely used conventional inhibitors. The
chemistries and acronyms used to describe all the inhibitors tested are given in Table 1.

1. IMPROVED SCALE INHIBITOR FOR MODERATE CONDITIONS.

By moderate condhions, we mean cases where formation water contains reasonable levels of
calcium, barium and strontium, and has pH values from about 5.0 to 7.5. An example of this is Forties
water (see appendix for details). Under these conditions, DETPMP and phosphinocarboxylic acid
(PPCA) perform less than ideally. Polyacrylic acid, although somewhat effective, does not have
adsorption - resorption properties suited for squeeze treatment.

The product we developed for moderate conditions is a phosphonocarboxylic acid (P-CA). This
chemistry is an alloy of the chemistry of phosphonates and polycarboxylic acids, and consists of a
phosphonatc group at the end of a polycarboxylic acid chain. As will be shown, the chemistry and
properties of phosphonocarboxylic acid are significantly different from that of phosphinocarboxylic
acid (PPCA).

Screening of polycarboxylic acids.

We compared P-CA to PPCA and pAA at various molecular weights using DETPMP as a control in
conventional bottle tests under conditions typical of the Forties Field. The results of these tests are
listed in Table 2.

Although all the polymeric inhibkors in the table are baaed on carboxylic acids, their responses to
Mw arc different. PPCA seems to be insensitive to Mw changes within the ranges studied. On the
other hand, better performance is attained with P-CA at lower Mw. For pAA, the trend is that higher
Mw produces better inhibition. In this screening test, DETPMP gave the highest BsS04 inhibition,
with the commercial P-CA inhibitor second highest.

Dosage - performance of PPCA vs P-CA.

Dosage performance profdes enable assessment of inhibition et%ciency, an importamt parameter in
providing effective squeeze life. In Figure 1, % BsS04 inhibition is plotted as a function of active
inhibitor dosage. As is well known, scale inhibitors often produce a characteristic S-shaped curve in
their dosage-performance profile. At the inflection point, tbe inhibitor dosage begins to be high
enough to show an effect of controlling the scale. Comparisons of the curves shows that, under these
conditions, P-CA requires about 27 ppm to reach the inflection point while PPCA requires about 40
ppm. Stated another way, it requires nearly 50 % more PPCA to produce the same inhibkion as P-CA
under Forties Field conditions at pH 6. It is clew from this figure that the required minimum inhibitor
concentration (MIC) of P-CA is far less than that of PPCA.

Adsorption screening.
P-CA was compared to PPCA for adsorption onto crushed Tarbert sandstone cores. The
composition of the Tarbert core samples used in these studies comprised 74- 78% quartz, 11.5 -12.5
% feldspar, 7-12 % autbigenic clay, 2 % muscovite mica and 0.5 % lithic fragments. Stock solutions
of 2500 ppm active inhibitor were adjusted to pH 3, 4, 5 and 6 using HC1 or NaOH. All tests were
prepared using 10 g of disaggregate rock poured into a 50 ml plastic bottle with cap. Twenty ml of

169/3
the test solution was pipetted into the bottle, shaken and placed in a 95 C oven for 24 hours. The
samples were then vacuum filtered through 0.22 p pore size filter.
As shown in Table 3, P-CA gives significantly more adsorption onto sandstone than PPCA. In
si~]m s~dies g.1DEfpMp also gave higher adsorption th~ PPCA, tdthough DETPMp wm
evaluated at pH 3 and 4 only. The data for DETPMP at pH 5 or higher was not given in the earlier
studies because they found that at 2500 ppm inhibitor, the phosphonate precipitated in sea water at 95
c.

Resorption tests - core flooding.

Dynamic corefloods were conducted compwirrg PPCA to P-CA in Clashach sandstone cores
saturated with high calcium Forties formation water (FW). Five to ten pore volumes of 50,000 mg/L
active inhibitor adjusted to pH 4.5 in synthetic sea water (SW) were injected into the core and shut in at
1050 C for 18 hours. Postflush was carried out at 105 C with 20SW/80FW at pH 5.5. At the
conclusion of the test, the core was flooded with methanol to displace the brine before drying and
examination by SEM for degradation of clays/carbonate and changes in pore morphology.

The inhibitor return profiles (Figure 2) show that P-CA has a longer squeeze lifetime in the useful
concentration region (a minimum of about 2 ppm active) by approximately a factor of two under these
conditions. No permeability decline was observed atler either of the P-CA or PPCA floods. In
addition, no residuaf polymer precipitate or silicate dissolution was observed during petrographic
examination.

Thermal stability.
Thermal stability tests were conducted on P-CA and PPCA at 2500 mg/L active inhibitor in
deoxygenated seawater at pH 5 held at 1700 C for seven days in sealed tetratluoroethylene-lined
pressure bombs. BaSO, inhibition efficacy at 24 mgll-. active inhibkor was then evaluated in 50 SW/50
Forties water atpH6after24hoursat850 C.

