m

SPE31125

Soekt y of Petrolewn Engineers

The Correct Selection and Application Methods for Adsorption

Scale Inhibitors for Squeeze Treatments in North Sea Oilfields
M. M. Jordan

SPE, K. S. Sorbic SPE, G. M. Graham

SPE, K. Taylor,

and Precipitation

K. E. Hourston + SPE and

S. Hennesseyt

Department of Petroleum Engineering, Heriot-Watt University, Edinburgh, U.K.

and t LASMO North Sea (Aberdeen).
Shell Exploration and Production (Aberdeen) , Total Oil Marine (Aberdeen)

COPYIMIIIIM., %CWIYof Petroleum Ergumrs,

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LA, 14-15 FebruW l%

INTRODUCTION

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ABSTRACT
Over the past three years, [he Oilfield Scale Research Group at
Heriot-Wat[ has conducted a number field studies to evalua[ed
scale inhibitors for both downhole squeeze application and
topside continuous injection for a number of North Sea
operating companies.
This paper presents an approach for
screening commercial sulphate and carbonate scale inhibitors
for field application. The screening results, which include data
from static/dynamic
inhibitor efficiency, static adsorption,
compatibility
and thermal stability are used to rank the
performance of commercial scale inhibitors. From this short
list, a small number ( I to 3) candidate products are taken on to
reservoir condition coreflooding.
In [he screening of topside
scale inhibitors, no adsorption tests are conducted.

The central factor governing the dynamics of the inhibitor

return curve in adsorption/desorption
treatments
is the
inhibitor/rock
interaction as described by the adsorption
isotherm, r(C).
This is a function of the inhibitor type,
molecular weight, pH, temperature, mineral substrate and the
brine strength and composition.2-s,7 -12 The precise form of
r(C) determines the squeeze lifetime, as has been described in
detail in a number of previous papers. 13-18The precipitation
squeeze process is based on the formation of a gel-like
calcium salt, usually of poly phospbinocarboxy lic acid scale
inhibitor, within the formation.
Precipitation
(or phase
separation) is controlled either by temperature and/or pH19-23
although it will generally involve a coupled adsorption
process.24

Results from adsorption and precipitation type coreflood will

be compared for polymer and phosphonate
chemistries
selected using these screening procedures.
Such coreflood
serve botb to evaluate the squeeze lifetime performance and to
assess the Ievcls of formation damage caused by the scale
inhibitor package.
Tbe strategy of deriving a dynamic
isotherm which can be utilised in computer modeliing of the
coreflood data to produce a Field Squeeze Slrategy will be
outlined. This systematic approach provides a set of effective
and economical me[hods for the chemical screening of scale
inhibitors.
This results in an improved field application
strategy with longer squeeze lifetimes, while rninimising
formation damage potential.

References and illustrations at end of paper

The downhole and topside formation of both sulphate and

carbonate inorganic scales can be a serious problem in oilfield
production operations. One of the most common and efficient
methods for preventing the formation of such deposits is
through the use of chemical scale inhibitor squeeze
treatments. 16 Two main types of inhibitor squeeze treatment
can be carried out where the intention is either (a) to adsorb
the inhibitor on the rock substrate by a physical-chemical
process using a phosphonate or a polymeric material; or (b)
to extend the squeeze lifetime of poorly adsorbing scale
inhibitors by precipitation (or phase separation) which is
commonly achieved by adjusting the solution chemistry
([Ca2+], pH, temperature) of a polymeric inhibitor such as
poly phosphino carboxylic acid (PPCA).

In this paper, our objective is to present a general methodology

for the screening of chemical scale inhibitors for both
downhole and topside applications.
This is illustrated by
results generated for application in four North Sea fields,
although [be Oilfield Scale Research Group have actually
applied these methods to over 20 fields. Use is made of static

523

SELECTION AND APPLICATION METHODS FOR SCALE INHIBITORS

and dynamic inhibitor efficiency tests, compatibility phase

envelope determination
and thermal stability data. The
information generated in these tests is then used in conjunction
with static adsorption tests to select a small number of scale
inhibitors
(typically,
1 to 3) for reservoir
condition
coreflooding. Up to this stage, the experiments are relatively
short and many products and conditions can be examined quite
quickly and cheaply. However, given the time and expense
involved in carrying out reservoir condition core floods, it is
only practical to carry out a few well-targeted floods on
carefully selected products.
The importance of correct
selection and final coreflood evaluation is highlighted.26-28
We emphasise that reservoir condition core floods must still be
carried out in order to obtain the dynamic isotherms to design
the Field Squeeze Strategy w6,15.17,2S.*6 and also [O assess any
levels of formation damage.27
SCALE PROBLEM

SPE31125

Water Injector Protection and Produced Water Reinfection

(PWRZ): Waterflooding is the most common recovery method
in oilfields in the North Sea. Although seawater is most
commonly
injected in the North Sea, produced water
reinfection
(PWRI) is becoming increasingly
common.
However, in onshore facilities, aquifer water or river water
may be injected. It is important during the initial stage of
water injection, or during PWRI, to prevent the formation of
insoluble scale which may result in localised well injectivity
impairment.
The method of protection [o date has be rather
empirical e.g. 50 ppm to 150 ppm of scale inhibitor is dosed
into the first 500,000 to 1,000,000 bbls of injected water and
later in this paper we will discuss a possible improved
application strategy.
EXPERIMENTAL
METHODS
EVALUATION OF SCALE INHBITORS

FOR

THE

EVALUATION
The selection of scale inhibitors for field applications of the
type discussed above has become more critical because of the
rapidly rising volumes of water which must be treated as many
North Sea fields mature. Clearly, the development of reliable
testing and screening methods for scale inhibitors is very
important.
Over recent years, the Oilfield Scale Research
Group (OSRG) at Herio[-Watt University has developed a
number of methods for screening commercially available scale
inhibitors
for downhole/topside
and water injection
applications.
These methods allow the inhibitors to be
evaluated and ranked into an order of suitability using tests of
the following type: (a) static and dynamic inhibitor efficiency
assessment; (b) bulk inhibitor adsorption onto disaggregated
core and mineral separates; (c) inhibitor/brine compatibility
phase envelope measurement; (d) determination of inhibitor
chemical stability. Test results from (a) - (d) then allow us to
make up a short list for continuation
into: (e) reservoir
condition coreflooding.
Successful core flooding will then
allow us to derive certain quantities which can be used in
modelling to develop the Field Squeeze Strategy, as
discussed elsewhere.6,1S,17,zsZ6 Detailed descriptions of the
various types of test are presented in the OSRG Laboratory
Procedures Manual. 29

