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SPE 29002

Static and Dynamic Adsorptionof Phosphonateand PolymericScale

InhibitorsOnto ReservoirCore From LaboratoryTests to Field
Application
M.M. Jordan,* K.S. Sottie,* and M.D. Yuan*, Heriot-Watt U.; Kate Taylor, Shell U.K. E&P;
K.E. Hourston, Total 011 Marine; Kari Ramstad, Norsk Hydro as.; and Paul Griffin, Enterprise Oil
●SPE Members

-W9ht IWS. SocMY of Petmbum Engin@rs, Inc.

This paper was pmpamd for presentation at the SPE Intwnathnal Sym~um on Oilfield CMW w in an A~Onb, TX, u. S.A - 14-17 *~V 1*

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* -d. haw nor hen rfMewd by the SocretY of Petroleum Er@near’a M we subw to cmectmn bythOaurhOrts). ThOmatOM, as Prwem@, do-m~*
wry poaitbn of the SaciMY of Petrotoum Engirwwa, w offiim, or members. P8PWS pmnnbd at SPE rnostings am wbjwt to publicdon reviw by Edhorial CommHton9 ot ttw Society
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ABSTRACT

In this paper, results from static tests have been used to
establish scale inhibitor adsorption mechanisms and levels in
... ...L—
consolidated reservoir cores and to ratm mmcmors for their
adsorption behaviour and, in some cases, squeeze return
lifetimes. The purpose of this rapid and simple type of bulk
adsorption measurement is to assist in the selection of
inhibitors for further coretlooding which should be carried out
on a minimum number of inhibitors. A bulk adsorption
sensitivity study can be canied out very rapidly compared with
~aref~]!v , carried
-—---- out
--- .reservoir
.. condition core floods. The
value of such rapid screening tests is evident although we
show that it is not always possible for all factors concerning
squeeze lifetime to be determined in this way. It is still often
necessary to carry out a much smaller number of reservoir
condition core floods for a few (usually between 1 and 3)
selected inhibitor products. This is necessary if the dynamic
adsorption isotherm, I’(C), is to be derived in order to develop
the “Field Squeeze Strategy” or for the assessment of
formation damage which might occur in the squeeze treatment.
A field example of this is presented briefly in this paper
aithough cietaik can “Mfound eiseiviiere.
INTRODUCTION
The downhole 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 scale inhibitor “’squeeze” treatments. 1‘6
Two main types of inhibitor squeeze treatment can be carried
out where the intention is either (a) to adsorb the inhibkor on
the rock substrate by a physical-chemical process using a
phosphonate or a polymeric material; or (b) to extend the
squeeze lifetime by precipitation (or phase separation) which
References and illustrations at end of paper
is commonly achieved by adjusting the solution chemistry
([Ca2+], PH. temperature) of a polymeric in~bitor such ss
I-.--.--L.--...1:-. UQ,U
. . ....4f~.DDPA>
piy pitospninwximwiyuv r em,.
In adsorptioddesorption treatments, the most important factor
governing the dynamics of the return curve is the
inhibitor/rock interaction as described by the adsorption
isotherm, r(C), which is a function of inhibitor type,
molecular weight, pH, temperature, mineral substrate and the
brine streng$ and com.position.2-5’7 -12 The precise form of
r(C) determmes the squeeze lifetime, as has been described in
detail in a number of previous papers. 13-18 The “precipitation
squeeze” process is based on the formation of a gel-like
calcium salt, usually of poly phosphhmcarboxylic 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
process24
In this paper, our objective is to review the role of static
adsorption tests involving phosphonate and poiymeric scaie
inhibitor adsorption onto crushed reservoir core. Bulk
adsorption tests of this type can be carried out very quickly
and a wide range of sensitivities of in-hiiiitor adsorption (e.g. to
PH. [Ca2+], temperature etc.) can be examined. In contrast,
reservoir condition core floods are very time-consuming and
expensive to carry out and, in field evaluation tests for a given
application, it is desirable to take only one or two inhibitors
forward to this stage. We find that higher levels of adsorption
in static tests often suggest higher levels of adsorption in
dynamic core flooding tests which usually result in longer
squeeze lifetimes. However, there are some subtleties
concerning the dtape of the dynamic adsorption isothexm,
r(C), which will not be detected by the crushed rock
adso@ion tests. Static adsorption tests may also be used to
suggest when a product might “be better empioyed in a

613
 2 STATIC AND DYNAMIC ADSORPTIONOF PHOSPONATEAND POLYMERICSCALE INHIBITORS
ONTO RESERVOIRCORE FROM LABORATORYTESTS TO FIELD APPLICATION
“precipitation” process since its adsorption level - even onto
crushed rock - is too low. Therefore, these tests may provide a
good method for inhibitor screening of materials which have
already been screened for inhibition efficiency, in order to
further select products for dynamic coreflomling. In applying
the results of bulk adsorption tests of this type, we find that the Tarbert Formation floods for comparative purposes. The
approach is only valid when the data is “grouped” into
substrate types; that is, for a given reservoir rock system,
products can be ranked based on these tests. 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 ,,6,15,17.25,26 and a]w to assess formatiOn
damage.27
EXPERIMENTAL DETAILS
Core Materials Used - Absorbents: The core samples used
for static adsorption tests were first disaggregate to 400pm.