The results (Table 4) show that P-CA retains its high BaSOl inhibition under these conditions.
Although PPCA is also unaffected, its performance remains considerably less than P-CA as previously
shown.

Compatibfity screening.
Compatibility of P-CA and PPCA were evrduated in sea water, Forties water and a 50/50 blend of
SW/FW at inhibitor concentrations ranging from 0.1 % to 10% (as is basis), and at temperatures up to
950 c.

As shown in Figures 3 and 4, P-CA has about the same compatibility as PPCA in Forties water and
slightly less compatibility in 50 SW/50 FW. In SW alone, both inhibitors are completely compatible.

Ecotoxicity studies.
P-CA was tested under OECD guidelines 3 for aquatic toxicity on a sediment reworker, sheepshead
minnow, marine algae and a marine cmstacearr (Table 5). In addition, biodegradation studies and
bioaccumulation studies were also conducted using OECD guidelines 1112.

From the results, the predicted no effect concentrations (NEC) for aquatic and sediment dwelling
organisms were calculated. The calculated CHARM 45hazard quotients (0.030 for sediment dwellers
and 0.070 for aquatic organisms) indicate that no significant adverse effects are predicted from the use
of P-CA. Under the Harmonised Offshore Chemical Notification Format c, P-CA would likely fall in

16914
hazard group C (notification trigger of 150 tons on platform use), downgraded by one group because
inherent biodegradation haa not yet been performed. Similar products have inherent biodegradation of
>20 Yo,which if the same for P-CA, would allow upgrading to hazard group D (375 tons notification
trigger).

2. HIGH PERFORMANCE SCALE INHIBITOR FOR HARSH CONDITIONS.

For harsh conditions we used synthetic Miller water (see appendix) to evaluate performance. This
water is characterised by extremely high levels of barium and low pH, which can produce a severe
scaling condition.

Static inhibition tests.

Three experimental multiciwboxylate polymers (SMCA-1, SMCA-2 and SMCA-3) were compared
to PVS and PPCA for barium sulfate inhibition under the harsh conditions typified by the Miller field
formation water at 20/80 and 50/50 SW/FW ratios at pH 4.2 (Tables 6,7 and Figures 5, 6). At
20/80//SW/FW, the largest quantity of barium sulfate scale is expected. At the 50/50 ratio, the driving
force for BaSOg scrde formation is highest even though the quantity of scale is predicted to be less than
at 2018011SWIFW 13.

At the 20/80 ratio (Figure 5), SMCA-3 was the most effective BaSOg inhibitor, maintaining about
80% inhibition at 15 ppm active. At 15 ppm, SMCA-3 was at least equal to 25 ppm PVS. PPCA had
the lowest inhibition in this seriesat31 -36% inhibition after 22 hours.

At 50/50//SW/FW (Figure 6), SMCA-3 remains the most effective, with SMCA-2 and PVS second.
The PPCA control was not effective under these conditions as expected.

Dynamic inhibition - tube blocking tests.

To ensure that the performance of the SMCA inhibitors would remain high under the somewhat
different mechanism of scale formation found under tube blocking conditions, brief comparisons were
made to DETPMP and the PPCA control using the 50 SW/50 Miller water ratio at pH 4. The tests
were run in a P-MAC apparatus at 90 C at 1 Bar, with inhibitor concentration at 8 ppm active.

As shown in Table 8, SMCA-2 did not produce plugging of the capillary after 480 minutes and
SMCA-1 required over 300 minutes. SMCA-3 was not yet run in this test, but is expected to perform
about equal to SMCA- 1 and SMCA-2. In contrast, DETPMP and PPCA plugged the tube at 110 and
120 minutes respectively.

Adsorption scmming.
SMCA was compared to PVS for adsorption onto cmshed Tsrbert sandstone cores. The sandstone
and test procedures were the same as used for the earlier studies with P-CA.

As shown in Table 9, SMCA-2 gives the highest adsorption onto sandstone, and PVS gives the
lowest adsorption. SMCA- 1 and -3 gave intermediate adsorption levels.

Resorption studies - core tloodng.

Dynamic corcfloods were conducted comparing SMCA to PVS in Clashach sandstone cores
saturated with Miller formation water (FW). Five to ten pore volumes of 50,000 mg/L active inhibitor
adjusted to pH 4.5 in synthetic seawater (SW) were injected into the core and shut in at 120 C for 16
hours. Post flush was carried out at 120 C with 20 SW/80 FW at pH 5.5.

169/5
 The squeeze inhibitor profiles of SMCA-2 and SMCA-3 after post flushing are presented in Figure
7. Effective concentrations of SMCA-2 and SMCA-3 are maintained up to about 75 pore volumes. By
way of contrast, PVS under the same conditions lasts only to about 10-15 pore volumes. It is likely
that the lower resorption of PVS is due to its lack of adsorption onto sandstone as shown in the
previous studies.

