Society of Petroleum Engineers

SPE 27389

Phosphonate Scale Inhibitor Adsorption/Desorption and the

Potential for Formation Damage in Reconditioned Field Core
M.M. Jordan, * K.S. Sorbie, * Ping Jiang, Ming Dong Yuan, and A.C. Todd, * Heriot-Watt U.,
and K.E. Hourston, * Total Oil Marine PLC
SPE Members

Copyright 1994, Society of Petroleum Engineers, Inc.

This paper was prepared for presentation at the SPE IntI. Symposium on Formation Damage Control held in Lafayette, Louisiana. 7-10 February 1994.

This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper,
as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect
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of where and by whom the paper is presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 750833836, U.S.A. Telex, 163245 SPEUT.

ABSTRACT
Scale inhibitor "squeeze" treatments are used extensively to
control problems with downhole carbonate and sulphate scale
formation. The return curve from an adsorption/desorption
squeeze is governed by the inhibitor/rock interaction which, in
tum, is described by the adsorption isotherm. Several factors,
such as pH, [Ca 2 +], temperature, rock mineralogy etc, affect
the adsorption level and the shape of the adsorption isotherm.
However, these same factors may also lead to deleterious
effects in terms of both formation damage and inhibitor
solution effectiveness; the latter effect is referred to in this
work as "fluid damage".
In this paper, results and discussion are presented on the
potential for formation damage and inhibitor fluid damage
when acid phospho nates are applied in clastic reservoir
formations. Results are presented from an extensive series of
phospho nate (DETPMP) scale inhibitor core flooding
experiments using Brent Group (North Sea) sandstone cores as
the adsorbing substrate. Careful effluent analysis along with
detailed petrography and permeability measurement before
and after core flooding are shown to be invaluable in assessing
the degree of formation damage (and "fluid damage") arising
due to several factors. Most of the points raised here are quite
general and they are illustrated by the specific field results.
This work therefore contributes to the development of safer
field applications of scale inhibitor squeeze treatments in the
light of individual reservoir petrography.
INTRODUCTION
Scale inhibitor "squeeze" treatments provide one of the most
common and efficient methods for preventing the formation of
sulphate and carbonate scales in producer weIIs.I-6 A number
of acid phosphonate inhibitors are commonly used for
downhole application in many oil reservoirs around the world.
The procedure for applying such a chemical treatment
normaIIy involves the following six stages; (i) a "spearhead"
package (a demulsifer and/or a surfactant) is injected which is
thought to increase the water wetness of the formation; (ii) a
dilute inhibitor preflush is often applied to push the spearhead
into the formation and to cool the near well bore region; (iii)
the main treatment is injected which contains the inhibitor
chemical, normally in the concentration range 2.5% to 20%;
(iv) the brine overflush is applied which is designed to push
the main treatment to the desired depth in the formation away
from the wellbore; (v) a shut in or soak period (usually - 6 -
24 hours) is allowed which is the time when the pumping of
the overflush stops and the inhibitor adsorbs on to the rock
substrate; (vi) finally, the well is brought back on production.
Several chemical and physical processes in these steps in a
scale inhibitor squeeze treatment may affect the inhibitor
adsorption characteristics. In addition, these same factors may
be responsible for various types of damage in the reservoir
formation.
Adsorption of scale inhibitors is thought to occur through
electrostatic and Van der Waals interactions between the
inhibitor and formation minerals. For phosphonates, it is
known that adsorption is a function of pH, temperature,
mineral substrate, and involves cations such as Ca2 +. 2-5,7-12
The precise form of the isotherm describing this adsorption
process determines the squeeze lifetime, as is described in
detail elsewhere. 13-18 In a number of previous papers, we
have discussed and explained how these various factors affect
inhibitor retention in porous media. In this work, our
objective is to review and illustrate how these same factors
may adversely affect aspects of both formation and "fluid"
damage. For example, the effcct of pH on phosphonate
inhibitor adsorption has been demonstrated. 9 ,10 However, the
low pH phosphonate inhibitors may cause a number of other
effects some of which are deleterious (e.g. carbonate cement
dissolution leading to sand production) or benign (e.g. minor
mineral pitting say on kaolinite and feldspar).