These materials were the same as those used in the
corresponding core floods and their mineralogies
summarised in Table 1. The disaggregation or crushing of arty
rock or mineral sample results in material of higher surface
area and with higher surface energy which is therefore more
reactive. As a result, the static beaker tests often give higher
values for adsorption than those observed in consolidated
sandstones containing these minerals as authigenic cements.
However, even taking into account these problems, the
important sensitivities to pH, calcium and temperature may be
in the correct direction for predicting and analysing
consolidated core flooding experiments in reservoir core. We
have previous demonstrated that this is the case for DETPMP
and PPCA adsorption onto quartz and clays.25*28
Experimental Procedures for Adsorption Tests: In the phosphonate
adsorption experiments, stock solutions containing various
scale inhibitors were prepared using synthetic seawater (Table
2). To determine adsorption of inhibitor as a function of pH,
stock solutions containing 2500 ppm active inhibitor were
prepared using seawater. For the tests, solution pH was then
,.–.1.
aajus~ea 10 the Mowing---- viaws. A, A +, 5 arid 6. T%:”
..-1 ----- 0 9 A
, ,11s -u
range was chosen since pH below 2 is irrelevant to field
squeeze treatments while, at higher pH (i.e. pH 27 at 25-C or
pH25 at 95”C), the 2500 ppm phosphonate inhibitor (11, Ila,
Ilb, 11c) has been found to precipitate from the seawater
solution 10$25 and thus genuine adsorption tests cannot be
performed.
The adsorption tests were carried out at various temperatures
(25”C, 75°C and 95”C) and most results are reported for
equilibration after 24 hours. After filtration at test
temperature and cooling to ambient temperature, the samples
were analysed for the inhibitor, calcium concentrations and
pH value. Each individual stock solution was also analysed
for the inhibitor and calcium concentration which are referred
to as the stock data. The inhibitor concentration difference
between the stock and the sample was used to evaluate the
adsorption level, rmax (quoted in mglg -> mg-inhibitor/g-
mineral substrate). The experimental details of the adsorption
and equilibration time tests are reported elsewhere. 10*u*27
Absorbents - Core Material: Details of all core floods which
were carried out in this study are summarised in Table 1.
These floods were carried out using consolidated reservoir
cores from the North Sea Basin, Reservoir conditioned
SPE 29002
inhibitor core flooding results will be presented for oil-
reconditioned cores from the Tarbert, Etive and Oseberg
Formations of the Brent Group and Forties Member of the
Sele Formation. Outcrop core (CIashach sandstone) was also
conditioned with the same Brent crude oil as was used in the
mineralogy of the Tarbert Formation and Clashach sandstone
are described briefly in Appendix A and in much more detail
elsew~m. 10.25.27
Inhibitar, Srufaetants and Brine: All of the inhibitors and
surfactants (spearhead chemicals) used in this study are
commercial y available products. Three acid phosphonates
(coded 11, Ha and Ilb; Penta-phosphonates - DETPMP) and a
partially neutralised phosphonate (coded I lc; Hexa-
phosphonate) were used in this work. The appropriate
dissociation of such phosphonates with pH has been described
previousl y.9~ 10 The polymeric inhibitors include a
phosphinocar-baxyiic acid (I3; F?CKj, two poiy acryiic acids
(coded 14 and 14b; PAA), one carboxylate copolymer (coded
are 14a) and two sulphonated copolymers 15 (poly vinyl
sulphonate, PVS ) and 15b sulphonated acrylic acid. Summary
details of these products are presented in Table 3.
The surfactants used in the present study were products
selected by service companies as being compatible products
for use with the reservoir oil and inhibitors to be applied in
these North Sea field cases. The brines used in this work
were synthetic North Sea brine (floods F3, F4, F7 and F8) and
formation water (floods E 1 to E4) made from dissolved salts
with the compositions given in Table 2. These brines were
filtered through a 0.22@ membrane filter prior to use.