Thermal stabifity.
Thermal stability tests were conducted on SMCA polymers versus other sulfonated polymers and
phosphonates at 2500 mg/L active inhibitor in deoxygenated sea water at pH 5 held at 1700 C for
seven days in seafed tetrafluorcdhylene-lined pressure bombs. BsS04 inhibition efficacy at 25 mg/L
active inhibitor was then evaluated in 20 SW/80 Miller water at pH 4.3 -4.6 after 22 hours at 750 C.

The results (Table 10) show that the SMCA polymers retain their high BaSO~ inhibition under these
conditions. The other sulfonated polymers tested also retain inhibition, but remain less effective than
the SMCA polymers. The two phosphonate polymers lose some effectiveness under these conditions,
as has been reported elsewhere 14.

Compatibility.
Compatibility of SMCA was evrduated in sea water, Miller water and a 50/50 blend of SW/FW at
inhibhor concentrations ranging from 0.1 % to 10 YO(as is basis), and at temperatures up to 95 C.

As shown in Figures 8-13, SMCA is more compatible than HEXA and SPCA in Miller water and
in 50 SW/50 Miller FW. DETPMP has a different compatibility profile than SMCA and it is difficult
to compare directfy to SMCA. PVS and SCP are both essentially compatible with Miller water and
SW/FW blends.

3. LOW TOXICITY, BIODEGRADABLE fNHIBITOR.

Process chemistry of poly(Aspartic acid).

Poly(Aspartic acid) (pAsp), has been shown to have both barium sulfate scale inhibition and
corrosion inhibiting properties M. ~s ~ombination of propties would be of considerable v~ue,
especially when combined with the inherent low toxicity and biodegradability of polyarnino acids.
However, we have found that tbe particular process used to manufacture this polymer has a major
impact on its properties 16. At present, there are three commercird processes used to make pAsp: (a) a
maleic scid/NH~ route, (b) thermal polymerization of L-aspmtic acid without acid catalyst, and (c)
thermal polymerization of L-aspsrtic acid using acid catalyst. The properties and advantages of each
process are summarized in Table 11.

In each of the processes, polysuccinimide is first formed (Figure 14). The polysuccinirnide is then
hydrolyzed with base to open the ring and form poly(Aspartic acid). The key differences among these
three processes are the formation of branched structures and control of moleculru weight. The
branched and linear forms of the precursor polysuccinimide are shown in the figure below. Detailed
studies of these structures have shown that tbe maleic acidhmnonia route to pAsp produces low
molecular weight products between 1000 and 2000 Mw, and highly branched polymers. Thermal
poly(Aspartic acid) produced without acid catalyst forms moderately branched polymers of about 4000
to 5000 Mw. Acid-catalyzed thermal pAsp allows control of Mw to between 5000 and about 40,000
with minimal or no branching.

lew
pAsp scale control.
Table 12 shows comparisons among the three processes along with a DETPMP control for barium
sulfate and calcium carbonate inhibition using jar tests simulating sea water/Forties water//5O/5O and
Miller Field water, respectively.

From the table, acid-catalyzed L-Aspartic acid process at 7,100 Mw provides the best barium sulfate
and calcium carbonate inhibition of the three processes. Thermal pAsp without catalyst (4700 Mw)
provides slightly less inhibkion and Msleic acid/NH, is the least effective of the polymers tested.

pAsp corrosion inhibition.

Poly(Aspartic acid) samples made by each of the three processes were compared to a formulated
commercial corrosion inhibitor using the Bubble Test method 1819.Briefly, the Bubble Test method
involved saturating about 400 MI of test solution with C02 and heating it to 50 oC. The corrosion rates
were measured by the linear polarization resistance method. The results of these tests are reported in
Table 13.

As in the scrde inhibition tests, the acid-catalyzed L-Aspsrtic acid process gives the lowest corrosion
rates of the three processes, with maleic acid/NHg giving the highest corrosion rates. Thermal pAsp
produces an intermediate corrosion rate under these conditions. The formulated commercial corrosion
inhibitor produces a lower corrosion rate than any of the unformulated pAsp inhibitors. Most
commercial corrosion inhibitors are incompatible with scale inhibitors and must be carefully fed to
reduce risk of coprccipitation with the scale control agent and conconrrnitant loss of both properties.
Since pAsp has scale and corrosion inhibiting properties, the incompatibility problem is eliminated. In
addition, pAsp has about 1000 times lower toxicity than conventional corrosion inhibitors, providing a
further advantage. It is hoped that properly formulated pAsp will provide a corrosion rate equal to that
of the commercial inhibitors currently available.

Effect of additfvea on pAsp scale and corrosion control.

We found that certain additives can markedly improve BaSO1 scale inhibition, and in some cases
slightly improve corrosion. The chemistry of the additives is not divulged due to patent considerations.
However, they can be described as low molecular weight, low cost and low-toxicity materials that are
not normally used in oil production. Table 14 shows BaSOd scale inhibition under the Forties Field
conditions as described in Table 12.