References and illustrations at end of paper

451
2 PHOSPHONATE SCALE INHIBITOR ADSORPTION AND THE POTENTIAL FOR FORMATION DAMAGE
In this paper, a range of factors are examined which affect the
normal performance and adsorption/desorption characteristics
of phosphonate inhibitors commonly used in field "squeeze"
treatments. However, the central concern here is to discuss the
possible formation damage aspects of these various factors.
The additional concept of "fluid damage" is also introduced to
describe the manner in which the inhibitor solution/rock
interaction can introduce species (e.g. iron) into solution
which "damages" this fluid in terms of its efficient
functioning. We demonstrate a range of effects using results
from a series of reservoir conditioned floods using
reconditioned field core from certain North Sea reservoirs
which contain the Brent Sand formations. A brief description
of the relevant mineralogy of the various cores is given and the
effects of a range of factors is illustrated. The aim is to
discuss several factors which affect formation and fluid
damage which may arise in scale inhibitor treatments in the
field. The list of factors which we consider is by no means
complete but forms the basis of some practical guidelines
which may help in the safe design of scale inhibitor squeeze
treatments.
EXPERIMENTAL DETAILS
Materials Used
Adsorbents - Minerals and Core Material: The quartzitic
material used in this study for the bulk adsorption tests was
crushed Hopeman (Clashach) sandstone (see Appendix A)
which was prepared as described elsewhere. 10 The sandstone
was crushed to pass through a 600 Jlm sieve. The clay
mineral separates used in this study were not separated from
reservoir or outcrop rock but were obtained through
commercial sources. The mineral samples were crushed and
separated into specific size fractions prior to X-Ray diffraction
(XRD) examination to determine purity.
The core flood experiments were carried out using
consolidated reservoir cores from the Brent Group, North Sea
Basin (see Appendix B). Detailed results will mainly be
presented for core floods carried out on Tarbert Formation
core.
Inhibitor, Surfactants, Brine and Assay Method: The
surfactant and inhibitors used in this study are commercially
available products. Two acid phosphonates based on
diethylene triamine penta (methylenephosphonic acid)
(DETPMP) were used in this work (coded Ila and lIb). The
appropriate dissociation of DETPMP with pH has been
described previously. 9,10 A full discussion of the effects of pH
and the Ca 2+ binding mechanism of phosphonate inhibitor
onto quartzitic surfaces and also clays has been presented
previously. 9,10,19
The surfactants used in this study were products selected by a
service company as compatible products for the reservoir oil
and inhibitors to be applied in a North Sea field case. Two
products were used: one contained polyalkoxy alkyl alchohol
ester and the other contained oxyalkylated alkylphenols and
carboxylic acid salts of carboxylic acid/polyamine reaction
products in water and isopropanol.
The brine used in this work was a synthetic North Sea
seawater made from dissolved salts with a composition given
452
SPE 27389
in Table I. This brine was filtered through a 0.22 Jlm
membrane filter prior to use.
The methods for determination of the inhibitor concentration
was the persulphate ultra violet method originally developed
by HACH20 and subsequently modified at this laboratory.
This procedure in synthetic seawater allows the determination
of DETPMP inhibitor concentration down to 0.25 ppm +/-
0.04 ppm. A Varian Atomic Absorption Spectrophotometer
was used for the analysis of lithium, calcium and iron.
ICPAES was used to determine silicon and aluminium
concentration within the effluent. For all of the calibrations,
the matrix matched standards were used to suppress the
interference of the brine.
Inhibitor Adsorption Beaker Tests
For the static beaker experiments to determine adsorption of
inhibitor (DETPMP) as a function of pH, a stock solutions
containing 5000 ppm II was prepared using seawater (Table
I). For 25'C and 95'C tests, solution pH was then adjusted to
the following values: 2, 4 and 6. The detailed experimental
procedure has been presented previously.9,1O, 19
Experimental Procedure for Corefloods
Field core plugs of diameter 2.5 cm were cut along the vertical
axis of the 10 cm diameter preserved Brent Group sandstone
core sample prior to organic solvent extraction (toluene and
methanol + chloroform) using a soxhlet. The most important
reservoir parameter in these core floods is the temperature
which is llO'C for the source reservoir of the Brent Group
core material. However, there will be cooling effects during
the spearhead and inhibitor placement stages which the actual
strategies for inhibitor core flood evaluation must reflect this.
The effluent fluid from the core floods was monitored for pH,
inhibitor, lithium tracer, iron, silicon, aluminium and calcium
ion concentrations. Although many field core floods have
been carried out, it is not possible to present all the details
here; instead two representative phospho nate inhibitor core
floods for the Tarbert Formation have been chosen to illustrate
some typical observations and the details of these two floods
(F3 and F4) are presented in Table 2. The main steps in these
floods broadly follow the field inhibitor treatment stages
described above and are as follows:
(i) Seawater saturation and core characterisation;
(ii) Oil reconditioning by ageing with dead Brent crude oil to
restore the sample to a more "appropriate" wettability
condition, waterflooding to Sor followed by spearhead
treatment;
(iii) Injection of the main DETPMP inhibitor slug (containing
tracer) at room temperature followed by a temperature rise to
llO'C and a 17 hour shut-in;
(iv) Seawater postflush or back production at llO'C until the
inhibitor concentration dropped below 5 ppm (active content).
After the flood cycle, the permeability was measured to
determine if the treatment had caused any degradation in
reservoir properties and a full mineralogical analysis was
carried out. Results from this analysis are also summarised in
Table 2.
SPE 27389 M.M. JORDAN, K.S. SORB IE, P. JIANG, M.D. YUAN, A.C. TODD AND K.E. HOURSTON
EXPERIMENTAL RESULTS
In this section, some typical results concerning the adsorption
of inhibitors onto clays and reservoir core material will be
presented simply as examples. The main purpose of this paper
is to illustrate the main formation damage (and fluid damage)
aspects of inhibitor treatments.
The adsorption sensitivity of DETPMP onto kaolinite is shown
in Figure 1 where it is compared with the adsorption level for
quartz. The level of inhibitor adsorption onto the clay (in
mg/g) is very high due to the high surface area of the clay
material. A more detailed discussion of the factors governing
inhibitor adsorption onto clays is presented elsewhere. 19
Typical effluents from the reservoir core flood experiments F3
and F4 (see Table 2) are shown in Figures 2 to 6. These
figures show the effluent profiles for phosphonate inhibitor
concentration, pH, [Ca 2+], iron, aluminium and silicon. The
adsorption/desorption aspects of these experiments are
discussed in other publications. 19,21 Here, we will use these
results to focus on formation and fluid damage issues and the
specific observations will be used to illustrated specific points.
F ACTORS AFFECTING FORMATION AND FLUID
DAMAGE IN SQUEEZE TREATMENTS
As for all near-well treatments, inhibitor squeeze jobs are most
safely carried out in the field when a good understanding of
the fluid/rock interactions exists. Factors such as pH,
temperature, mineral substrate and cations such as Ca2+ can
govern the adsorption behaviour (adsorption isotherm) of the
phospho nate inhibitor. However, they may also lead to a
range of deleterious effects resulting in formation damage and
reduction of fluid effectiveness. These various issues are
considered in this section and, to assist our discussion below, a
summary table which outlines the effect of various parameters
on both (i) inhibitor adsorption; and (ii) formation and fluid
damage, is presented in Table 3. In this section, we will use
results from the bulk adsorption studies on clays and reservoir
condition core floods (F3 and F4, Table 2) to illustrate various
points.
Mineralogy
Quartz: Quartz is chemically very inert when exposed to
acidic inhibitor species and would not appear to undergo