Assay Methods: The methods for determination of the
inhibitor concentration was the
persulphate/ultraviolet method originally developed by
HACH29 and subsequently modified at this laboratory. This
procedure in synthetic seawater allows the determination of
phosphonate inhibitor concentration down to 0.25 ppm +1-
0.04 ppm. For the analysis of phosphinocarboxy lic acid
pa, (.d.,i ~a) u,- ,...at+ . v.mrcinn nf tk= methnd nf N.fumhv ~flgj
{~-= ~J9 -- =— - .-. ”.”.. -. --- . ... ... . . -- -.---J---,
Riley30 which has been chosen in preference to the standard
Hach method as it is more accurate and reproducible at low
concentrations (c 5 ppm). This procedure in synthetic brines
allows the determination of phosphinocarboxylic acid (PPCA)
concentration down to 0.50 ppm (+/- 0.06 ppm). The analysis
of polyacrylic acid and the co-polymer was carried out using
Hyamine 1622.31 The analysis of the two sulphonated acrylic
acid copolymers was carried using the Pinacyanol chloride dye
method.31 *32 A more recent survey of inhibitor assay methods
is presented elsewhere .33 A Varian Atomic Absorption
Spectrophotometer was used for the analysis of lithium
(tracer), calcium and iron. For all of the calibrations, the
matrix matched standards were used to suppress the
interference of the brine.
Experimental procedure for Core-s: Field core plugs of
diameter 2.5 cm were usually cut along the vertical axis of the
10 cm diameter preserved sandstone core samples. In floods
F3 and F4, the cores were cleaned by hot organic solvent
extraction (toluene and methanol + chloroform) using a
soxhlet while the core used in floods El to EA was cleaned by
mild miscible cleaning using toluene followed by methanol at
room temperature. One of the most important reservoir
parameters in these core floods is the temperature; this is
614
SPE 29002 M.M. JORDAN, K.S. SORBIE, M.D. YUAN, K. TAYLOR, K. E. HOURSTON, K. RAMSTAD AND P. GRIFFIN
11(YC for the source reservoir of the Tkrbert l%. core rtiaieriai
,ic-d ft@c-----~ and F4 and is I07°C for floo(k El to E4 ~d
“—. ip ..”
F7, F8. However, there will be cooling effects during the
spearhead and inhibitor placement stages which must be
~eflec!ed in.. tfie
.. - ~CM~I strategies for inhibitor core flood
evaluation. The effluent fluid from the core floods was
monitored for PH. inhibitor, lithium tracer, iron, and calcium
ion concentrations. Although many field core floods have
been carried out, it is not possible to present all the details
here. Instead, representative phosphonate and polymer
inhibitor core floods from North Sea reservoirs have been
chosen to illustrate some typical observations. Similar
proceduxs are described elsewhere.25*27*34*35A summary of
the experimental details of some of these floods is presented
in Table 1.
After the flood cycle, the permeability was measured to
determine if the treatment had caused any degradation in
reservoir properties. A full mineralogical analysis was camied
out on the post-flooded core material and thk was compared
with the mineralogical results for untreated core samples.
The original mineralogy of each core is summarised in Table
1. Some aspects of how this mineralogy changes after
treatment with inhibitor is discussed elsewhere.27
EXPERIMENTAL RESULTS: COMPARISON OF
PHOSPHONATE AND POLYMER ADSORPTION
ONTO DISAGGREGATE RESERVOIR CORE
This study focuses on scale inhibitor adsorption onto
disaggregated reservoir core from the Brent Group formations
and the Forties member of the Sele Fm. in the North Sea.
Although these formations are sandstones and are principally
made up of quartz, they contain significant quantities of clays
as summarised in Table 1. The bulk adsorption results
presented in this section will later be compared with the
inhibitor return curves from reservoir condition core fioods in
correspondkg (consolidated) field cores. The objective of this
work is to determine whether the bulk adsorption tests can
give us some indication of the behaviour in the core floods.