As shown in the table, the additive has increased the effectiveness of pAsp for BaSOi inhibkion to a
level beyond that of conventional scale control agents.

Corrosion control has also been improved by a small percentage with this additive. The mechanism
of action of these addbives is not certain, and research is ongoing to determine the reasons for the
dramatic performance improvement obtained.

Biodegradability.
Poly(Aspartic acid) made by each of the three processes was studied for biodegradability in
modified Storm tests, i.e., COZ evolution (similar to OECD test 30 lB, fresh water) and carbon
removal. COZ evolution does not fully assess biodegradability. Incomplete COZ evolution could be
attributable either to incomplete biodegradation or assimilation of carbon by the bacterial population.

169/7
On the other hand, the carbon removaf measurements give the total amount of polymer consumed by
the organisms, which is subsequently degraded to CO, or assimilated by the cells. If the carbon
removal data also shows incomplete removrd, then the bafance would be undegraded materiaf at the
conclusion of the test. Undegraded polymer in these tests may accumulate in the environment,
assuming no further degradation occurs beyond the plateau reached at 28 days in these tests. Due to
the variable nature of these tests, numerous samples were tested in the modified Sturm test as presented
in Figures 15 and 16.

Carbon removal and C02 evolution of acid (H~PO~ catalyzed pAsp is essentially 100%, indicating
complete biodegradation and no accumulation in the environment. Evaluation of thermal polyaspartic
acid (uncatafyzed) by the two tests shows that biodegradation of polymer made by this process is
approximately 7570, indicating that there is a risk of some accumulation in the environment by these
measures. Polyaapartic acid made by the maleic acid/NHq process generally produces about 60-7070
biodegradation, afso indicating a risk of accumulation in the environment.

Additional biodegradability studies on 7,100 Mw pAsp were conducted in sea water using OECD
method 306. In repeat tests, biodegradation reached approximately 70% in 28 days, which is
considered ready biodegradability. This result is consistent with CHARM recommendations 5, which
suggests a safety factor of 70% he applied to ftesh water tests. This result implies that the other
processes for making pAsp, which typicrdly give 60- 75% biodegradation in fresh water tests would
likely be degraded 40 to 60% in sea water under OECD method 306, and would thus not be considered
readily biodegradable.

4. MECHANISTIC STUDIES - STABILITY CONSTANT AND ADSORPTION.

A comprehensive expkmation of the role of inhibitor functional group, ionic matrix and adsorbent
substrate on the mechanism of adsorption is given in reference 10.

A straightforvmd method of comparing the fundamental properties of inhibitors without knowing

details of the functionafities present (e.g., sulfonate, phosphino, or carboxyl) is to measure their
apparent stability constants. This approach often allows evacuation of effects of polymer structure
such as type of sulfonate monomer and the proximity of other fmrctionalities that can make an acidic
group stronger or weaker.

Stability constant.
The stability constant of a Iigand (in this case an anionic polymer) is defined from the equilibrium
constant, &:

[ML]
K=
[I@] [L-]

The stability constant is equal to log &. A higher stability constant means that the polymer (L-n)
has a higher affinity for the metrd ion (M+). A difference of one unit in the stability constant equals

169/8
an order of magnitude difference in the metal-polymer affinity. By way of contrast, the acid
dissociation constant below (IQ, is actually the reciprocal of the equilibrium constant with M equal
to P:

[H+] [A-]
~.
[HA]

The p~ is equrd to -log L, with larger numbers indicating greater affinity of the anion (polymer)
for ~. At haff neutralization, pIQ = PH.

We determined the calcium stability constants for the four polymeric inhibitors: SMCA, P-CA,
PPCA and PVS. The results in Table 15 show that P-CA and SMCA have much higher stability
constants than PPCA, with PVS having the lowest stability constant.

Stability conatsnt versus adsorption.

A plot of % inhibkor adsorbed at pH 5 as a function of apparent stability constant (Figure 17) shows
a linear relationship.

The relationship also holds true for pH 3, but is further from a straight line. Thus, other factors
being equal, the higher the stability constant, the greater the adsorption. The data become more linear
as pH is raised because the measured stability constant includes the entire molecule at its endpoint,
which is generally about pH 6 or 7. At pH 5 or below, the molecule is incompletely ionized and not all
the ionizable functional groups are participating. A more direct comparison can be made if the
apparent stability constant is measured using only the ionized parts of the molecule in the calculation.

DETPMP was not included in this series because the adsorption studies for it were not performed at
the same time, introducing an additional variable into any correlations. However, the reported stability
constant of DETPMP ranges from about 6.6 to 7.1, which suggests that it may favor excessive
adsorption and precipitation under certain conditions, such as very high calcium and pH >5.

CONCLUSIONS.

1. A new polymeric inhibitor for moderate oilfield conditions, phosphonocarboxylic acid (P-CA),
gives significantly improved prforrnance over PPCA (phosphinocarboxylic acid). Among the
attributes of P-CA are

improved BaS04 inhibition.

increased adsorption on sandstone.
improved resorption profile resulting in longer expected squeeze life.
. good compatibility.
low toxicity.