dissolution in any of the cases studied here. Simple silicates
such as quartz and feldspar adsorb significantly less inhibitor
than the same mass of clay due both to the lower surface area
and the weaker surface charges. This is shown clearly for
kaolinite in Figure 1 and elsewhere for other clay
minerals. 19 ,21 Quartz would also appear to be preferential
water wet for all of the cases presented here and appears to
have no particular surface affinity for water/oil emulsions (see
below).
Feldspar: Feldspar is more reactive than quartz but is less
affected by acidic inhibitor than clay minerals. Diagenetic
effects such as secondary porosity development due to
dissolution of detrital grains and/or authigenic feldspar
overgrowth can cause planes of weakness in feldspar structure
which will be selectively attacked by acidic solutions such as
acid phospho nates, as shown in Micrographs 1 and 2. Acid
dissolution along cleavage planes results in the localised
453
3
migration of feldspar laths within pores. These may result in
formation damage but our results indicate that this is not
always (or, indeed, often) the case.
The dissolution of feldspar and clay minerals can result in a
decline in the mechanical strength of the core after flooding.
This weakening of the rock cement was more evident in core
from flood F4 (inhibitor lIb) where 3-4 cm of the rock easily
crumbled with only slight pressure. Feldspars exposed to
inhibitor lIb (Flood F4) are much more extensively leached
and this has resulted in grain fragmentation. There are
feldspar fragments contained within the emulsion globules
observed in flood F4 (see Micrograph 6 and discussion
below).
Clays: Clay minerals within the reservoir formation adsorb
larger quantities of phosphonate inhibitor than either quartz or
feldspar,19, 21 as shown in Figure 1. This can be attributed
principally to the large surface area of clay minerals.
However, clays can be adversely affected by the action of acid
phosphonates. The type and relative diagenetic timing of
authigenic clay cement are important when considering the
potential for formation damage in a given reservoir. The clays
within flood F4 and F3 comprise kaolinite, chlorite and illite
as shown in Table 2.
Chlorite was corroded in all post treatment samples and
appeared to be the most sensitive mineral to the acid inhibitor.
This observation was confirmed by XRD examination of
minerals within the < 8 J..lm size fraction (i.e. quartz, kaolinite,
feldspar, chlorite and illite/muscovite mica) where chlorite
was the only mineral to show a measurable decline in the
amount within the post flooded samples. The effect of such
acidising treatments could be to increase permeability but,
unless chelating agents are used, this may cause iron
precipitation. 22 ,23 Experimental work by Lievaart and
Davies 24 has shown that there is also a risk of generating
formation fines by acid treatments. These fines could cause
greater formation damage than the clay cements due to the
blockage of pore throats. The chlorite content in the specific
case to be discussed in this paper is sufficiently small (1 - 3%,
Table 2) that it has an insignificant effect on the properties of
the formation. However, the level of iron observed in the
effluent from the Tarbert cores may be as high as 600 ppm as
shown in Figure 5. This may cause some "fluid" damage in
terms of the inhibitor effectiveness, as discussed further
below. The potential both for direct formation damage and
fluid damage in other reservoirs having a higher concentration
of chlorite should be considered.
After the inhibitor treatment in floods F3 and F4, the kaolinite
showed no evidence of significant migration within pores but
the edges of vermiform kaolinite and kaolinite books did show
an unevenness typical of a dissolution texture. The dissolution
was a result of the acid inhibitor corroding the mineral during
injection and shut-in at elevated temperatures. In flood F4, the
amount of kaolinite dissolution appeared to be greater (Table
2) and there was some evidence of kaolinite migration. Oil
emulsion globules were commonly attached to kaolinite books
and verms and this is discussed in more detail below.
Illite grains showed no significant dissolution texture after
core flooding with inhibitor solution. However, in flood F4, as
with kaolinite, there is evidence of some illite migration and
entrapment within emulsion.
4 PHOSPHONATE SCALE INHIBITOR ADSORPTION AND THE POTENTIAL FOR FORMATION DAMAGE
Authigenic clay minerals formed early during burial
diagenesis and followed by either quartz or feldspar
overgrowth result in a rock will be more strongly cemented
and less likely to undergo fines migration due to salinity
changes. Detrital clays that have not undergone much
recrystallisation or late stage authigenic clay minerals which
line pores will be more likely be affect by salinity changes.
Permeability of reservoir rocks can be adversely effected by
changing the chemical composition of pore fluids and this is
especialIy true for rocks containing swelling clay minerals
(e.g. montmorillonite). The water sensitivity of a reservoir is
dependent on the critical salt concentration.(CSC) Clays
dispersion and suspension is caused by fresh water; if the
brine salinity is below the CSC, the clays are moved through
the rock until they build up at a pore constriction. If the brine
sali.nity is above the CSC, the clays flocculate (clays attract
one another and settle out) onto the pore walls before they can
be carried to a pore throat. 2S Sharma and co-workers
suggested that, as well as brine salinity, flow velocity was also
a critical factor in whether or not clay minerals would be
released from pore walls. 26, 27
Heavy Minerals: Pyrite (FeS2), zircon (ZrSi0 4 ), apatite
(Cas(P0 4 h(OH,F,Cl), rutile (Ti~) are all commonly
occurring heavy minerals in Brent Group sandstone and are
expected to adsorb a moderate amount of inhibitor. Of these
minerals, only pyrite and apatite are affected adversely by acid
phosphonate treatments. Apatite during injection and shut in
may release small amounts of phosphorous which will
contribute to the phosphonate inhibitor concentration during
assay of produced water sample. This contamination will only
occur for a few days of production until the bulk of the
inhibitor returns. Pyrite will also be affected by acid
phosphonate treatment releasing both iron and sulphate ions.
Sulphate returns higher than seawater levels have been
observed in produced water samples from Brent sand rich in
pyrite (5 - 25%) at the onset of back production. Iron release
due to acid dissolution of pyrite is the more significant
problem since this results in "fluid" damage as described
below. In the floods reported here, the pyrite content is small
1%, Table 2) but probably contributes to the high Iron
levels in solution effluent from both floods.
Carbonate: Carbonate minerals are very common in small
quantities within most Brent Group sands. These minerals are
commonly the first cements to form within the compacted
sediment with the result that they are responsible for part of
the m'echanical strength of the rock. Acidification caused by
acid phospho nate squeeze treatments in such carbonate
cemented areas of a reservoir will result in the dissolution of
the cements. This may result in a decline in the rock
mechanical strength, possibly along with fines migration (if
the carbonate cements held any other minerals by overgrowth),
and/or sand production (if they were the sole cementing
material). In certain North Sea cases where the well was
completed and perforated in carbonate cemented zones, the
application of acid phosphonate has resulted in significant
sand production. The type of carbonate, the quantity present
and its (diagenetic) timing relative to other authigenic cements
is critical. The order of reactivity of the commonly occurring
carbonates to acid solution is as follows:
Calcite > Dolomite > Ankerite > Siderite
(CaC03) (Ca,Mg(C03h) (Ca,Mg,Fe (C~h) (FeC03)
454
SPE 27389
Small amounts of early cementing carbonate will cause more
of a problem in terms of mechanical strength of the rock than
larger quantity of late stage cement which occur after other
less reactive authigenic cements have formed, such as quartz
or feldspar. Early dolomite and siderite are much less reactive
and so tend to be dissolved only after repeated squeeze
treatments whereas calcite can be almost total removed from
the near well bore area in a single treatment. In terms of the
effect of injected solution chemistry, carbonate minerals have