Penta-pkosphonate and PPCA A&orption on Disaggregate
Tarbert Fm. Core: The differences in the adsorption
W.- “. yr+n-.nhnnnte
. .. . . nf
hnhnv;rwr ...”r.. ---- - (~!;
, ~ETp_MP) and PPCA (13) on
reservoir core from the North Sea (Tarbert Formation) are
compared in Figure 1. As noted above, this formation is
~e]ative!y clay rich With kaolinite being the principal clay
mineral. The solutions used have the same active content of
inhibitor (2,500 ppm active) to allow direct comparison
between the data. At 25-C and 95*C, the amount of 11
adsorption exceeds that of 13 at similar pH values. As in the
phosphonate adsorption measurements onto quartz, higher
adscxpticm of phesp!mnam al pH 2 and 6 relative to pH 4 is
again observed and can be attributed to a hydrogen bondhg
mechanism at low pH and a calcium bridging effect at higher
pH va!ties. 10~25!27.28 n.is is cenfirmd by the dec!ine in
[Ca2+] as pH increases shown in Figure 2, which again
indicates that the role of calcium is exactly as described
previous. 10925s27j2s
PPCA adsorption in Figure 1 at 95*C shows a slight increase
with pH rather than a maximum, as was seen for pure
kaolinite.28 However, this observation is probably due the
smaller proportion of kaolinite relative to quartz and it is very
615
3
l:L. 1.,
Ilmel k., *L:=: ~r~- ~ ;. ;nd~d due !Q enhanced calcium
y Ulab Luaa AL. V-SW .“ . ..”
bridging which is favoured at higher temperatures.
In order to compare the product to product variation between
the same phosphonate inhibitor types, repeat adsorption
experiments onto Tarhert Fm. core material were carried out
on two commercial products (I 1a and I lb). Results are
presented in Figure 3 which show that these products behave
in an almost identical manner when the concentrations are
corrected for active inhibitor content.
Hexa-phosphonate, Sulphonated acrylic and Poly vinyl
sufphonate Adsorption on Disaggregate Tarbert Fm. Core:
We now examined the differences between a hexa-
phosphonate, a sulphonated copolymer and poly vinyl
sulphonate (PVS) adsorption onto reservoir core from the
North Sea (Tarbert Formation). The inhibitor adsorption data
for these materials is shown in Figure 4. At 95*C, the amount
of hexa-phosphonate adsorption exceeds that of the
sulphonated acrylate which itself shows higher adsorption
than the PVS at similar pH values. As for the penta-
phosphonate adsorption measurements, higher adsorption of
hexa-phosphonate at pH 2 and 6 relative to pH 4 is again
observed and can be attributed to a hydrogen bonding
mechanism at low pH and a calcium bridging effect at higher
pH values. 1W%27*28 Thistypeof mechanism is not evident
(or expected) for the two sulphonated polymers - the
sulphonated acrylate and the PVS. The higher level of
adsorption observed for the sulphonated acrylate compared
with the PVS is due to the higher proportion of carboxylate to
sulphonate groups. ‘Ilk would suggest that the squeeze life of
the sulphonated acrylate copolymer would be longer than that
of the pure PVS.
The decline of [Ca2+] as pH increases, seen in Figure 5 for the
hexa-phosphonate, is more steep than for the penta-
phosphonate which iiid~~~i~~ that hex&=ph~@orta!e
interaction with calcium is stronger than the interaction
observed for penta-phosphonate. The calcium trends for both
the sulphonated acrylate and PVS are similar with little
evidence of interaction of inhibitor with calcium being
suggested by this data. Note that the blank seawater case in
Figure 5 shows some decline in [Ca2+] with pH.
Inhibitor Adsorption Levels onto Forties Member core:
Results in Figure 6 show the adsorption behaviour for a hexa-
phosphonate (I lc) and two polymers (poly acrylates - 14a and
14b) onto cmshed Forties Member core at 9SC. The general
trends here are as expected from our previous results and both
poly acrylates show very similar behaviour. We note from
Figure 6 that 11b has a lower level of adsorption than the
polymeric inhibitors (14a and 14b) at 95*C, pH 2. As the pH
rises above pH 4, at all temperature the adsorption of 11b is
greater than for any polymer inhibitor (through calcium
binding). It is evident from the calcium results in Figure 7
that the general mechanistic view of adsorption discussed
above also applies here. 10~5J27*28
Summary of Inhibitor Bulk Adsorption Results on
Disaggregate Reservoir Core Material: Several generic
types of scale inhibitors have been evaluated in terms of their
observed levels of adsorption in bulk static tests onto reservoir
core material under a variety of conditions. Our main finding
is that the levels of adsorption in the disaggregated reservoir
 4 STATIC AND DYNAMIC ADSORPTION OF PHOSPONATE AND POLYMERIC SCALE INHIBITORS
ONTO RESERVOIR CORE FROM LABORATORY TESTS TO FIELD APPLICATION
material are broadly consistent with the mineralogical
composition of the rock as discussed elsewhere. 10~27*28
Furthermore, the sensitivities (to temperature, pH, [Ca2+]) of
the adsorption level for the various inhibitor types are very
similar which strongly indicates that the same adsorption
mechanisms are involved. 10*Z*27J8
EXPERIMENTAL RESULTS: RESERVOIR
CONDITION CORE FLOODS
This study now seeks to establish whether the bulk adsorption
measurements on the disaggregated core correlate with the
consolidated core flood results. The actual adsorption levels
are not expected to be the same; it is the mechanisms, the
trends and the relative ranking of scale inhibitors for
adso@on that we might expect to be similar.