180/9
 2. A new sulfonated multicarboxylic acid (SMCA) polymer class has been shown to have excellent
performance over conventional chemistries under harsh oilfield conditions. Among the attributes of
SMCA under harsh conditions are

markedly improved BaS04 inhibition at low pH.

increased adsorption over other polymers used in this application.
improved resorption profile over PVS.

3. A process for making highly biodegradable poly(Aspartic acid) has been identified that provides
scale control and corrosion inhibition in a single molecule. Poly(Aspartic acid) provides the following
advantages:

Risk of performance loss due to incompatibility of scale and corrosion inhibitors is eliminated.
. Toxicity of pAsp is about 1000x less than conventional corrosion inhibitors.

4. The process used to make poly(Aspartic acid) affects key properties due to differences in
branching and Mw of the resulting polyamino acid

Maleic acid/NHg process, although lowest in cost, provides the poorest scale and corrosion

control, and limited biodegradability in 28 day tests. This is likely due to the highly branched
structures that result from this process.

The L-Aspartic acid process without catalyst has adequate scale control properties, marginal
corrosion control and incomplete biodegradability as measured by modified Sturrn tests. These
properties are likely to be related to the intermediate branching that occurs with polyamino acids made
by this process.

L-Aspmtic acid, acid-catalyst process provides the best scale control and corrosion protection of
the three pAsp processes evaluated. Complete biodegradability of pAsp made by this process is also
noted. The superior properties of pAsp made by this process likely derive from the essentially non-
branched structures that are produced.

5. We provided a simple mechanistic evaluation procedure, which shows how stability constant
measurements can be predictive of adsorption characteristics of an inhibitor, even if the details of
composition are not known.

ACKNOWLEDGEMENTS.

We would like to express sincere appreciation to Dr. K.M. Yocom for pAsp and biodegradability
studies, to J.J. Karwoski for application studies and to T.F. McCallum for synthesis work.

REFERENCJL!L

1. Wwren, E.A. and Smalley, P.C., North Sea Formation Water Atlas, Memoir No. 15, The
Geological Society of London, publisher, 1994.

2. ECETOC. 1993. Environmental hazard assessment of substances. European Centre for

Ecotoxicology and Toxicology of Chernicrds, Brussels, Belgium. Technical Report No. 51,92 pp.

169/10
3. OECD. 1995. Guidance document for aquatic effects assessment. Organization for Economic Co-
operation and Development, Paris, France. OECD Environment Monographs No. 92, 116 pp.

4. Schobben, H.P.M., Karman, C.C., Scholten, M. C.Th., van het Groenwoud, H.. 1994. CHARM 2.0.
TNO Laboratory for Applied Marine Research, Den Helder, Netherlands, 34 pp.

5. Vik, E.A. and S. Bakke. 1994. CHARM: An environmental risk evaluation model for offshore E&P
chemicals: Technical background report on the use of safety factors for environmental information and
fraction released to the environment, Phase 1. Aquateam-Norwegian Water Technology Centre A/S,
Report No. 94-005, Oslo, Norway, 29 pp.

6. MAFF Directorate of Fisheries Research, Guidelines for the UK Revised Offshore ChernicaJ
Notification Scheme in Accordance with the Requirements of the OSPARCOM Harmonised Offshore
Chemical Notification Format, July 1996.

7. Hendriks, R. and Henriques, L., The Implementation of CHARM in The Netherlands, paper No.
11, 7tb International Symposium of Oilfield Chemicals, Geilo, Norway, March 17-20, 1996.

8. Duccini, Y., Dufour, A., Hamr,W.M., Sanders, T.W. and Weinstein, B., Novel Polymers as Scale
Inhibitors for Squeeze Treatment, paper No. 7, 7th International Symposium of Oiltield Chemicals,
Gcilo, Norway, March 17-20, 1996.

9. Jordan, M.M., Sorbic, K. S., Yuan, M.D., Taylor, K., Hourston, K. E., Ramstad, K. and Griffin, P.:
The Adsorption of Phosphonate and Polymeric Scale Inhibitors onto Reservoir Mineral Separates,
presented at the Fitlh International 011 Field Chemicrds Symposium, March 1994, Geilo, Norway.

10. Sorbic, K. S., Ping Jiang, Yuan, M. D., Ping Chen, Jordan, M.M., and Todd, A. C.: The Effect of
pH, Calcium and Temperature on the Adsorption of Phosphonatc Inhibitor onto Consolidated and
Crushed Sandstones, SPE 26605, presented at Society of Petroleum Engineers, Houston, TX, 3-6
October 1993.

11. OECD 1989. Guideline for testing of chemicals: Partition coefficient (n-octanol/water), High
Performance Liquid Chromatography (HPLC) method. Organization for Economic Co-operation and
Development, Paris, France. OECD Guideline 117, 14 pp.