In the development of a new field, a vital first step is to

evaluate the expected scale problem and to attempt to
predicted the type of scale and its relative severity. It is also
important to determine the likely location where the scale
might form within the production system; i.e. is the location
principally down-hole, typical of sulphate scale, or further up
the well and into Ihe topside facilities, more typical of
carbonate scale. A number of software packages are available
to predict sulphate scale and carbonate scale. The accuracy of
these packages is principally controlled by the quality of the
water chemistry input data used to carry out the scale
prediction.
If from detail software modelling of formation
water and injection water mixtures (or purely formation water
in naturally depleted reservoirs), it is deemed necessary to
employ some type of scale prevention strategy, the stages
below outline one systematic evaluation route which we have
found particularly useful in field applications.
A number of different types of scale prevention strategy may
be applied in field production systems and these are briefly
reviewed below:
Downhole
Protection
Using Squeeze
Treatments:
Downhole squeeze treatments are one of the most common
methods for tackling both sulpha[e and carbonate oilfield
scales, I-6 This type of treatment protects the near wellbore
region and production system. The scale inhibitor solution is
injected into the formation and displaced out some distance by
overflushing, usually with an injected brine. This type of
treatment may well last months to years depending on a
number of factors, such as the nature of the inhibitor chemical,
the severity of the scaling problem, the volumetric water
production, reservoir chemistry etc.

A brief description will be given of the purpose of, and the

procedures used in, each of the methods mentioned above:
Static Inhibitor Efficiency Tests: In this type of inhibition
efficiency test, formation brine and injection brine are mixed
in proportions which
give both: (i) the largest mass of
precipitated scale; and (ii) the highest supersaturation index.
These quantities are specified by [he scale prediction codes at
down hole and topside temperatures/pressures.
Static type
experiments
are performed
to evaluate sulphate scale
inhibition efficiency, typically over test periods of 2 to 24
hours. Early time behaviour of the inhibitor in such static tests
is more associated with nucleation inhibition, whereas, later
time behaviour is related to crystal growth inhibition.
Therefore, this type of lest may be used to probe the various
mechanisms through which the different types of scale
inhibitor operate. 30 Such bottle tests are limited to 95C and
carbonate scales cannot be evaluated properly using this
approach, due to the absence of pressure control. There has
been much discussion on the practical details of how such
experimental tests should be performed, and recommendations
have been eiven.31 However. OSRG have found that the
recommended methods are not as reliable and reproducible as

Topside/Safety
Valves Protection. The scaling problems
within many fields in the North Sea require two stages of
protection involving (a) downhole scale prevention (described
above); and (b) topside/safety valve protection, In the upper
parts of the production system, it is in many cases possible to
continuously inject a small quantity of scale inhibitor into the
produced fluid stream, prior to the downhole safety values.
This chemical will then prevent the formation (or adhesion) of
scale from the point of injection until the disposal of the
produced water from the platform.

524

MM JORDAN, K,,S. SORBIE, G. M. GRAHAM, K. TAYLOR. K.E. HOURSTON AND S. HENNESSEY

[hrssc developed more recently,zg~z
These tes[s arc
superficially quite simple, but great care must be taken in
carrying thcm out as discussed elsewhere. g~z
Dynamic Inhibitor Efficiency Tests (Dynamic Tube Blocking
Tests): This type of test is very popular in the industry and can
be conducted with bicarbonate in the system in order [o
examine carbonate scale inhibition, since the test equipment
can easily be back-pressured.
In tube blocking [csts, lhc
inhibitor solution has a relatively short residence time within
the scaling coil, typically from seconds [o a few minutes,
depending on the flow rate.
Thus, such tests tend to
preferentially examine tbc nucleation inhibition mechanism
al[hough some me~surc of crystal grow[h retardation may be
given since this relates m the scale deposition within the tube.
It is clear tha[ the some interpretation of [he sta[ic and dynamic
tube blocking [csts is required in the light of the principal
mechanism Ihrough which the scale inhibitor under test is
thought to operate. w clearly, a scale inhibitor may bc cboscn
IO piss ccr[ain tes[s but that (he mechanism in the test may
not relate [o that which would be appropri~te in {he field.
Static Inhibitor Adsorption:
In static inhibitor adsorption
tests, ~hc scale inhibitor solution and crushed reservoir core
(from the tonnation into which [he chemical is to bc squccmd)
arc brought to equilibrium under a know set of test conditions.
Such measurements arc conduced over a range of pH which
the scale inhibitor may encounter during injection and
production. From these tests, which are carried out for eisch
scale inhibitor, it is possible [o rank the scale inhibitors from
good 10 poor in Ierms of their probable adsorption
performance in the reservoir. Typically, a good adsorption
Icvel, r, at a moderate inhibitor concentration (say, -2500
ppm) would bc in the range f_ = 0.5-4 m.g/g (mg of inhibitor
pcr g of core). This type of testing has been carried out within
the OSRG for a number of years and the results clearly show
that inhibitor with good Ievcls of adsorption give Iongcr
squeeze Iifc and that inhibitors with poor adsorption yield
short squeeze lifetimes;
the latter group may then bc
squecz.c
considered
as candidates
for prccipi[ation
lreatnlents.9-~J
The disaggrcgation or crushing of any rock or mineral sample
resul[s in material of higher surface area and with higher
surface energy which is therefore more reactive. As a result,
the s[aiic beaker tests often give higher values for adsorption
[ban those observed in consolidated sandstones containing
[hcsc minerals as authigcnic cements, However, even taking
into account these problems, the important sensifhifie.~ to pH,
calcium and temperature may be in the correct direction for
predicting
and analysing
consolidated
core flooding
We have previous
experiments
in reservoir
core.
demonstrated that this is the case for penta phosphonatc
(DETPMP) and phosphino carboxylic acid (PPCA) adsorption
onto quartz and clays. ~s,~s
Scafe [nhibitor/IJrine Compatibility:
Man y format ion and
produced brines are rich in divalent cations such as calcium,
magnesium, barium and strontium. Some scale inhibitors have
very good tolerance to these divalent cations and others do
not; a compatibility phase diagram can be constructed for most
inhibitor types. ]o The formation of a prccipita(cd scale
inhihitor/divalcnt
ion complex is the principle hy which
precipitation squcczcs operate.
However, the premature
525-