possibly the greatest effect. Calcite will react rapidly on
contact with acidic inhibitor solution to release calcium and
raise the pH and calcium ion concentration. The control of
calcium concentration and pH are of critical importance if
precipitation of phospho nate inhibitor is to be avoided as
shown in Figure 7. Phosphonate forms a calcium-inhibitor
complex which has a lower solubility at higher pH values.
The dissolution of siderite and ankerite can release a
significant quantity of iron into the produced water with the
potential problems discussed below.
In reservoirs where carbonate is perceived to be a problem,
then a near neutral form (pH 5 to 6) of phosphonate may be
more suitable for application. However, as the pH of the
phospho nate inhibitor solution approaches neutrality (pH - 6),
its tolerance to high calcium formation water is lower
especially at elevated temperature. This can be overcome by
using a seawater or fresh brine preflush to displace the high
calcium waters and to cool the near well bore area.
Formation Fluid and Squeeze Chemical Damage
Iron Release: The amount of iron released from the formation
minerals within a reservoir during the inhibitor application is
important for the following reasons:
1) As a multivalent cation, iron may enhance
adsorption of inhibitor species onto the formation;
2) Iron can cause reduction in inhibitor efficiency; and
3) Iron can effect the inhibitor detection methods used
to determine inhibitor concentration in produced
water.
The release of iron from the formation will occur for the most
part from the dissolution of carbonate (i.e. siderite), heavy
minerals (i.e. pyrite) and iron bearing silicates (i.e. chlorite).
Iron release may also occur due to corrosion of the tubular by
the acid phospho nate, if sufficient care is not taken to protect
the tubulars with a corrosion inhibitor. The most significant
release of iron into the produced water occurs during the first
few days of back production, where the concentration may be
in the range - 50 to 800 ppm. This will readily decline as the
bulk of the inhibitor returns to the well bore, but even 5 ppm
iron can have a detrimental effect on inhibitor efficiency.
The iron effluent results from floods F3 and F4 are presented
in Figure 5. During the injection of inhibitor solution, the pH
fell rapidly due to the acidic nature of the inhibitor slug
(Figure 4). The decline in pH was accompanied by a rise in
the amount of iron in the effluent. The amount of iron
released during inhibitor injection was greater in flood F3 (43
ppm) than in flood F4 (12 ppm). As noted above, the source
of this iron was probably from the dissolution of chlorite (iron
magnesium silicate) and pyrite (iron sulphide) both of which
were present within the rock (Table 2; Appendix B).
SPE 27389 M.M. JORDAN, K.S. SORBIE, P. JIANG, M.D. YUAN, A.C. TODD AND K.E. HOURSTON
Fe 3+ is much more insoluble than Fe 2+ in the pH range of
North Sea downhole environments. Only a few minerals
contain Fe 3+, principally chlorite and smectites, and Fe 2+ is
much more abundant from the dissolution of pyrite and
carbonate. This ferrous iron would be stable to a pH range of
6 to 8. This means that, although Fe 2 + can form an
iron/inhibitor complex, it is less likely to cause precipitation.
Precipitation will only occur more readily at low iron
concentration when the Fe 2+ is oxidised to Fe3+ out of the
downhole environment. This has been observed in our
reservoir condition core flood experiments where an
iron/inhibitor complex has been observed in the cooled
collection tubes after standing for some time (Figure 5).
AIISi Precipitation and Gels: The aluminium and silicon
release from flood F3 is shown in Figure 6. Acid
phosphonates tested on the Brent sandstone cores in this study
have never caused enough silicon or aluminium dissolution to
result in the formation of precipitates or gels. The level of
silicon and aluminium observed in core effluents 25 ppm)
did not appear to affect inhibitor efficiency. For example, the
injection of low pH (- 2) acid phosphonate inhibitor causes
more aluminium than silicon dissolution. However, the
dissolution of clay mineral and slight dissolution of feldspar
never results in more than lOs of ppm of AI in solution.
Aluminium from clay mineral structures rather than silicon is
preferentially removed by acid phospho nate during the
injection of the inhibitor slug. During back production,
however, the effluent contains more silicon although the pH
range (typically, 4 to 5.5) is well inside the single phase region
for both aluminium and silicon hydrates.
Calcium Incompatibility and Precipitation: Calcium has
been shown to have a significant effect in enhancing the
adsorption of phosphonate inhibitors, within the pH range 4 to
6, on both quartz and on certain clays. I 0, 19 Phosphonate
inhibitor will precipitate to form a sparingly soluble
phosphonate/calcium complex for certain combinations of the
calcium ion concentration, inhibitor concentration,
temperature and pH as shown in Figure 7. Broadly speaking,
the inhibitor/calcium precipitate forms more readily as pH,
temperature and [Ca 2+] all increase. Since many formation
waters contain levels of calcium concentration above that of
seawater (- 420 ppm), then precipitation can occur if the
inhibitor comes into contact with such brines. The formation
of this phosphonate/calcium complex may result in a
permeability decline and very short squeeze lifetimes. Even
when the solubility is above the threshold,7 the dissolution
kinetics 6 may prevent a suitably high inhibitor concentration
over the return production period. The problem of high
calcium formation water may be overcome by preflushing the
formation with seawater to displace the calcium from the rock.
In addition, this process cools the formation which also
increase the calcium tolerance of the inhibitor slug.
A second source of high levels of dissolved calcium in
solution is when the dissolution of carbonate minerals occurs
as discussed above.
Placement Strategy and Pump Rates
In all squeeze treatments, the placement of the chemical into
the formation to the desired depth is of critical importance. As
phospho nate is pumped into the formation, it is being adsorbed
so reducing the concentration of inhibitor within the inhibitor
455
5
slug. It is evident from Figure I that the rate of adsorption on
mineral substrates is quite rapid (6 hours at 25C) and this is
even faster at high temperature (2 hours at 95"C). We have
shown in previous simulations,17 that the non-equilibrium
adsorption characteristics can be exploited to ensure deeper
placement in the formation. For example, we may lower the
temperature in the near well bore area by preflushing the
formation with relatively cool injection brine. 18 The effect of
this cooling is to slow the adsorption of inhibitor which will
allow placement to the desired depth in the formation. The
pump rates should be high but below fracture pressure and due
consideration should also be given to the potential for fines
migration at high flow rates. 26, 27
Application of Surfactants and Demulsifiers
Surfactants and demulsifiers are commonly used in the
"spearhead" stage of a squeeze, prior to the application of the
main inhibitor slug treatment. The intention in applying a
spearhead treatment is thought to be to increase the water
wetness of the formation, which is expected to increase the
adsorption level of the phospho nate. In the course of this
treatment, some of the residual oil is often mobilised by the
surfactant. In Figure 8, effluent profiles of inert lithium tracer
are shown for various stages of flood F4. Lithium tracer
floods were performed at: (a) 100% brine saturation after
solvent cleaning; (b) at residual oil, Sor; (c) within the
inhibitor slug, after the spearhead treatment. The difference
between the original brine-saturated and residual oil flood in
Figure 8 gives us an accurate measure of Sor. The intermediate
curve after the spearhead in Figure 8 allows us to determine
exactly how much additional oil the surfactant has removed.
Our results have shown that, in tests using similar Brent sand
cores and identical inhibitors, the use of a particular surfactant
spearhead resulted in a longer inhibitor return profile l9 and
this behaviour was probably due to enhanced water wetness of
the core. However, in some cases, a significant decline in
permeability has been observed which was attributed to
emulsion formation by the spearhead chemical.