12. OECD 1992. Guideline for testing of chemicals: Biodegradability in seawater. Organization for
Economic Co-operation and Development, Paris, France. OECD Guideline 306,29 pp.

13. Yuan, M.D., Todd, A. C., Sorbic, K. S.: Sulphate Scale precipitation Arising from Seawater
Injection - A Study with Aid of a PC-Compatible Prediction ModeY, Department of Petroleum
Engineering, Heriot-Watt University, Edinburgh, 1992.

14. Wilson, D., Novel Polymeric Scale Inhibhor for High Barium, Low pH Reservoirs, UK
Corrosion/95, 1995.

15. Harm, W.M., Zini, P. and Swift, G.: Biodegradable Poly(Aspartic acid) as a Multifunctional
Additive for North Sea Extraction Operations, poster presented at 4tb International Workshop on
Biodegradable Polymers, Durham NH, October 11-14, 1995.

169/1 1
16. Freeman, M.B., Paik, Y.H., Swift, G., Wolk, S. and Yocom, K.M. : Biodegradable Detergent
Polymers - Poly(Aspartic Acid), paper Presented at American Chemical Society National Meeting,
March, 1994.

17. Freeman, M.B., Paik, Y.H., Swift, G., Wilczynski, R., Wolk, S. and Yocom, K.M. :
Biodegradability of Carboxylates: Structure-Activity Studies, Chapcter 10, ACS Symp. Series 627,
Hydro~els and Biodegradable Polvmers for Bioarxiications, American Chemicrd Society (1996).

18. McMahon, A.J. and Harrop, D.: Green Corrosion Inhibitors: an Oil Company Perspective, Paper
No 32, presented at Corrosion/95, Orlando, FL, March 26-31, 1995.

19. Webster, S., Hamop, D., McMahon, A.J., and Partridge, G.J.: Corrosion Inhibitor Selection for
Oilfield Pipelines, Corrosion/93, Paper No. 109, Houston TX March, 1993.

20. Harm, W.M.arrd Robertson, S.T., Control of Iron and Silica with Polymeric Dispersants,
presented at the International Water Conference, Pittsburgh, PA, October 21-24, 1990.

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 Table 1- Description of Inhibitors Evaluated

Inhibitor Chemical Description Mw(]) or FW

P-CA phosphonocarboxylic acid polymer 3800

PPCA phosphinocarboxylic acid 3100
pAA pdyacrylic acid 2000 or 4500
SMCA sulfonated multicarboxylic acid polymers 3000 to 4000
Pvs polyvinyl sulfonate 7300
SPCA sulfonated phosphlnocsrboxylic acid 3000
SCP sulfonatc4i copolymer 3000
DETPMP diethylenetriamirre(pentamethylenephosphonic acid) 573
HEXA tripropylenetetramine(hexarnethylenephosphonic acid) 738

(1)All ~olymer~ ~em ~emu~ relative tOpolyacrylic acid standards. The phosphonate formula weights ~e
literature values.

Table 2- Effect of Irddhitor Chemistry and Mw on BaSOi Inhibition

Forties Field Conditions (50/50 SW/FW, 85 C/24 bra, pH 6,24 ppm active polymer)

Inhibitor Description Mw % BaSOd Inhibition

pAA 2000 26.1

pAA 4500 37.5
PPCA, experimental 3110 32.8
PPCA, experimental 3620 25.4
PPCA, experimental 4090 33.3
PPCA, commercial 316Q 39.1
P-CA, commercial 3810 66.2
P-CA, experimental 4800 52.0
P-CA, experimental 7400 46.2
DETPMP -- 83.7

Table 3- Static Inldbitor Adsorption onto Crushed Sandstone

(Tarbcrt Core,950 C, reported as mg inhibitor/g sandstone)

Inldbitor pH 3 pH 4 pH 5 pH 6

PPCA 2.37 2.22 2.16 2.20

P-CA 3.14 2.94 3.58 3.77

169/13
 Table 4- Thermal Stability at 170 C
(% BaSOl Inhibition, Forties Field conditions)
(average of 3 replicates)

w Zxlal!S
P-CA 62.6 68.8
PPCA 32.2 32.3
DETPMP 71.4 76.8

Tbennal stabMy test condhions: 25Cllmgll active inhibitor in deoxygenated SW at pH 5 held at 170 C for 7 days.
Forties Field conditions: 2Appm active (as acid) inbibkor, 50/50//SWiFW, pH 6.4-6,7,85 C, 24 hr.