Inhibitor return effluents are presented for two reservoir core
systems. However, the results from several other reservoir
condition core floods are presented only in summary form.
Presentation of the fill details of rdl floods is beyond the scope
of this paper although some are described elsewhere.25~27*34
Table 4 summarises the comparison of the “average” bulk
adsorption on the disaggregate reservoir core with the return
time (in pv) to a chosen inhibitor threshold level from the
corresponding reservoir condition core flood. The “average”
bulk adsorption level is defined as the value at a representative
set of conditions (temperature and pH, in particular) in the
bulk tests which are closest to the conditions at which the core
flood was carried out. Of the results referred to in Table 4,
only the effluents for the comparisons of F3/F4 ((i) below) and
E2/E3((ii) below) are presented.
We do not present the corresponding calcium and pH effluents
for the reservoir condition core floods although all of these
data are available for all the floods in Table 4. This data
confirms that the adsorption mechanisms described above also
apply in the core system (i.e. hydrogen bonding at low pH,
calcium involvement etc.) 10~25*27~34~35 A large number of
resuks of this type are presented in other papers. 10~25*27~M*35 hexa-phosphonatc is up to three time as efficient as the penta-
The detailed bulk adsorption and core flood comparisons are
presented belwo.
COrnnariWMI(i):
~—. ----- ,.,. of the .him
-J ---- nenrknhns.hn.ntm
..- r---—
r----r. ---. —--”
in Tarbert Formation core. The bulk adsorption levels for
these two phosphonates were similar on crushed Tarbert core
as shown in Figure 3. The inhibhor effluent concentrations in
the corresponding reservoir condition core floods F3 (Ila) and
F4 (Ilb) at 1100C in the Tarbert core are shown in Figure 8.
The corresponding bulk adsorption levels onto the Tarbert
core in Figure 1 (and in Table 4) are seen to be quite similar.
Therefore, the expectation is confirmed that the similar bulk
adsorption levels in the same disaggregated rock system lead
to quite similar lifetimes to inhibitor threshold (in pv) in the
consolidated core flood.
In these floods, it was found that the calcium concentration in
the effluent from both floods was significantly reduced in the
*4v
w-l,
mart mf
~.u. “.
th.
“,-
-crfl,
p“..,.
sch -.;,+
”.., p,,”u. IL-W.,..,..
,.””- .-,,
i. kth
,,, w.,,
the calcium concentration returned to input level within 3 pore
volume of postflush. This early reduction in calcium
concentration was due to adsorption onto the rock as an
inhibitor/calcium complex; note that it is not a precipitation.
SPE 29002
It corresponds to the precise mechanism described above in
our bulk adsorption studies. 10~25*27*M~35
Comparison (ii): of adsorption of a phosphonate (IZC) and
polymer (14b) in Forties Member core. In this case, from the
bulk adsorption results in Table 4, we wouid expect the
phosphonate return curve in the Forties member consolidated
core to be correspondingly longer. Figure 9 shows a
comparison of the inhibitor return effluents in floods E2 (IIc)
and E3 (14b) in the Forties member core at I07”C. In this
case, the amount of initial adsorption after shut-in and post
flush (at 107”C) was rather smaller than in the above two
floods due to the intermediate nettability of this core material.
The results in Figure 9 show that, even although the level of
inhibhor adsorption is low the length of time required for the
phosphonate to fall below 1 ppm active was 12 times longer
than for the polymer under identical conditions. This would
appear to confirm the static adsorption test results in Table 4
which show that the phosphonate @) had considerably higher
levels of adsorption than the polymer (E3). The return curves
in Figure 9 clearly show that this bulk adsorption result carries
over to the reservoir core flood return observations.