Examination of the plugs after flooding in the case of floods
F3 and F4 indicated the presence of an oil emulsion in both
floods. The emulsion occurred as globules of material
adhering to the sides of pore or partially blocking pore throats.
These globules were larger and more abundant in core from
flood F4 and, for this flood, associated feldspar fragments and
partially dissolved clay minerals were also observed within the
emulsion as shown in Micrograph 6. The emulsion does not
appear to adhere to the quartz grains but would appear to have
a stronger affinity for kaolinite and feldspar and this is clearly
seen in Micrographs 4 and 6. Analysis of the emulsion by
microprobe revealed that no phosphorus was present proving
that precipitated inhibitor was not present in the globular
material. A large carbon peak was seen in the electron
microprobe analysis of this globular material but no carbon
peak was seen on the adjacent quartz which appeared to be
completely free from oil (see Micrograph 4). Clay minerals,
particular kaolinite appeared to have the ability to adsorb
certain oil components (possibly asphaltenes) as has been
observed by previous workers. 28 Micrograph 4 shows the
association of the oily material with the kaolinite only, with
the adjacent quartz being virtually oil free.
6 PHOSPHONATE SCALE INHIBITOR ADSORPTION AND THE POTENTIAL FOR FORMATION DAMAGE
The original liquid permeability to seawater recorded for the
Tarbert Formation core floods (F3 and F4) are similar with
values of 441.2 mD and 556.6 mD, respectively. The
subsequent permeability behaviour at each stage of the
treatments is summarised in Table 2. The corresponding
pressures at the core inlet during floods F3 and F4 are shown
in Figure 9. The dramatic decline in permeability at the end of
the experiment in the case of flood F4 (Figure 9) was due to
the formation of the observed oil emulsion within the core and
the dissolution and migration of clay particles, as discussed
above.
From the results presented here, it is clear that the application
of the correct spearhead package for a squeeze treatment is
critical in order to avoid formation damage and it may also
play an important role in extending the squeeze lifetime.
DISCUSSION AND CONCLUSIONS
In this paper, we have considered how various factors, which
are known to affect the adsorption characteristics of
phosphonates and other types of scale inhibitors, impact the
formation damage aspects of a field squeeze treatment. For
example, low pH in solution may increase the level of
pnosphonate adsorption through a hydrogen bonding
mechanism.7, 10 However, this may also cause a range of other
effects such as feldspar pitting, chlorite dissolution, iron
release etc, which may have a deleterious effect on the
reservoir formation or on the effectiveness of the inhibitor
solution. Such effects have been illustrated using results from
a series of reservoir condition scale inhibitor floods in cores
from certain Brent Group formations in the North Sea. The
value of petrographic evaluation of core material before and
after flooding is clearly demonstrated. This allows us to
analyse results on both formation damage (e.g. permeability
decline) or fluid damage (e.g. presence of iron) in terms of the
changes in core mineralogy which can be directly observed.
The main conclusions of this study are as follows (Table 3):
(i) The same factors which affect inhibitor adsorption may
also lead to certain deleterious effects in terms of formation
and fluid damage. These main factors are: pH, [Ca2 +],
temperature, spearhead treatment and the specific
mineralogical composition of the formation, especially the
clay content.
(ii) Quartz is not significantly affected by the low pH acid
phosphonates used in scale inhibitor squeeze treatments.
However, pitting and breakup of feldspar has been observed
and, in conjunction with other effects (e.g. emulsion
formation) this may contribute to formation damage
(permeability decline).
(iii) Clays are more sensitive to the low pH inhibitor solutions
with chlorite being the most reactive. Indeed, the chlorite
content is significantly reduced due to acid dissolution and this
contributes to the high levels of iron in solution. Kaolinite
showed little evidence of significant migration within pores
but the edges of vermiform kaolinite and kaolinite books did
sometimes show an unevenness typical of a dissolution
texture. Some illite migration was evident in one flood where
it appeared trapped in an emulsion which was caused by the
spearhead treatment. The diagenetic history of the authigenic
456
SPE 27389
clays will probably have an important bearing on the likely
formation damage potential of these minerals due to either
fines migration or chemical dissolution.
(iv) Carbonate minerals may be dissolved by low pH
inhibitors to give higher levels of [Ca 2+] in solution which
may lead to two main problems. Firstly, formation weakening
and resulting sand production may occur if the carbonate is a
principal cementing mineral. Secondly, inhibitor
complexation and precipitation may occur if the solution
calcium level increases significantly.
(v) The solution may be "damaged" by the presence of high
levels of iron which may result from mineralogical sources
such as chlorite or pyrite dissolution (or from the tubulars).
Iron can enhance adsorption of inhibitor species onto the
formation; it can cause reduction in inhibitor efficiency; and it
can affect the inhibitor detection methods used to determine
inhibitor concentration in produced water.
(vi) The issue of oil conditioning of the field core and the
related "spearhead" treatment has important implications for
the wettability of the formation minerals, their inhibitor
adsorption characteristics and the potential for formation
damage. From our observations, we noted that the oil
emulsions which formed appeared to be most readily
associated with the clay minerals, mainly kaolinite, in the field
cores studied. Feldspar pitting and slight kaolinite damage
and mobilisation was made much worse in some cases by the
presence of this oil emulsion where these mineral fragments
gathered and contributed to the permeability decline. This was
not observed in many cases and appears to be associated with
the nature of the emulsion which is formed. This matter
requires further more systematic investigation.
ACKNOWLEDGEMENTS
The authors would like to thank the following companies for
funding the work of the Heriot-Watt University Oilfield Scale
Research Group (OSRG): Agip, Baker Performance
Chemicals, BP Exploration, Chevron, Elf, Exxon Chemicals,
Kerr-McGee, Marathon, Shell, Statoil, Texaco and Total. We
also acknowledge members of the Department of Geology,
University of Manchester for their assistance with SEM and
XRD analysis. The technical support of colleagues in the
OSRG during the preparation of this manuscript is also
gratefully acknowledged.
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Scale Inhibitor Squeeze Performance: Core Test and
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4. Meyers, K.O., Skillman, H.L. and Herring, G.D.:
"Control of Formation Damage at Prudhoe Bay, Alaska,
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1034, June 1985.
5. Przybylinski, J.L.: "Adsorption and Desorption
Characteristics of Mineral Scale Inhibitors as Related to
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M., Riley, H. and Gurden, S.: "The Modelling of
Adsorption and Precipitation Scale Inhibitor Squeeze
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the SPE International Symposium on Oilfield Chemistry,
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"Sorption and Fate of Phosphonate Scale Inhibitor in the
Sandstone Reservoir: Studied by Laboratory Apparatus
With Core Material", SPE21714 presented at the SPE
Production Operations Symposium, OK, 7-9 April 1991.
8. Kan, AT., Cao, X., Yan, X., Oddo, J.E. and Tomson,
M.B.: "The Transport of Chemical Scale Inhibitors and
Its Importance to the Squeeze Procedure", paper No. 33
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R.M.S.: "The Effect of pH on the Adsorption and
Transport of Phosphonate Scale Inhibitor Through
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M. and Todd, A.C.: "The Effect of pH, Calcium and
Temperature on the Adsorption of Phosphonate Inhibitor
onto Consolidated and Crushed Sandstone", SPE26605
presented at the SPE Annual Fall Conference, Houston,
TX, 3-6 October 1993.
II. Breen, P.J. and Downs, H.H.: "The Use of Adsorption