Table 5- Summary of Aquatic Toxicity Studies on P-CA

Species Description Endpoint Value

(95% CI)
CoroRhiunr volutator Sediment reworker 10 day EC50 >10000 mgilw
CJpri;odon variegates Sheepshead minnow 96 ~ LC50 >1000 m~-
Skeletonema costatum Marine algae 72 hr EC50 >9000 mg/L
Acartia tonsa Marine crustacean 48 hr LC50 950 mglL

Table 6- Barium Sulfate Inhibition

(95C, pH 4.2,20 SW/80 Miller FW,l

Chemical Ptrm (Active) 2 Hour Mesrr 22 Hour Mesn

SMCA-1 10 33 36
15 57 59

25 70 67

SMCA-2 10 22 25
, 15 44 40
, 25 56 53

PPCA Commercial 10 41 31
15 54 36
,,,, 25 65 34

Pvs 10 30 32
15 44 44
, 25 58 48

169/14
 Table 7- Barium Sulfate Inhibition
(95C, pH 4.2,50 SW/50 Miller FW)

ChemicaJ PD m (Active) 2 Hour Mean 22 Hour Mean

SMCA-1 25 18 5

50 33 8
, 75 45 9

SMCA-2 25 19 14
50 41 28
54 30
75

PPCA Commercial 25 12 2
, 50 20 3
75 27 5

Pvs 25 15 5
, 28 7
50
75 33 7

Table 8- Dynamic Inhibition Teat Results

Inhibitor Mw Time Before Plugging, minutes

Blank (no polymer) -- 60
PPCA control 3200 120
DETPMP 573 110
SMCA-1 3500 M80
SMCA-2 2750 307

Table 9- Static hddbitor Adsorption onto Crushed Sandstone

(Tarbert Core,950 C, reported as mg/g)

Itddlitor pH 3 pH 4 pH 5 PH 6

SMCA-1 2.19 2.17 2.78 2.58

SMCA-2 3.97 4.01 4.41 4.17
SMCA-3 3.03 2.53 2.52 0.98
Pvs 0.41 0.97 0.64 0.26

169/15
 Table 10- Thermal Stability at 170 C
(% BaSOq Inhibition, Miller Field conditions)
(all data arc single data points, except where noted)

3.daYs
-- mm
SMCA-l 55.3
SMCA-2 -- 48.0
SMCA-3 51.8 53.7
SPCA 35.6 36.2
Pvs 30.8 31.9
SCP 32.2 33.6
DETPMP 36.2 14.8
HEXA 47.8 34.7

average of 2 repeats.

Miller Field conditions: 25 ppm active (as acid) inhibitor, 20/8CWSW/FW,pH 4.3-4.6,75 C,22 hr.
Thermalstabilitytest conditions 2500 mgll active inhibitor in deoxygenatedSW at PH 5 held at 170Cfor 3 or 7 days

Table 11- Comparison of Proceaaes to Manufacture poly(Aspartic Acid)

Manufacturing Process Polymer Characterization Advantages

Maleic acid/NHg Mw 2K Drdtons; highly branched lowest cost

L-aapsrtic acid, no catalyst Mw 4-5K Daltons; branched improved scale control

L-aapartic acid, acid-catalyzed Controlled Mw from SK to about improved scale control

40K Daltons; linear polymers improved corrosion control
complete biodegradability

169/16
 Table 12- pAsp Scale Inhibition Jar Teat Results

% BaS04 % CaC03
Proeesa Mw or FW (1) Inhibition (2) Inhibition (3)

(Control, without inhibitor) .- 0 0

Maleic acid/NH, 2,000 4 47
L-Aspartic acid, no catafyst 4,700 21 65
L-Aspartic acid, acid catalyst 7,100 25 75
L-Aspmtic acid, acid catalyst 12,500 21 66
L-Aspartic acid, acid catalyst 22,000 22 55
(DETPMP control) 573 29 50

(1) Mw of the polymers relative to industry standard polyrrcrylk acid starrdards were as follows: Maleic/NH,
= 2,00Q L-Aspartic acid, no catrdyst = 4,700; L-Aspartic acid, acid catalyst = 10,000, 18,000 and 28,000
respectively.
(2) SwEorties Field water//5O/5Oat 85 oC, 24 mg/L solid inhibitor added
(3) Mi]ler Field water at 95 oC, 25 mg/L solid inhibitor added.

Table 13- pAsp Corrosion Irddbition Bubble Test Results (1)

Corrosion ram mpy
Process Mw Initial 2 bra 4 hra 6 hrs 10 hra

Maleic acid/NH, 2,000 -- 129 50 48 41

L-Aspartic acid, no catalyst 4,700 -- 125 25 23 20
L-Aspartic acid, acid catalyst 7,100 122 138 21 17 15
L-Aspartic acid, acid catalyst 22,000 105 119 20 17 15
(Formulated commercial
inhibitor control) -- 128 140 3 3 2

(1) Forties Field water, 25 mg/L solid inhibitor, 50 C, 1 bat C02, PH 5.6.