Comparison (iii): of a penta- and a hexa- phosphonate in
Tarbert core. Figure 10 shows the coreflood return profiles
for two phosphonate floods - one penta-phosphonate (F3) and
one hexa-phosphonate (F1O) in Tarbert Formation core. From
the static adsorption tests, the hexa-phosphonate has a much
higher level of adsorption over all pH values (Figure 4)
compared with the penta-phosphonate (Figure 3). Figure 10
indicates that the hexa-phosphonate gives an apparently
shorter return life even although its adsorption level is
significantly higher than that of the penta-phosphonate. This
observation highlights two subtleties on which the bulk
adsorption tests give us no information. Firstly, the actual
length of the return curve depends on the chosen inhibitor
threshold concentration, Ct (the concentration at which the
inhibitor will prevent the scale problem - at a specified level of
performance). Indeed, for many formation waters, since the
phosphonate at preventing barium sulphate scale per ppm of
active chemical, the concentration level can be slightly
misleading. Thus, in Figure 10, the 2ppm level of the hexa-
11. nmi ..w Ilh phosphonate at 1400 pv is equivalent to -6 ppm of penta-
..- ___
phosphonate which dropped below 5 ppm at 1100 pv of
postflush. Secondly, the static maximum adsorption level,
rmax, at a given inhibitor solution concentration (2500 ppm
active, in this case) takes no account of the shape of the
dynamic adsorption isotherm, r(C), which actually governs
the full shape of the return curve as explained
previously. 13*14*15*35This is considered further below in the
discussion of Static and Dynamic Adsorption Isotherms.
Comparison (iv): of adsorption andprecipitatian of the same
polymer. Bulk adsorption results in Figure 1 indicated that
the polymer adsorption level was relatively low. For this
reason, two inhibitor floods were conducted using the same
polymeric inhibitor as an adsorption treatment in one flood
tlnrvl.
‘, —.,
and as a precipitation treatment in the other. Fi-wre 11 shows
the effluent profiles of these two floods where, for Flood El,
the return profiles is for the adsorbed polymer and Flood E5 is
the corresponding return profile of the same polymer
formulated with calcium to precipitate at reservoir
temperature. The difference in the return profiles is clear and
616
SPE 29002 M.M. JORDAN, K.S. SORBIE, M.D. YUAN, K. TAYLOR, K. E. HOURSTON, K. RAMSTAD AND P. GRIFFIN
the precipitation mechanism would appear to have extend the
~etl~- PrQfi!~ by rno~ than 5 times to the same 1 ppm (active)
threshold level. The use of the bulk static adsorption tests in
this context is to show that the adsorption level of polymer 14a
W* y~~ ]Ow - much below the level of the phosphonate for
example. Thus, its performance as a pure adsorption
treatment would probably be unsatisfactory - and this is
confumted in Figure 11. However, the lifetime can be greatly
extended by inducing precipitation. The question of whether
this precipitation treatment using a polymeric inhibitor would
exceed the adsorption treatment using a phosphonate cannot
be answered using bulk static adsorption tests. For such a
comparison, dynamic core flooding would have to be carried
out.
Summary of Results: The results in Table 4 can be used to
~Qns~~t scatter Plots of Static Adsorption Level (mg/g) VS.
Core Return “Lifetime” (in pv) in an instructive way only
when the data is grouped appropriately. The data grouping
must refer to the specific core conditioned system within
which the comparison of bulk adsorption and core flood return
results can “mmeaningfully made. This is shown inF@we !2
(cf. El, E2, E3, E4) and Figure 13 (cf. F3, F4, F5, F7, F8, F18)
where the correct groupings have been selected. It is clear
from these results that the higher levels of bulk adsorption on
~h~di~~g=~gat~ reselvoir rack - within a comparable group -
lead to longer return times in the reservoir condition core
floods. However, we cannot compare results from very
different systems. For example, the bulk adsorption associated
with floods El and E3 for the polymer adsorption in the
Forties member show similar bulk inhibitor adsorption levels
as bulk measurements corresponding to floods F3, F4 and F5.
However, the return lifetimes in floods F3, F4 and F5 are
much longer than those for floods E 1 and E2. Because of the
very different nature of these different cores (in mineralogy
and nettability, for example), this type of ungrouped
comparison is not valid. As noted above, such static
adsorption tests can also be used to indicate when chemicals
should be formulated as precipitation treatment based on static
adsorption pro~rties.
STATIC AND DYNAMIC ADSORPTION ISOTHERMS
As noted above, there are some subtleties which cannot be
resolved solely by static adsorption tests and, therefore, care
must be used in interpreting such tests. This is clear from the
comparison between the bulk adsorption levels of the penta-
and hexa-phosphonates and their corresponding return curves.
-. .-
ltus can only oe understood ...I. . .+&
Wllell ,- ~AuI...J.-
~. .min- the
...w Anmqic
-,.. . .. . .
adsorption isotherms from the reservoir condition core floods
using these two products. The dynamic adsorption isotherms
(derived as explained elsewhere 3*14*35) for these two
phosphonate inhibitors are presented for Tarbert formation
cores in Figure 14 (penta-phosphonate Fk@s F3 and F4;
hexa-phosphonate Flood FltJ Table 1).