formation of such a precipitate during injection or early back

production can result in near wellbore formation damage.
Scale inhibitors are tested for their brine compatibility at 100%
SW, 50:50 SW:FW and 20;80 SW:FW over an range of
concentrations from 20% to 500 ppm inhibitor. In this test,
pure adsorption products should not show any incompatibility,
Products used in prccipita[ion squeeze type treatments will be
cxpcctcd to show a window of incompatibility,
but its is
essential to be able to evaluated and utilised this where
appropriate.
Thermal Stability: Thermal stability evaluation is important
where reservoir temperatures are sufficiently high - say,
exceeding 130C. Around this Icmperalure, certain scale
inhibitors show a significant decrease in their apparent
inhibition efficiency. Therefore, it is important to assess the
extent of efficiency decline so that only thermally stable
chemicals arc applied in higher temperature
reservoirs.
Thermal degradation will also results in short squeeze lifetime
as [he inhibitor molecules may be reduced in molecular
weight, due [o either hydrolysis or free radial attack at elevated
temperature in low pH and high TDS (total dissolved solids)
brines. Such lower molecular weight species may then show
lower levels of retention within the formation. 1~os~
Reservoir Condition CoreJooding:
As noted above, all of
the previous tests are relatively short and inexpensive to
perform and many can be carried OUI on a wide range of
commercially available scale inhibitors - say, up to -20.
From these initial screening tests, only a small number of
scale inhibitors (say, i to 3) should be taken forward to core
flooding since this is both time consuming and expensive.
The most important factors in carrying out relevant reservoir
condition scale inhibitor core flooding arc: (i) to choose a core
sample that is, to the best of geological/mineralogical
judgement, representative of the formation zones to be
treated; (ii) to restore the sample to the appropriate we[tability
conditions; (iii ) to cstabl ish the correct reservoir temperature
using synthetic brine of the appropriate composition and at the
correct pH. The effluent from the coreflood is monitored for
iron, calcium and other critical
pH, inhibi[or concentration,
ion concentrations.
In addition, [he pressure is monitored
throughout the experiments and the mineralogical composition
of the core is determined both before and after the flood is
carried out. This not only rdlows the inhibitor return profiles
to be defined, hut also enables any formation damage [o bc
assessed. The main steps in these floods broadly follow the
fickl inhibitor treatment stages described below and are as
follows:
(i) Seawater saturation and core characterisation;
(ii) Oil reconditioning by agcing with dead crude oil to restore
the sample m a more appropriate we(tability condition;
walcrflooding to Sor, followed by spearhead treatment (in
most floods):
(iii) Injection of the main inhibitor slug (containing [racer) at
room temperature,
followed hy heating to
reservoir
temperature and a shut-in;
(iv) Seawater or formation water postflush or back production
a[ reservoir temperature un[il the inhibitor concentration drops
below the minimum inhibitor concentration (MIC) for scale
prevention, for that case; typically, 0.2-2 ppm active content;

SELECTION AND APPLICATION METHODS FOR SCALE INHIBITORS

After the tlood cycle, the permeability

was measured to
determine if the treatment caused any degradation in reservoir
properties. A full mineralogical analysis was carried out on
the post-flooded core material and this was compared with the
mineralogical results for untreated core samples.
The use of the reservoir condition core flood results to design
an improved Field Squeeze Strategy has been described in
several previous papers. b,15,i72s2b,3s,3bThe core flood effluent
is analysed to find the adsorption isotherm, r(C), which is
then used in the field modelling. i31* The derivation of the
adsorption isotherm, its significance and its use in modelling
field squeeze treatments has also been discussed in detail in
other publications. ,]~-]5!1726,27
SCALE INHIBITOR

EVALUATION

STRATEGY

The above test methods may be combined in a number of ways

to produce the most appropriate
screening
stages for
commercial
scale inhibitor selection for a given field
application.
There are some broad groups of tests that are
more useful depending on the type of application problem
which is being tackled.
For example, a producer well
treatment, a topside application or an injector well treatment
will each require a slightly different test schedule as shown in
the inhibitor test flow charts in Figures 1 to 3. These are
discussed further below.
Producer Well Treatment:
The screening methods required
for down bole squeeze treatment are the most involved of the
three evaluations.
Static and dynamic inhibitor efficiency
screening should be carried out with the most efficient
chemical being carried onto static adsorption studies. At this
stage, the chemicals with good adsorption characteristics are
tested for compatibility with various field brines; see Figure 1.
The inhibitors with good efficiency but poor adsorption also
remain in the test program but are taken onto compatibility
testing to determine whether it is possible to apply such
products in a precipitation type squeeze treatment. After the
compatibility tests, a pure adsorption type chemical which
showed no incompatibility
problems may then be taken
However,
if the reservoir
forward to core flooding.
temperature is > 130C, the final product or products should
also be tested for their thermal stability. At this stage, any
potential precipitation products would also bc tested for
thermal stability. From the results of these tests, one or two
products are selected to be applied in a reservoir conditioned
coreflood.
The adsorption isotherm, r(C), would then be
derived for the various inhibitor/substrate sys[ems. l~lq
Field scale modelling using the various adsorption isotherms
would then be performed and the chemical which gave the
optimum performance would be the preferred product. Note
that the optimum product in this sense would be the one
which gave the best economic performance in terms of the
indicators being used by that company; e.g. volume of
produced water treated, least downtime (deferred oil),
guaranteed 6 month squeeze life etc. This computer modelling
approach b.1j17.2s2b would be employed to develop the Field
Squeeze Strategy for the first squeeze on a well. After the
first field squeeze, the inhibitor return data may be used to aid
in further extending the squeeze life on the same and other
wells within the field,ci 526

526

SPE31 125

Topside Continuous Injection Treatments:

The screen ing
methods required for topside scale inhibitor starts with static
and dynamic inhibitor efficiency testing, Products which have
good inhibition
efficiency
are further evaluated
for
compatibility
with produced fluids and other production
chemicals they may encounter in the topside process plant; see
Figure 2. The most efficient and compatible chemicals must
finally be tested for analytical interference effects, This stage
of the testing is unique to topside chemicals. If the downhole
chemical has been chosen, it is important to select a topside
chemical that will not interfere with its analysis. For example,
if a phosphonate was being used for downhole application, it
would not be recommended to select another phosphonate for
topside use. However, a phosphorus containing polymer could
be used for the topside treatment, if appropriate chemical
separation stages were employed prior to inhibitor analysis. If
two non phosphonate Iabelled polymers were used - one for
downhole and the other for topside - it would not be possible
to separate them chemically. To get round such a case, it is
possible to switch off the topside continual injection pumps a
few hours prior to taking a produced water sample to prevent
contamination.
Clearly, this may present some risks and is
probably not good operating practice,
Water Injection Well Treatments and PWRI: The screening
methods required for a water injector treatment should start
wi[h sta[ic and dynamic inhibitor efficiency in order to asses
the most effective scale inhibitor; see Figure 3. Adsorption
tests should then be carried out to determine which of the
chemicals has the lowest level of adsorption.
For a water
injector, the lower the level of inhibitor adsorption, the further
it will propagate into the near wellbore region. This is exactly
the opposite property required by a good squeeze chemical.
Chemicals with good efficiency and poor adsorption could
then be further tested to evaluate their compatibility
properties; see Figure 3. Chemicals with poor compatibility
would not be recommended for application due to the risk of
pseudo-scale formation in the near wellbore formation
resulting in a decline in well injectivity. The present empirical
approach of 50 ppm to 150 ppm of scale inhibitor within the
first 500,000101,000,000
bbls could be improved by utilising
a mini-squeeze
strategy whereby a small squeeze type
treatment is carried out using a slug of between 2.5% and 10%
which would be injected until it filled the initial 30 cm to 50
cm of the near well bore. The high concentration of the slug
would result in better propagation of the inhibitor into the
formation. The slug would be flushed into the reservoir and
the water injection would continue but the injected water
would no longer require to chemical treatment.
Such a
treatment strategy is particularly important for PWRI since, in
these cases, the mixed injection (seawater) and produced brine
itself may have some scaling tendency, If this were the case,
then dosing with a low level of inhibitor (say 10-100 ppm)
would be ineffective since the higher adsorption would retard
the inhifitor front relative to the mixed brine front. Thus, the
mixing scaling brine front would (out run the inhibitor and
would start to form scale which may be filtered out and may
cause formation damage. This would even be the case if the
Thus, for PWRI
injectors were thermally
fractured.
application, it is even more important to use a concentrated
slug treatment strategy, especially if the inhibitor exhibits
moderate or high levels of adsorption.

M.M. JORDAN, KS. SORBIE, G. M. GRAHAM, K, TAYLOR, K,E. HOURSTON AND S. HENNESSEY
Examples of results from different scale inhibitor screening
studies will be used to illustrate some of the points made
afmve.
EXAMPLES

OF SCREENING

Compositions
in Table 1.

of all brines used in this study are summarised

sulphona[ed poly acrylate - would have been the most

appropriated material, hased on the adsorption tests alone,

RESULTS

Scaling Tendency and Inhibition Efficiency Screening: In

tendency
in terms of
Figures 4 and 5, the scaling
supersaturation and mass of precipitate are presented for a
typical Brent type formation water. The flowing down hole
temperature and pressure was 98-C and 350 bar, at the well
head safety valves it was 82C and 140 bar and at the separator
on the platform, it was 40C, and 20 bar, Using this data, is
was possible to predict the sulphatc scaling tendency for the
entire downhole to production system, In terms of [he mass of
scale, only barium sulphate is a problem and it was predicted
to be most severe during early seawater breakthrough
(maximum precipitation at 10% SW). The mass of scale was
not significantly affected by the temperature. The maximum
supersaturation was predicted to occur at sf)~. seawater (SW)
and 50% formation water (FW) and was significantly affected
by the decline in opera[ing temperature and pressure. This
information immediately indicated that the amount of scale
inhibitor required to control the initial seawater breakthrough
would be relatively
small but that, during later stage
breakthrough, more inhibitor would be required: Iikewisc,
more inhibitor would also be required as the produced fluid
cooled during production.
Figures 6 to 8 show the barium
sulphate inhibitor efficiency of a penta phosphonate and a
hexa phosphonate scale inhibitor at a 50:50 SW:FW ratio over
the range of temperatures encountered across the operating
system. It is clear from these figures that 3 ppm active of
either inhibitor is sufficient to control scale at 98C. More
than 3 ppm of penta phosphonate is required at 82C but 3
ppm of hexa phosphonate is adequate. At 40C, more than 4
ppm of both penta- and hexa phosphonate would be required.
If the early seawater break [bough case is examined, it is clear
from Figure 9 that I ppm of the hexa phosphonate would
control the scaling problem whereas more than I ppm of the
penta phosphonate would be required. This type of eftlciency
evaluation allows the severity of the scale problcm to be
estimated and the appropriate chemical type and concentration
treatment can be established through the entire production
facility.
Stalic Inhibitor Adsorption Tests: In Figure 10, the static
adsorption levels onto crushed Tarbert Formation rock of four
generically different inhibitors are shown as a function of pH
(Inhibitor concentration = 250Q ppm; T = 95C). It is clear
that the terpolymer and the sulphonated acrylic acid adsorb [o
a lesser extent compared with the pen[a phosphonate which
adsorbed less than [he hexa phosphonate. From this data, it is
possible to infer that the penta- and hexa phosphonate should
be evaluated in adsorption type coreflood.
The terpolymer
and sulphonated acrylic copolymer, if they are sufficiently
good in their inhibition performance, may bc evaluated as
precipitation
squeeze
chemicals
by examining
their
compatibility and soluhility characteristics. If these same four
chemicals had been evaluated for application in a water
injector treatment or for PWRI, rather than for a producer well
treatment,
then the poorest adsorbing
chemical - the
527