Thermodynamics in the Development of Scale Inhibitors
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12. Graham, G. M. and Sorbie, K. S.: "The Effect of
Molecular Weight on the AdsorptionlDesorption
Characteristics of Polymeric Scale Inhibitors on Silica
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l3. Sorbie, K.S., Wat, R. M. S. and Todd, A. c.:
"Interpretation and Theoretical Modelling of Scale-
Inhibitor/Tracer Core floods" , SPE Production
Engineering, pp. 307-312, August 1992.
14. Sorbie, K.S., Wat, R.M.S., Todd, AC and McClosky, T.:
"Derivation of Scale Inhibitor Isotherms for Sandstone
457
7
Reservoirs", Royal Society of Chemistry Publication -
Chemicals in the Oil Industry: Developments and
Applications, Edited by P.H Ogden, 1991.
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Squeeze Treatments", Presented at the Water
Management Offshore Conference, Organised by IBC
Ltd., Aberdeen, 22-23 October 1991.
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the Scale Inhibitor Squeeze Process", SPE16263
presented at the SPE International Symposium on
Oilfield Chemistry, San Antonio,TX, 4-6 February 1987.
17. Sorbie, K.S., Yuan, M .. D. and Todd, A.C.: "The
Modelling and Design of Scale Inhibitor Squeeze
Treatments in Complex Reservoirs,"SPE21 024 presented
at the SPE International Symposium on Oilfield
Chemistry, Anaheim, CA, 20-22 February 1991.
18. Yuan, M. D., Sorbie, K. S. and Todd, A C.: "A Near-
Well Simulator for Modelling Scale Inhibitor Squeeze
Treatments," paper No.24 at the NACE Annual
Conference, Nashville, TN, 27 April-I May 1992.
19. Jordan, M.M., Sorbie, K.S., Jiang, P., Yuan, M.D. Todd,
AC and Thiery, L.: The Effect of Clay Minerals, pH,
Calcium and Temperature on the Adsorption of
Phosphonate Scale Inhibitor onto Reservoir Core and
Mineral Separates", NACE Annual Conference,
Baltimore, Maryland, 28 February - 4 March 1994.
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Handbook, Hach Company, Colorado, p.516, 1989.
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Taylor, K., Hourston, K. and Ramstad, K.:
"Mineralogical Controls on Inhibitor Adsorption/
Desorption in Brent Group Sandstone and their
Importance in Predicting and Extending Field Squeeze
Lifetimes", SPE27607, presented at the SPE European
Production and Operations Conference, Aberdeen,
Scotland, 15-17 March 1994.
22. Almon W.R and Davies D.K.: "Regional Diagenetic
Trends in the J .ower Cretaceous Muddy Sandstone,
Powder River Basin", In Aspects of Diagenesis. Eds
P.A Scholle and P.R Schluger Spec. Pub. Soc. Econ.
Paleont. Miner. ,26., pp 379-400, 1979.
23. Curtis C.D., Ireland B.J., Whiteman J.A., Mulvaney R.
and Whittle c.K. : "Authigenic Chlorites: Problems with
Chemical Analysis and Structural Formula Calculations",
Clay Minerals, 19,pp471-481, 1984.
24. Lievaart L. and Davies D.R: "The Role of Fines During
Acidizing Treatments", Marine Petrol. Ceo!. ,4, pp127-
131,1987.
25. Khilar, K.C. and Fogler, H.S.: "Water Sensitivity of
Sandstone", SPE 10103, presented at the SPE Annual
Technical Conference, San Antonio, TX, 5-7 October
1981.
8 PHOSPHONATE SCALE INHIBITOR ADSORPTION AND THE POTENTIAL FOR FORMATION DAMAGE
26. Shanna,M. M., Yortsos, Y.C and Handy, L.L.: "Release
and Depostion of Cays in Sandstone", SPE 13562, SPE
International Symposium on Oilfield and Geothermal
Chemistry, Phoenix, AZ, 9-11 April 1985.
27. Sharma, M.M and Yortsos, Y.c.: "Permeability
Impainnent Due to Fines Migration in Sandtones", SPE
14819, PP 91-101,1986.
28. Fassi-Fihiri, 0., Robin, M and Rosenberg, E.:
"Wettability Studies at the Pore Level: a New Approach
by the Use of Cryo-Scanning Electron Microscopy",
SPE22596 presented at the 66th SPE Annual Fall
Conference, 6-9 October 1991
29. Pettijohn,F.l., Potter, P.E. and Siever, R.S. Sand and
Sandstone, Springer, Berlin, 1972
30. McKeever, P. 1.: "Petrography and Diagenesis of the
Permo-Triassic of Scotland", In Parnell, 1. (ed), 1992,
Basins on the Atlantic Seaboard: Petroleum Geology,
Sedimentology and Basin Evolution. Geological Society
Special Publication 62, pp 71-96, 1992.
31. Glasmann,1.R, Lundegard, P.D, Clark, R.A, Penny, B.K
and Collins, I.D.: "Geochemical Evidence for the History
of Diagenesis and Fluid Migration: Brent Sandstone,
Heather Field, North Sea", Clay Minerals., 24, pp 255-
284, 1989.
32. Scotchman, I.C, lohnes, L.H and Miller, R.S.: "Clay
Diagenesis and Oil Migration in Brent Group Sandstones
of NW Hutton Field, UK North Sea", Clay Minerals.,
24, pp 339-374, 1989.
33. Schramm, L.L., Mannhardt, K. and Novosad, 1.1.,
"Electrokinetic Properties of Reservoir Rock Particles",
Colloids and Surfaces, 55, pp309-331, 1991.
Appendix A
Hopeman Sandstone (Permo-Triassic): This is also known as
Clashach sandstone and was quarried near Elgin in North East
Scotland. The rock is an arenite 29 and the Hopeman sandstone
can be classified as a quartz arenite, with about 5% feldspar
and> 94% quartz. The dominant feldspars are orthoclase with
microcline and plagioclase being subordinate. Haematite,
where it occurs, occasionally coats grains. Other iron minerals
are present within the rock including detrital pyrite. Trace
amounts of illite were detected in the XRD analysis of the < 8
!lm size fraction from the rock. Cementing minerals are
evident within the sandstone with quartz being the most
significant. Up to 7% of the rock is composed of syntaxial
quartz overgrowths. 30 There is some evidence of post
overgrowth feldspar and quartz dissolution occurring later in
the diagenetic history of the rock.
Appendix B
Brent Sands, Tarbert Formation (Middel Jurassic): From
examination of the cored samples, the sub-arkosic arenite is
subrounded to subangular, well sorted and comprises: 80%
quartz, 7 - 9% feldspar, 8-10% kaolinite, 1 - 3 % illite, 1 - 2%
458
SPE 27389
chlorite, 1 - 2 % muscovite mica and 0.5% lithic fragments.
Quartz overgrowths, kaolinite, chlorite and illite are the main
pore-filling minerals. Feldspar composition in the rock is
dominated by k-feldspar and is almost devoid of any
plagioclase feldspar.
The processes of greatest importance for reservoir quality in
this Brent Group sandstone are compaction, k-feldspar
dissolution, kaolinite precipitation, quartz precipitation, and
illite precipitation 3l These processes are discussed below in
chronological order.
Kaolinite occludes significant amounts of pore space, filling
both primary intergranular and secondary pores. Kaolinite is
the most significant mineral in tenns of surface area presented
to fluids within the reservoir. As the mineral is not a late stage
precipitate lining the pore but is enclosed by later quartz
overgrowths, it is unlikely to suffer from fines migration due
to salinity or pH changes in the pore fluids during squeeze
treatments.
Volumetrically, quartz is the most important authigenic
mineral within the Tarbert Formation sampled. Quartz
diagenesis post-dates both kaolinite precipitation, feldspar
dissolution and has a resulted in significant loss of reservoir
quality. Kaolinite can commonly be seen incorporated in the
outer parts of quartz overgrowth, indicating that precipitation
of the outer parts of the quartz overgrowth is synchronous with
or post-dates the precipitation of kaolinite.
Diagenetic illite is present in small quantities 1-3 % within the
samples and exhibits a matted morphology in scanning
electron micrographs. The illite is always observed in close
association with kaolinite plates, commonly overgrowing
patches of kaolinite thus indicating that illite generally post-
dates kaolinite. The relationship between illite and quartz
would appear to indicate that illite post-dates the quartz
overgrowths within this section of the Tarbert Fonnation.
Chlorite forms a volumetrically minor cement with a grain-
coating morphology of intergrown crystal platelets. Chlorite
comprises about 1-3 wt% of the rock but is possibly the most
interesting mineral as it will be the most reactive to acidic
solution during inhibitor treatments. Iron will be produced in
solution as a result of this reaction.
In many Brent sandstones, poikilotopic calcite cement is an
early diagenetic feature which occurs after the initial stages of
sediment compaction. 3l , 32 In the samples analysed in this
study, there is little evidence of carbonate (calcite, siderite
ankerite or dolomite). The absence of any carbonate from the
Tarbert Fonnation sampled in this study is quite unusual when
compared with many of the North Sea reservoirs in the Brent
Group rocks (e.g. NW Hutton, Heather, etc).
 TABLE 1