The first point to note from Figure 14 is that the maximum
dynamic adsorption level at high inhibitor concentration is
higher for the penta-phosphonate than for the hexa-
phosphonate; i.e. dynamic rp.m > rhc.a. In pafiicular, the
dynamic hexa-phosphonate adsorption level is well below its
corresponding bulk adsorption levels onto the Tarbert crushed
core (Figure 4). However, in this case, it is evident that there
is a considerable amount of additional calcium available
617
5
(Figure 6; (UCO)C, > 1) from the crushed core material itself.
Since the hexa-phosphonate has a stronger affinity for
. . . ._ :..... I..n,-l”’”ll
calcium, then enhanceo absorption tiy Ca!clulll W,,US1..SXnay
be occurring.
A second point, concerning ihe Obser?d !Wg !W-
concenrration inhibitor return profile for the hexa-phosphonate
(Figure 10) 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 Cl= 5-10 ppm, the slope of the
adsorption isotherm for the hexa-phosphonate is steeper than
that of the penta-phosphonate; i.e. (i31WC~, > (ar/i3C&.
The return velocity of the inhibitor in the threshold region,
V*, depends directly on the inverse of thk slope as follows:
vC,=vfluid[
I +(p/$) (arl~)a]
This has been explained in several previous
publications6~9 .10*13*14)15*25and all terms are given in the
Nomenclature. It is precisely because of these two central
properties of tine dynamic isotherm (i.e. ~wnu > ~h~~ and
(aI%C)~n > (aHaC)w.J that the relative behaviour of the
two different types of phosphonate is as observed in Figure 10.
Indeed, the consequences of such “cross-over” of the
..,., ha,..n= in
~aU,,,=,,,,= , :he ,=..
lnw c~n~~n~rati~n region were previously
predicted25 before the actual occurrence in Figure 15 was
found.
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).
FIELD SIGNIFICANCE OF THE RESULTS
The use of crushed core adsorption resuhs to screen inhibitors
is clearly a rapid and useful technique in the scale inhibitor
selection process although it does not give the complete
information required to design a field squeeze treatment. The
use of the reservoir condition core flood results to design an
improved “Field Squeeze Strategy” has been described in
several previous paPers.6. 15.17.26.34.35 The core flo~
effiueni is atiaiysed 1~
--* 14:35 ;G fi~~ the atjsmphn k?!krm:
I’(C), which is then used in the ,field modelling. The
derivation of the adsorption isotherm, its significance and its
use in modelling field squeeze treatments has also been
di~~u~~ in de~il in other publications.lO~ 13-15~17*26~27*34~35
An example of a field a plication of this procedure is
described in a recent paper !6 and more details can be found
there. Only a brief description of results is presented here for
illustrative purposes. Using derived adsorption isotherm data
from Flood F3, sensitivities indicated that the overflush size
was the most significant practical sensitivity for affecting the
squeeze lifetime, as illustrated in the modelled field returns in
Figure 16 (some practical details given inset). The ovefflush
was therefore successively increased in the field in subsequent
scale inhibitor squeezes in the same well where the treatments
were into the Brent Tarbert Formation. The field returns for
these successive treatments are presented in Figure 17 and
these results show that significant improvements in squeeze
 \

6 STATIC AND DYNAMIC ADSORPTION OF PHOSPONATE AND POLYMERIC SCALE INHIBITORS SPE 29002
ONTO RESERVOIR CORE FROM LABORATORY TESTS TO FIELD APPLICATION
lifetime can be made by optimizing the field application adsorption tests are not intended to replace dynamic
strategy. core flooding.

In order to carry out this type of field assessment, it was
essential to have the dynamic isotherm, r(C), from the
appropriate reservoir condition core flood. As noted above, it
is not possible to obtain this from bulk , adsorption
measurements since the bulk or “static” isotherms do not give
a correct estimate of the shape of the isotherm in the threshold
region (i.e. the important quantity @r/~C) is incorrectly
.----------- 13-15* 17~25~27*34~35 ~erefore$ it is stiil necessary
messurexi).
to carry out the core flooding measurements if we wish to
make an engineered design of the scale inhibitor squeeze
treatments in the field for a given product. In addition, it is
necessary to carry out core flooding to assess whether any
formation damage will occur due to the application of a
p~Iic&w ......- ... . .
inhihitor/spearhead system and this issue has been
discussed in a previous paper. 27 The bulk adsorption tests on
crushed core cannot be used to assess formation damage.