Inhibitor/Brine
Compatibility
Testing:
The low calcium
brines of the Brent province of the North Sea are not regarded
as being problematical in terms of incompatibility between
produced fluid and scale inhibitors; typically, [Ca2+ ] = 300 to
900 ppm.~7 In several other fields in the North Sea, formation
brines exist where [Ca2+ ] = 4,000 ppm to 5,500 ppm (in some
reservoirs, [he calcium levels are much higher). Such brines
can result in incompatibility and it essential to carry out tests
to identify this and to design ways around this problem.
Alternately, we may utilise the high divalent levels to design
controlled precipitation treatments in order to extend the
squeeze lifetime
In this case, no incompatibility
of the inhibitor chemicals
should bc observed at reservoir temperature
in a 50:50
SW:FW brine, for a simple adsorption squeeze. If such a
problem did exist, it is often possible to design around it by: (i)
using a more compatible chemical; (ii) designing a preflush for
the squeeze treatment to push the formation water away from
the near wellbore and hence prevent mixing of formation
water and the scale inhibitor slug; (iii) adding a chelant [o
increase the divalent ion tolerance of the inhibitor slug along
with adding a preflush in the squeeze design. These solutions
to the problem have been applied in the North Sea by many
operators and their supporting service companies.
To illustrate
the problem of inhibitor
incompatibility
(precipitation) during either injection or backflow, a flooding
experiment was conducted using Brae Formation reservoir
core. The compatibility maps for various inhibitors with a
50:50 FW:SW brine (see Table 1) are show in Table 2. Figure
1I shows the differential pressure profiles for two inhibitor
treatments conducted in identical cores at 132C. The hexa
phosphate used in these test was applied as an adsorption type
treatment and the sulphmrated acrylic acid was applied using a
precipitation type formulation. During the early stages of back
flow after a 24 hour shut-in, the polymer precipitation flood
differential pressure remained constant during the entire
treatment indication no formation damage, However, on back
flow from the hexa pbosphonzrte flood, the pressure rapidly
rose and then very slowly declined as the brine flowed through
the core, The rise and steady decline was due to precipitation
of the hexa phosphonate not during shut in but during the early
backflow then the high calcium formation water (2000 ppm
Ca) swept through the core resulting in precipitation of a
pseudo scale (calcium/inhibitor complex). As the inhibitor
slowly dissolves the differential pressure fell but this type of
damage could result in a significant
period of reduced
production initially in a producer well even if the squeeze life
that resulted was quite appreciable as shown in Figure 12.
If incompatibility occurs across a wide range of seawater
mixing ratios and inhibi[or concentrations (e.g. 2070 to 500
ppm), then the inhibitor should not bc applied. However, if
the incompatible region occurs at 20% to 5 Yo, then injection
of the chemical inlo the formation following a preflush will
not result in precipitation during injection of the main slug.
The chemical
will only precipitate
when it has been
overflushed into the hot region of the reservoir. This type of
strategy can be carried out safely only if experimental work is
carried out to asses the compatibility of the chemical as a

SELECTION AND APPLICATION METHODS FOR SCALE INHIBITORS

function of inhibitor concentration

ratios.

at various (FW:SW) brine

Thermal Stability; The need for thermali y stability testing is

recommend at temperatures above 130C. In Figure 12, the
returned profiles from a hexa phosphonate and sulphonated
acrylic acid flood in Brae Formation core are present during
the backflow stage of the experiment,
Samples of the two
scale inhibitors were collected and their inhibition efficiencies
were compared to original inhibitor samples not flowed
through the core. In Figure 13, the significant decline in the
efficiency of the hexa phosphonate scale inhibi[or is clearly
seen relative to that of the sulphonated acrylic acid. Although
the polymer has a lower overall efficiency, it has not been
degraded to the same extent. The need for such thermal
stability testing is clear and can now be conducted in high
temperature, pressurised, teflon lined steel bombs.
From the static
Results from Dynamic Corejloods:
adsorption and inhibitor efficiency tests, it would appear that a
hexa phosphonate in many cases has better inhibitor efficiency
and higher adsorption than a penta phosphonate. The higher
adsorption may lead us to suspect that the squeeze lifetime of
the hexa phosphonate would be much longer than that of the
penta phosphonate. The return profiles of a penta phosphonate
and a hexa phosphonate are compared in Figure 14 and there is
an apparent inconsistency.
This can only be understood when
we examine the dynamic adsorption isotherms in the low
concentration region from the reservoir condition core floods
using these two products. The dynamic adsorption isotherms
(derived
as explained
elsewhere i3]4) for these (WO
phosphonate inhibitors are presented for Tarber[ formation
cores in Figure I5.
The observed long low-concentration inhibitor return profile
for the hexa-phosphonate is very typical of this type of scale
inhibitor (see Figure 14) and can only be understood by
considering the shape of the dynamic adsorption isotherms in
the low-concentration steeply-rising region as shown in Figure
15. In the threshold concentration region, where C t = 1 -3
ppm, the slope of the adsorption isotherm for the hexaphosphonate is steeper than that of the penta-phosphonate; i.e.
The return velocity of the
(ari~c)hca
>
(~rfic)penta.
inhibitor in the threshold region, Va, depends directly on the
inverse of this slope as follows:
VQ = Vflui&l[I + ( p/$) @r/~C)Q 1

[1]

This
has
been
explained
in several
previous
publications 6g10[3J4,15,*5 and all terms are given in the
Nomenclature. Thus, the direct correlation of return lifetime
with the static adsorption level must be interpreted carefully in
the light of the shape of the dynamic isotherm (which is not
evident in such static tests).
In Figure 16, three inhibitor return profiles are presented each
conducted with the same active concentration of inhibitor in
the treatment slug, similar core, postflush brine and at the
same temperature.
The two generic scale inhibitors used in
these studies were a penta phosphonate and a phosphino
carboxylic acid. The core material was from the Etive
Formation and the produced fluid was a 50:50 mix SW/FW
Brent type water,
Flood CI used a penta phosphonate
precipitation formulation, CII used phosphino carboxylic acid
528