Composition of Synthetic North Sea Brine used in this study

Ion Composition (mgll) Compound Composition (gil)

Na+ 10,890. NaCI 24.0738

Ca 2 + 428 CaC126H20 2.3395

Mg2+ 1,368. MgC126H20 11.4362

K+ 460 KCI 0.8771

S04 2- 2,960. Na2S04 4.376

Cl- 19,766 pH of brine after degassing was adjusted to pH 5.5

TABLE 2

Summary of Inhibitor Core Floods:F3 and F4.

Experiment ID. Flood 3 (F3) Flood 4 (F4)

Core Length (cm) 14.610 14.280
Core Diameter (cm) 2.629 2.629
Core Weight (gram) 161.8 157.39
Porosity ( % ) 23.7 % 23.47
Dead Volume (ml) 3.2 3.26
inlet & outlet 0.5 & 2.7 0.5 & 2.76
Confining Pressure(psi) 1000 1000
Back Pressure (psi) 90-110 80-90
Permeability (mD)
Initial 441.2 556.6
After demulsification 153.8 307.3
Final 216.9 52.8
Pore Volume (ml)
Initial 18.8 18.14
After demulsification 13.8 14.26
Initial water saturation 31.5 % 32.6 %
Residual oil saturation 31.4 % 30.0 %
Inhibitor flood & SW 30 30
Ipostflush f1owrate(m/hr)
Residence Time (min.) 27.6 28.52
PV of SW postflush at
5.5 ppm active inhibitor 1080 828
Brief Summary of Mineralogy of Core Used in
Floods F3 and F4.
Mineral types Flood F3 & Flood F3 &
F4 before F4 After
Quartz 80% 80%
Feldspar - microcline 7-9% 7-9%
- orthoclase
muscovite mica 1% 1%
Lithic fragments 0.5% 0.5%
Clay types - kaolinite 8-10% 5-9%
- chlorite 1-3% <1%
- illite 1-3% 1-3%

Pyrite <1% <1%

Comments Sub-arkosic Red stained

arenite, well inlet face low
cemented, mechanical
pale grey in strength
colour

459
Table 3: Factors affecting scale inhibitor adsorption and potential formation damage
Factors Effects on Inhibitor Adsorption Potential for Formation or Fluid Damage

MINERALS

Quartz Adsorbs inhibitor depending on pH, [Ca 2 +], Fairly inert - mild dissolution and little likelihood
Temp. etc; lower adsorption than clays due to of formation damage.
lower surface area and charge structure;
(Refs. 4, 7-10).

Feldspar As quartz. More reactive than quartz; severe pitting

observed in some cases resulting in small lath like
fragments which may mobilise.

Clays

Kaolinite Clays adsorb much higher levels of inhibitor than Increase in reactivity to low pH inhibitor solution
Illite quartz due to high surface area and charge in order kaolinite < illite < chlorite. Pitting of
Chlorite structure; level also depends on pH, [Ca 2 +], kaolinite seen - possible fines migration. Chlorite
Temperature. (Ref. 19). dissolution leads to high iron levels ("fluid
damage"). Some evidence of preferential oil
Smectites and other emulsion wetting on kaolinite, fines coagulation
swelling clays and formation damage (see below).

Carbonates

Calcite Carbonates will adsorb fairly high levels of Carbonate dissolution decreases in order calcite,
Dolomite inhibitor at moderate to high pH (>5). Carbonate dolomite, ankarite, siderite. Can cause fines
Ankerite dissolution occurs at low pH. migration and sand production if carbonates form
Siderite principal cements. Resulting high [Ca 2+] may
cause precipitation of inhibitor-calcium complex.

Pyrite Pyrite will adsorb as much inhibitor as non-clay Acidification can cause iron release which results
silicates; probably some iron-inhibitor surface in fluid damage (see below).
binding.

SOLUTION
CONDITIONS

Salinity Ionic strength affects the surface potential (~
potential) which in turn affects the inhibitor
adsorption; divalent and trivalent ions are charge
determining (Refs. 10,19,33).
Ca2+ ion concentration has little effect on
inhibitor adsorption at low pH but it is involved
in inhibitor complexing and binding at higher pH
for both quartz and clays (Refs. 4, 7, 8, 10, 19).
Changing the salinity of the formation brine can
cause fines migration and clay swelling, in some
cases. Brines used in this work have a high
salinity and this is not observed here.
High calcium ion concentration may lead to the
formation of an insoluble inhibitor-calcium
precipitate; this may lead to permeability
reduction. Is also the basis of certain
"precipitation" squeeze processes.

pH Inhibitor adsorption onto both quartz and clays Acid phosphonates may lead to carbonate cement
strongly influenced by pH; through hydrogen or chlorite dissolution (see above); these may
bonding at low pH (-2) and by Ca2+ - binding at result in fines migration, sand production, high
higher pH (>5). (Refs. 9,10,19). Ca2+ or iron in solution etc.

Iron As a multivalent cation, iron can enhance Iron in solution is damaging in several respects:
inhibitor adsorption at high pH (>4). (i) can cause iron-inhibitor complex to
precipitate; (ii) can affect inhibitor efficiency
even at 5-lOppm; (iii) reduces the sensitivity of
the inhibitor analysis for most chemical assay
methods. May be produced as a result of low pH
solution with certain minerals (e.g. chlorite, pyrite
etc) or from tubulars.

TEMPERATURE Has strong influence on adsorption and Precipitation of calcium-inhibitor complex at

precipitation of inhibitor. Higher adsorption onto elevated temperature may cause formation
quartz and clays at higher temperature. Increases damage.
the rate of adsorption. (Refs. 10, 19)

SPEARHEAD Surfactant/demulsifier in spearhead tends to Some spearhead chemicals form undesirable

(oil type and wettability) increase the water wetness of the formation. This emulsions which may preferentially wet certain
results in higher inhibitor adsorption. minerals (e.g. kaolinite); these may then
accumulate other acid etched fines reSUlting in
formation damage (permeability decline).