Table 14- Effect of Additive on BaSO, Scale Inhibition by pAsp

Additive % BaSO,
Inldbitor Mw Concentration, ppm Inhibition
L-Asp, acid catalyst 7,100 0 13
L-Asp, acid catalyst 7,104I 4.8 100
L-Asp, acid catalyst 12,500 0 14
L-Asp, acid catalyst 12,500 4.8 100

169/17
 Table 15- % Adsorption end Apparent Stability Constant of Polyaneric Irddbitors

% Inhibitor Adsorbed 1)
Inhibitor Apparent Stability Constsnt pH 3 pH 5

SMCA -3.5 79.0 88.0

P-CA 4 62.8 71.6
PPCA 2.5 47.4 43.2
Pvs -1 8.2 12.8

m from Z. ~ of 2500 ~pm solution of active inhibkor solution applied to 10 g of cmshed T~befi smdstone
at 95 C, calculated by (mg inh]b]tor adsorbed per g sandstone/mg applied inhibitor) x 100.

Appendix

Ionic Composition of Forties Wster, Miiier Wster sndSesWster

(Aii Compositions in mg/L)

50/50 .2W80 W50 2WS0

Ion Fortlas Sea Water SWiFortias SWIForties Miller Sea Watar SW/Mlllar SW/Millar
Na 29370 103su 20134 25674 36mo 10690 23445 30s7s

K 372 460 416 390 2500 460 14s0 2092

Mg 504 136a 936 677 203 136a 764 434

Ca 2803 42S 1618 2333 2100 42S 1264 1766

Sr 574 287 459 450 225 3ao

Sa 252 126 202 1000 500 803

c1 52360 19766 38063 45a41 65@30 19766 42363 55953

So4 2960 14s0 592 2960 1440 592

169/18
 Figure 1

Dosage Performance of P-CA vs PPCA

100 T

90

20

10

0
o 5 10 15 20 25 30 35 40 45 50

ppm Active Polymer

Figure 2
Squeeze Inhibitor Resorption Profilas
for P-CA and PPCA

14- I

12- -;

F ..,
g
~
lo- -

c!
~ P-CA
~
.=
..*.. PPCA
g
~8 --
c
8
&6 --
.X y
.-
Z
= 8
~4 --
.?

2
2 -- Q,

.,, ,
=...~.~.. .*** .. . . .. . .. . . . . . . . . . . . . . . . .
I
o~
50 100 150 200 250 300
o
Desorpticm (Pore Volumee)

169/19
 Figure 3
Compatibility of P-CA va PPCA
(Forties Formation Water)

m
L]
*PPCA

Compatibility Region

OL
30 40 50 60 7(J
..
W
..
Yu
I
.,a!)0
20
Temperature ~C)

Figure 4

Compatlbllity of P-CA
(50/50 Forties Formation Water/Sea Water)

12-

10
~
%
m
=8

66 ~~
.%
s
.-
Z
g
%4 ~~

$
n
2 ~~

0
40 50 60 70 80 90 100
20 30
Tamperatura ~C)

169/20
 Figure 5

Barium Sulfate Inhibition

(95C, 20 SW/80 Miller FW)

It
15 ppm PVS
25 ppm PVS
15 ppm SMCA-3
25 ppm Sh6CA-3

2 hours 22 hours
Residence Time

Figure 6

Barium Sulfate Inhibition

(95C, 50 SW/50 Miller FW)

80, 1

70

604

950 ppm PVS

75 ppm PVS
50 ppm SMCA-3
975 ppm SMCA-3

2 hours 22 hours
Time

169/21
 Figure 7
Squeeze Inhibitor Profiles
for SMCA-2 and SMCA-3

EEi

0 50 100 150 200 250 300

Resorption (Pore Volumes)

Figure 8
Compatibility of SMCA-3 Inhibitor
(Miller Formation Water)

Compstibillty Region

20 30 40 50 60 70 80 90 100
Temperature ~C)

169/22
 Figure 9

Compatibility of SMCA-3 Inhibitor

(50/50 Miller Formation Water/Sea Watar)

20 30 40 50 60 70 80 90 t 00
Tempereture ~C)

Figure 10

Compatibility of Commercial DETPMP Inhibitor

(Miller Formation Water)

12-

10
@
2
m Compatibility Region
98

:6
.=
~
c
=
E4
g

&!
2 ~~

X///
o
20 30 40 50 60 70 80 90 100

Temperature ~C)

169/23
 Figure 11

Compatibility of Commercial Phosphonete Inhibitors

(50/50 Miller Formstion Water/Sea Water)

20 30 40 50 60 70 80 90 100
Temperature ~C)

Figure 12

Compatibility of Commercial SPCA Inhibitor

(Miller Formation Water)

o
20 30 40 50 60 70 60 90 100
Temperature ~C)

169/24
 Figure 13

Compatibility of Commercial SPCA Inhibitor

(50/50 Miller Formation Watar/See Water)

I
20 30 40 50 60 70 80 90 100
Temperature ~C)

Linear Form

JkkkX- o 0 0 0:

Figure 14- Linear vereue Branched poly(Succinihnide)

169/25
Figure 16

169/26
 Figure 17

/. Inhibitor Adsorbed ve Stebility Constant

90-

80-

70- .

~60.

:50.

s
.2 40-
.-
5
=
*30-
0

20-

10

0 ]-. +-
1 2 3 4
Stabiiity Constant

169/27