SPE31 125

as a precipitation
treatment
and CIII used the pen[a
phosphonate in a conventional adsorption treatment.
The
minimum
inhibitor concentration
(MIC) at downhole
conditions (9 I C, Figure 17) was found to be 0.25 ppm for the
PPCA and 1 to 2 ppm for the penta phosphonate. At wellhead
conditions (70C, Figure 18), 0.5 ppm would be required for
the PPCA while 2 ppm would be needed for the penta
phosphonate,
When the MIC of the two type of generic
inhibitor is taken into account it is possible to evaluate the
scale inhibitor properly. PPCA takes 100 pv of postflush to
reach its well head MIC and 146 pv 10 reach its downhole
MIC.
Precipitated
penta phosphonate
takes 512 pv of
postflush to reach is wellhead MIC and 526 pv to reach done
hole MIC whereas it takes the adsorption treatment takes 573
pv to reach well head MIC and 596 pv to reach bottom hole
MIC values. It is clear from these results that the penta
phosphonates in adsorption and precipitation returns vastly
extend beyond the PPCA precipitation
treatment,
even
although its MIC is between 4 and 8 time lower than the penta
phosphonate tested at the same conditions.
Normally, the precipitation of a generic species would result in
a considerable extension in squeeze life. However, we note
from Figure 16 that there is a cross-over in the curves and the
lifetime of the penta phosphonate adsorption is slightly longer
than that of the penta phosphonate precipitation
treatment.
The reason for this apparent anomaly is due to the volubility of
the precipitate formed in this test. The precipitate solubdity is
far too high for this very fresh Brent type produced water and
this results in rapid dissolution of the scale inhibitor and the
higher concentration for longer during the early stage of the
flood (Figure 16) which removes inhibitor mass making the
squeeze rather shorter than for a simple adsorption. In Figures
19 and 20, the isotherm derived from the three flood are
present and the reason for the flood results described above
can be clearly explained.
Note that, for a precipitation
treatment, we refer to the apparent adsorption and the process
is described by a pseudo-isotherm; this is not strictly true as
the model for precipitatiorddissolution
process is rather
different. 24 However, it serves our purpose here to make
comparison between the different floods in a more quantitative
manner.
The first point [o note from Figure 19 is that the maximum
dyrurnic apparent
adsorption
level at high inhibitor
concentration is higher for the penta-phosphonate precipitation
than for the penta-phosphonate
adsorption;
i.e. dynamic
r W,,W> pt.!.nd$ This is due to a considerable amount of
additional calcium being available witbin the precipitation
formulation.
Since the penta-phosphonate
has a stronger
affinity for calcium, then enhanced adsorption by calcium
bridging may be occurring for the adsorption treatment but, if
precipitation occurs, the amount of apparent adsorption is
much greater. In the threshold concentration region, where C,
= 1 to 2 ppm, tbe slope of the adsorption isotherm for the
penta-phosphonate
is slightly steeper that of the pentaphosphonate precipitation treatment; i.e. (~r/=)P,.t.
ads >
@f7dC)P-h. Pp, This would explain the slightly longer squeeze
life for the penta adsorption treatment (see Equation [1]). The
maximum adsorption for the PPCA is much lower than even
the penta phosphonate adsorption and the gradient of the
PPCA treatment is much less steep than either phosphonated
in the concentration region above 0.5 ppm and only in the very

M.M. JORDAN,

K..S. SORBIE.

G, M. GRAHAM,

low concentration region does [he PPCA precipitation

steeper particularly in the range O.I to 0.25 ppm.
SUMMARY

K. TAYLOR,

K.E. HOURSTON

AND S. HENNESSEY

profile

AND CONCLUSIONS

In this paper, we have considered how it is possible to use

static and dynamic
tests to evaluate
scale inhibitor
performance
in the field.
Inhibition
efficiency,
static
adsorption, inhibi[or/brine compatibility and thermal stability
tests have been applied to rank inhibitors for field application.
This relatively rapid type of evaluation can assist in the
selection of inhibitors for further coreflooding which should
be carried out on a minimum number of products (typically, I
to 3). The value of such rapid screening tests is very evident
although it is still essential to carry out a much smaller number
of reservoir condition core floods for the shortlisted products.
This is necessary if the dynamic adsorption iso[herm, r(C), is
to be derived in order to develop the Field Squeeze
Strategy ,,6.1s ,17,25.26 or for the assessment of formation damage
which might occur in the squeeze treatment. ~b Details of the
various experimental
tests are quite lengthy and arc
summarised in the OSRG Laboratory Procedures Manual.9
The main conclusions arising from this study are as follows:
(i) Scale prediction represents the first step in the cvalwttion
procedure where the nature of the scale and the extent of the
scale problem can be estimated from the downholc to the
topside production system.
(ii) Both static and dynamic inhibition efficiency tests provide
accurate and reproducible methods for evaluating various sctde
inhibitors for given problems.
However, because diffcrcn[
me[hods may probe specific mechanisms of inhibition, some
care must be exercised in interpreting the results of such tests.
(iii) hulk adsorption tests on the disaggregated core material
broadly give the same .semifivirie.r of inhibitor adsorption (to
pH, [Caz+], and temperahsre) as those subsequently found in
the core floods. Therefore, adsorption is probably due to the
same rrlechmism in both the mineral separates (reported in
previous papers {) ~ 2f2s) and in [he core material. When
interpreting bulk adsorption measurements, some cognizance
must he taken of other more subtle factors which do not appear
in such tests.
The two main ones noted in this work arc
illustrated in the comparison between the bulk adsorption and
core flood re[urn behaviour
of the penta- und hexaphosphonatcs,
For these products, the MIC values arc
different and this affects the mvaning of return lifetime. Also,
the shape of the isotherm of the hexa-phosphonate results in a
radically different form of the inhihitor return profile in the
core floods. This Iat[er issue can only be studied in dynamic
core floods as cxplhined in the (ext.

(vi) Some limited reservoir condition core flooding is

recommended on the shortlisted screened scale inhibitors for
applications in producer wells. These allow the inhibitor
adsorption isotherm to he derived and the initial squeeze
design may then be designed by computer modelling.
Coreflooding also allows any formation damage to be assessed
prior to application the field.
NOMENCLATURE
inbihitor threshold concentration;
inhibi[or - dicthylcnc triamine penta (methylene
phosphoric acid);
minimum inhibitor concentration for acceptable
MIc
level of scale prevention:
PAA
inhibitor - poly acrylic acid;
PPCA
inhibitor - poly phosphino carboxylic acid;
inhibitor - pdy vinyl sulphonate;
Pvs
pv
pore volumes;
velocity of the threshold inhibitor concentration
Va
value through the porous medium;
velocity of the (luid through the porous medium;
Vfl,,id
rock bulk density;
rock porosity;
:
r(c)
inhibitor dynamic isotherm which depends on
concentration (also Temperature, pH, Caz+ etc..);
r ma.
maximum static inhibitor adsorption level in a
crushed core test (mg/g);
r pala
maximum dynamic inhibitor adsorption level
&
rhcx,
trom core floods for the penta- and hexapbosphonatcs (mg/g);
(arnc)~ slope of the dynamic adsorption isotherm at the
threshold inhibitor concentration level;
(~ r/rdC) ~,xa slope of the (hcxa- and penta-phosphonate)
&
dynamic adsorption isotherms near the threshold
(dr/,3C)wnla inhibitor conccn[ration level;
c,
DETPMP