460
 Micrograph 1 (MMJ061)
Micrograph 1 (MMJ061, Pre-Treated Sample)
Secondary electron micrograph of an authigenic potassium
feldspar overgrowth around a detrital feldspar grain surface
(kf) at the edge of a pore. The grain surface is slightly pitted
due to dissolution of the mineral by the pore fluids during
diagenesis of the sediment. This is the typical fabric displayed
by feldspar grains from the Tarbert Formation. Note the clean
surfaces of all mineral grains within the micrograph.
Micrograph 4 (MMJ279)
Micrograph 4 (MMJ279, Post treated sample)
Secondary electron micrograph of vermiform kaolinite (vk)
being enclosed by quartz overgrowth (q). There is little
evidence of kaolinite dissolution at the edges of the crystals.
There is no evidence of dislodgement and migration of
kaolinite within this pore but in others some migration of
kaolinite is evident. The lack of fines migration is probably
due to the kaolinite booklets being cemented in place by the
quartz overgrowth. The globular material on the surface of the
kaolinite is an oil emulsion. This material is found exclusively
on the surface of kaolinite but is absent from the surrounding
quartz.
Micrograph 2 (MMJ283)
Micrograph 2 (MMJ283, Post-Treated Sample Flood F4,
Inlet Face)
Secondary electron micrograph of a potassium feldspar grain
surface (kf). This grain is considerably more pitted than that
seen in Micrograph I. The extensive dissolution to this grain
has been caused by the corrosive acid phosphonate used in the
squeeze treatment. The highly corroded feldspar grain has
started to break down into lath shaped fragments. These may
then move through the pores resulting in pore throat
constriction
Micrograph 5 (MMJ136)
Micrograph 5 (MMJ136, Pre-Treated Sample)
A typical pore morphology seen in the Tarbert Formation
samples. Early vermiform kaolinite (vk) is enclosed by later
euhedral quartz (q). The presence of later authigenic cement
has restricted the pore throat. Note the clean surface of the
core with little evidence of fines.
Micrograph 3 (MMJ133)
Micrograph 3 (MMJ133, Pre-treated sample)
Secondary electron micrograph of pseudo-hexagonal kaolinite
booklets (k) at the edge of a pore being enclosed by later
quartz overgrowths (q). This type of relationship is very
common within the Tarbert Formation samples examined in
this study. Note the microporosity which occurs between the
individual clay sheets and booklets.
Micrograph 6 (MMJ29S)
Micrograph 6 (MMJ295, Post-Treated Sample Flood F4,
Outlet Face)
Micrograph of a restricted pore throat. The restriction is due
the presence of an oil emulsion (oe) and the entrapment of
feldspar (kf) and kaolinite (k) fines. The pore would appear to
have originally been lined by kaolinite (k) which has later
been coated in an oil emulsion. During the course of the flood
small particles released from the dissolution of K-feldspar
have migrated into the restricted pore throat blocking it still
further. This type of restriction is very common in core F4.
 20

~
Ci>
18
16 /

:

14
!
i
=
0

.
0
'"
'1:1
12
10
8
--- Quartz + solution without Ca at pH 295"C
Kaolinite + solution without Ca at pH2 25"C
Kaolinite + solution without Ca at pH 2 95"C
< 6
.....
....
4 mEl

0
2 /
0 5 10 15 20 25 30
Contact time (hours)
Figure 1. Static adsorption of 5000 ppm Il phosphonate
inhibitor at pH 2 over 30 hours onto kaolinite and quartz

1.2
0
at 20C -+l~ at 110C

....
U
U 1.0 ,
=
0
:::<U
shut in 17 h""':
& SW postflush

..... 0.8

=
"
=0.6
0 Flood T3
U

.-;.
58,OOOppm active inhibitor
'1:1
0.4
~

-
pH = 2.00

.
E 0.2
0
---0-- Li
Ca
Z inhibitor
0.0
0.0 2.5 5.0 7.5 10.0 12.5
Pore Volume
Figure 2. Normalised frontal profile of Lithium, Calcium and
Inhibitor Ila for flood F3.

E 120 - Flood F3 - (58.000ppm. 29% active) pH=2.00

Q.
Q. - Flood F4 - (43.500ppm. 29%-active) pH=2.43
-; 100
~
...~ 80
e
8= 60
.
'0
:c:a 40
.s
~ 20
::: 5 ppm

<" ---~---------------
o~~~~~~~,-~~~~~~-.~~~~~

o 200 400 600 800 1000

Postflush Pore Volume
Figure 3. Comparison of inhibitor returns in the effluent
during seawater postflush in floods F3 and F4.

462
 50000 6
8'C. at 20C - . : .... at 110C
~
40000 Flood F4:
=
.S!
.... shut in 18 hr . 43,500ppm active 5
~ & SW postflush inhibitor 11 b
....'"' at pH 2.43, SWat pH 5.50
=41
<.J
30000
=
U
Q 4
==C.
20000
....'"'
Q

:E
:c inhibitor 3
....= lOOOO
pH
41
.::....
<.J
-< 0 2
0.0 2.5 5.0 7.5 lO.O 12.5 15.0
Pore Volume
Figure 4. Inhibitor and pH effluent profiles during
injection and postflush for flood F4.

600
-- Flood F4. atiIOOC
550 -- Flood F3. at 110C
500
8'c. 450
~ Initia1low values due to ferric iron inhibitor complex.
400
=
.S!
....~ 350
Iron concentration was probably similar to that recorded for flood F3

....'"' 300
=
41
<.J
Q
U
= 250
200
Q=
....
'"' 150
lOO

oL========::d
50

o 2345678
Sw postflush pore volume
Figure 5. Iron concentrations profiles for floods F3 and F4 during
9 lO

inhibitor shut in and Sw postflush.

30
------ AI concentration
5 25
c. -- Si concentration
c.
=
.S!
.... 20
~
....'"'
= 15
41
<.J
=
Q
<.J
.... 10
=
41
5
1ii
41
5 ~
0
0 50 lOO 150 200 250 300
Pore volumes of postflush
Figure 6. Silicon and aluminium release from Brent sandstone
core into effluent during desorption of flood F3

463
'[ 00000 r,c;:;---rc;-------;:;;::;;;:;;::::;;:;;;;;:::;;;;;;;;;;;:::l
~
c
~<U
.
C 10000
..,'"
c
..,o
c
.S
:; 1000
'0
..
'"

:c.s A
:c.s 100
"~
o 250 500 750 1000 1250 1500 1750 2000
Calcium concentration in solution (ppm)
Figure 7. The phase diagram of phosphonate Inhibitor and calcium
complex at pH 4, 5 and 6 and 95C.

-=
--
U
1.0 Initial Li flood
S ---0-- after oil resatuation
Li with II b/SW after
C demulsification
0.8
.S
....
C 0.6
'"C
..,'0"
J 0.4 Residual oil saturation:
Sor; 30.0 %
."
'"
.~
-; 0.2
..S
0
Z
0.0
0 5 10 15 20 25 30 35 40
Cumulative Volume (ml)
Figure 8. Lithium effluent profiles at different
stages of flood F4.

20

-
-<>-- Flood F3 Differential pressure
18
.:;; Flood F4 Differential pressure
~ 16
.'"= 14

.'"'"
=-'"
12
10
~ 8
.'"
C
~
6
4
is 2

200 400 600 800 1000

Postflush Pore Volume
Figure 9. Profile of differential pressure across the core during
seawater postflush for floods F3 and F4.

464