ACKNOWLEDGEMENTS
The authors would like to thank the following companies for
funding the work of the Heriot-Watt University Oilfield Scale
Research Group (OSRG): Amcrzrda Hess, Amoco, Baker
Performance
Chemicals,
BP Exploration,
Deminex, Elf,
Enterprise Oil, FMC Ltd, Marathon, Nalco/Exxon Energy
Chemicals, Norsk Hydro, Shell, Statoil, Texaco, Total Oil
Marine turd TR Oil Services. Particular thanks arc extended to
Shell UK, Lasmo North Sea wrd Total Oil Marine for their
permission to usc field and experimental data in this paper.
The support of colleagues in the OSRG is also gratefully
acknowledged.
REFERENCES

(iv) Inhibitor/brine compatibility tests essentially establish the

phase diagram of the scale inhibitor and indicate whether this
problem cm be overcome by redesigning the squcczc (hy
preflushing, adding chelants etc. ) or whether the product is
unsuitable for application in the reservoir under investigation.
(v) Thermal stability involves testing for the degradation in
inhibitor efficiency during coreflood studies or in s[~tic
autoclave type hxts. Wc s[rongly recommend carrying out
thermal stability tests on the scale inhihitor when the reservoir
tcmpcrtrturc is (n excess of 130C.
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K..S. SORBIE,

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26.

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28.

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(Eds.), North Sea

Warren, E.A. and Smalley
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Appendix A: Mineralogy of the Sandstones Used

summary

presented below.
eIsewhere.25,27

Graham, G. M., Jordan, M. M., Sorbic, K. S., The

Oilfield
Scale
Research
Group
Laboratory
Procedures Manual; Version 2.0,
Heriot-Watt
University, September 1995.

30.

AND S. HENNESSEY

33.

A brief

29.

K.E. HOURSTON

of the

sandstones

A fuller

account

used in this study is

has been published

Brent Group Sandstone, Tarbert Formation (North Sea):

From examination of the cored samples, this sub-arkosic
arenite is subrounded
to subangular,
well sorted and
comprises: 82% quartz, 7- 9~o feldspar, 8- 10% kaolinite, I Yo
muscovite mica, 1% carbonate and 0.5% lithic fragments. The
main pore filling materials are quartz overgrowths, kaolinite,
chlorite and illite.

Etive Formarion, moderate to well sorted sub arkosic arenite

sub angular and comprises: 78% quartz, I 1% feldspar, 5%
kaolinite + illite, 2% muscovite, 1% carbonate, 2% pyrite.
Oseberg Formation poorly to moderately sorted, sub arkosic
arenite, angular to sub angular and comprises: 76% quartz, 8?Z0
feldspar, 6% muscovite, 2% carbonate and 8% kaolinite +
illite.

W., et al. An Evaluation of the Jar Test

and SrS04 Scale Inhibitors, paper no. 18,
at [he NACE Corrosion92,
Nashville,
27 April - I May, 1992.

Brae Formation:
The Brae Formation core used in this work
contains 0.5% muscovite mica, 2-4 % authigenic clay occurs
in minor amounts (illite 90%, kaolinite 10% of total clay);
authigenic carbonates were not evident.

531

TABLE

Composition

Synthetic seawater
Ion Composition ( m~)

Na+

ca2+
Mg2+
K+
so42clsr2+
Ba2+

10,890.
428
1,368.
460
2,960.
19,766
Z2ro
Zero

of synthetic

North

Sea brine and Formation

water

Formation water (FW)for Floods CI to CIII

Ion Composition (msdl)

Formation water for sealing predictions

Ion Comoos ition (mall)

9,180
214
32
225
zero
14,090
24
48

solution concentration
4(YC 5WC
Sulphonated aeylic acid
15% Y
Y
10% Y
Y
5%
YYYYYY
Y
:2%
;
Y
0.05%Y
Y

Hexa phosphonate
+ Chelant

5rc
Y
Y
Y
Y
Y
Y

FW for FloodsF28toF31
Ion Composition @.@

6,350
145
25
140
Z&m

35,650
2,0Q0
200
2,150
zero

10,434
25
20

63,500
450
1.000

Table 2
Test composition 50% Seawater 50% Formation water used
chemical type
Solution concentration
4(YC 5WC Wc
PPCA
NNNN
15% N
NNNNN
IO% N
5%
Y
Y
Y
YYY
;?%
YYYX
0.05% Y
Y
Y

Solution concentration
40C
15% Y
10% Y
5%
Y
1%
Y
0.5% Y
0.05% Y

used in this study

60C
:YY

in floodsF28toF31
Test temperature
7WC 80C WC

YY
;Xx
x
x

IX

Test tesnperatum
7(YC 8WC 9(YC
YY
;
Y

:Y
Y

Y
:Y
Y

Test temperature
WC
70C 80C 90C
YYYY
Y
:
:
:
lNNN
YNNN
YYNN

Y= solution clear
N= Solution shows significant evidence of incompatibility i.e. precipitation

10VC
NN
NN
xx
xx
xx
xx

13tYc

lWC
YY
YY
YY

13(YC

;X

YY

100-c
YY

130C
Y

;N
NN
NN
NN

Fig. I-Scale inhibitcm screening stages for a producer well

Fig. 2-We

inbibircu Screening stages for topside

pmteaion

gOOd

I Iwd

\
good

I gwrf

v
Precipitation type treatment

reservoir < I 3tYC

-oir

<I 3WC

(-

RL?l:-dation
.. .
Fig, 3- Scale inhibitor screening srages fors water injector well

Dropped
from
lest pmgranr

poor

good

pxlr

80

BaSCM,98C, 350 bar

60

40

20

0
0.0

0.4

0.2

Seawater
Fig. 4-Sulphate scaling
and topside conditions,

0.6

1.0

0.8

fraction of produced

water

tendency prediction for bottomhole,

Brent type formation water

well bead

.,.
SrSC)4,98C, 350 bar
BaS04, 91TC, 350 bar
In

/---

CaS04, 9~C. 350 har

oh

SrS04, X2-C, 142

BaS04,

82-C,

CaS04,

82C,

SrSC)4, WC,

BaS04,

WC,

41YC, 20 bar

86
4
20
0.2

0.6

0.4
Seawater fraction

of produced

0.8

534

1.0

water

Fig. 5-Sulphate scaling tendency prediction of supersaturation

wellhead and topside conditions, Brent type form;tion water

142 bar
20 bar

CaS04,

10-

0.0

har

142 har

for bottomhole,

20 bar

100

\(l

(,(

4(1

:[1

II
~

24
Sample

time

(hours)

Fig. 6-Unseeded
barium inhibitor
;it s():50 (S\V:F\\),
98-C (bottom

efficiency
hole}

test

100

80

60

40

211

()
2

24
Samples

time

(hours)

Fig. 7-Unseeded
barium inhibitor
efficiency
at 50:50 (SW: FW), 82 C (wellhead)

535

test

3 ppm

active

in (he 50:50

Hexa

inhibitor
solution

phosphonatc

80-

penta phosphonate

60-

40-

20 -

0
2

24
Sample

time

(hours)

Fig. 8-Unseeded
barium inhibitor efficiency
at 50:50 (SW:FW),
40C (topside)

test

lW

80-

(1[)-

-lo -

2(3 -

(l

24

2
Sample

time (hours)

Fig. 9. Unseeded
barium inhibitor efficiency
at 10:90 (SW:FW),
40C (topside)

536

tests

Adsorption tes[ [emp. 95mC

Inhibitorconcentration = 2500 ppm active
4

Hexa phosphonate

Penta phosphonate

Ter polymer

Sulphonated acrylic acid

()
4

pH

Fig. 10-Inhibitor adsorption data for selected phosphonate

polymers inhibitors on crushed Tarbert Fm. core.

3.0

and

Brae type Formation

F30. Sulphonate

132.C

F31. Hexa phosphonate

2.5 /

inhibi[or

precipitation

followed

by slow dissolution

phosphonate
dissolved

acryhc acid

resul[s in spike

prec]pita[e

of hcxa

un[il

most

and [he d! fferential

is

pressure

IS constant

1.5-

1.0

El

0.5-

0.0
0

10

25

30

35

40

45

15

20

Postflush

50

pore volumes

Fig.1 l-Comparison
of differential pressure across Brae type Fm
cores during inhibitor postflush, Floods F30 and F31 at 132C

537

20

Brae lype COm

132.C

18
16

F30 Sulphona[ed
~

14

F31

acrylic

Hexaptmsphonate

acid precipitation
adsorption

treatment

12
10

8
6
2 ppm active inhibitor

4
2
o

200

400

600

Postflush

800

1000

1200

pore volume

Fig.12-Comparison
of hexa phosphonate inhibitor concentration
during late stage desorption for floods F30 and F31 at 132C.

16 ppn) .,, [IL< llcxa

\ W I;W

100

phosphonate,

{(1 711, I; fficiency

3.0 IplII,I .,, I w ,,,lIIh, ,ul.tIcd acrylic

teat Temp.

ac!d

97 (

90

sulphonatcd acryllc acid rw4 floodd

sulphonatcd acrylic acid Flooded

80

hexa phosphonate

not flooded

70

hexa phosphonale

floodsd

60
50
40
30
20
10
0

Fig.

Sample Time (hours )

2.1

clficiency of chernical~ which have been

from thc core compared with nun h~ii( treated chemicals

13-inhibitor

de;orbrd

538

80
Tarbefl

Formation

Core

Floods,

T.

Flood FIO (hexa-phnsphonate,

1 I WC.

I Ic, pH = 5.41)

50

40

305 ppm active inhibi[or

20-

lo-

300

150

450

600
Postflush

1050

I200

750

900

pore volume

1350

1500

-->

returns in the effluent

Fig. [4-Comparison of penta. and hexa.phosphonate
during seawater postflush in floods F3 and F1O on Tarbert Fm core at 110.C.

al

,/

a
g

,.
..

L
0.5-

,.
.
.,
,,~~,..
, ,:
,,
, .
f ,.
,,.
,,
,,>
?,,
;
,

0.0 *
o

,
15

10

Inhibitor

Concentration

(ppm)

I
20
-->

IJig.15-Low concentration region of the adsorption isotherms for the pentaand hexa-phosphonates
in Figure 14; Tarbert Formation core at 110C.

539

25

10
Penis phosphonale

PPCA

Precipitation.

precipitation,

Pema phosphonate

Etive, Cl

Efive, Cll
adsorption,

Eli ve, CIII

-1
6
5
4
321.5 ppm

10.5 ppm

o-f

lcO

200

300

400

500

600

700

800

Postflush

pore

volumes

Fig. 16-Active inhibitor concentration in the effluent from the three

floods during back production on Etive Fm core at 91C.

100

91C,0.25ppm
91 C,0.5ppm

80

91C, l.Oppm

91 C,2.0ppm
60

40

20

0
Icnto

;idsc)rb

Pcnt:l pI-CCIp.
Inhihitor

PI(-A

]M,$LIP.

type

Fi~. 17- Seeded barium ~ulph;ltr inhibiti~~n cl1icicnc~ lests;

Iinw
2 hours
condili(~ns => S0:50 (F}V:SIJ ), :11 91C, WIIIpl V\

540

70c,o.25ppn

7WC,0.5ppm
70C, l.Oppm
u

70C,2.Oppm

40

20

0!
Pen[:) ~lLIlp

Penta .Idwrb

Inhibitor

11(-,1 pl,.clp

type

Fig. 18- Sreded barium sulphatc inhibition {,tficiency tests;

conditions => 50:50 (FW:S\k I, at 70C, >!rnple time 2 hours

Penra phosphorrate

precipilafion,

Perrtaptxmphonatc

adsorption,

Elive Fro., C1

E[lve Fm. CUl

1
00

0
0

500

1000

1500

2000

2500

Concentration

moo
(ppm

3500

4000

4500

active)

Fig. 19-Adsorption isotherms from floods CI, CI1 and ClII;

shows higher concentration
region of Figure 16.

541

5000

0.3C

0.25

0.20

0.15

0.10
~

0.05

,:~i
, ,.:
{,....
0

~ipitation,

Pentaphosphonate

Etive Fro., CI

adsorption,

Etive Fm. CIIl

000

Pentaplmsphonate

Concentration

(ppm active)

Fig. 20-Adsorption isotherm from the floods CI, CII and CIII;
shows the very low concentration region of Figure 16.

542