SUMMARY AND CONCLUSIONS
In this paper, we have considered how it is possible to use
static tests to establish scale inhibitor adsorption mechanisms
and levels in consolidated reservoir cores and to rank
inhibitors for their adsorption behaviour and (possibly)
squeeze return lifetimes. This relatively rapid and
straightforward type of bulk adsorption measurement can
awist
------ .in.. the
---- selection
-------- .. of inhibitors -- for fu~thH
-- ----------
which should be carried out on a minimum number of
inhibitors. For example, a full bulk adsorption sensitivity cart
be carried out on several products on two or three crushed
reservoir samples in less than one week. However, the way in
which we pefi”orm a very detailed and cioseiy monitored
reservoir condition core flood takes between 4 and 5 weeks for
one core. The value of such rapid screening tests is very
evident although it is still essential to carry out a much smaller
nurn.~r of reservoir condition
--. .—. .. . .. CQre floods for a few (usuallv
\—— ——..,
between 1 and 3) selected inhibitor products. This is
necessary if the dynamic adsorption isotherm (llC)) is to be
derived in order to develop the “Field Squeeze Strategy” or for
the assessment of formation damage which might occur in the
squeeze treatment. An example of this is presented briefly in
this paper although details can be found elsewhere.26 The
main conclusions arising from this study are as follows:
(i) bulk adsorption tests on the disaggregated core material
broadly give the same sensitivities of inhibitor adsorption (to
pH, [Caz+], and temperature) as those subsequently found in
*h.. c*.-
●.” ““l”
fk,+c
1.—..
Th,=r,=fnra
. ,,”. “.”, -,
d.m.ntinm
GSU.7”Sp.”..
i c rwmhnhlv A,,.= tn the
.- ~. ““U”. J ..”- .“ . ..”
same mechanisms in both the mineral separates (reported in
previous paps 1Q 12>25,28) and in the core material. These
results suggest that there is a correlation between observed
adsorption level in the disaggregate core and the return
lifetime to threshold levels (in pv) in the corresponding
consolidated reservoir core.
(ii) the bulk adsorption tests on disaggregate core form the
basis of a faster (than core flooding) screening method which
is able to rank various inhibitors for their adsorption behaviour
in a systematic manner. However, the data must be grouped
appropriately according to the rocldreservoir system before
comparisons between products can be made. Static inhibitor
(iii) in interpreting bulk adsorption measurements, some
cognizance must be taken of other more subtle factors which
do not appear in such tests. The two main ones noted in this
work are illustrated in the comparison between the bulk
adsorption and core flood return behaviour of the penta- and
hexa-phosphonates (inhibitors 11a and 11b; Table 4). For these
products, the threshold inhibition efficiencies (i.e. Ct values)
are different and this affects the meaning of return lifetime.
Also, the shape of the isotherm of the hexa-phosphonate
results in a radically different form of the inhibitor return
profile in the core floods. This latter issue can only be studied
in dynamic core floods as explained in the text (see below).
(iv) with the above provisos, the bulk adsorption data in this
study suggests that such tests are a valuable method of
screening scale inhibitor chemicals (which have been pre-
screened for good inhibition efficiency) to suggest a final one
or two products and method of application strategy for the
chemical (adsorption or precipitation) for reservoir
conditioned coreflooding and subsequent field application.
(v) to obtain the dynamic isotherm, r(C), for squeeze
treatment design, it is still necessary to carry out reservoir
condition core flooding which is then applied in the
development of the “Field Squeeze Strategy”. A field example
coreflooding
----- . . . . . is presented which shows that the predicted sensitivity to
factors such as overflush volume are found in the field, and
that using this approach has allowed the adsorption squeeze
lifetime to be extended.
..-. .*., *. . -.,--
NUMJLNCLA 1UIUL
c, inhibitor threshold concentration;
DETPMP inhibitor - diethylene triamine penta (methylene
phosphoric acid);
PAA inhibitor - .m!y ac~lic acid;
PPCA inhibitor - poly phosphino carboxylic acid;
Pvs inhibitor - poly vinyl sulphonate;
pv pore volumes;
v~, velocity of the threshold inhibitor concentration
value through the porous medium;
Vfluid velocity of the fluid through the porous medium;
rock bulk density;
: rock porosity;
r(c) inhibitor dynamic isotherm which depends on
concentration (also Temperature, pH, Ca 2+ etc..);
rmax maximum static inhibitor adsorption level in a
..-.UMIGU
Cl ”L..A---- .-”. /—-/-\.
LAM C lGSL (Ul~~),
r W.,, & rhexa maximum dynamic inhibitor adsorption level
from core floods for the penta- and hexa-
phosphonates (mg/g);
@rnc)Ct slope of the dynamic adsorption isotherm at the
threshold inhibitor concentration level;
@r/W2~, slope of the (hexa- and penta-phosphonate)
& dynamic adsorption isotherms near the theshold
(~r/@wnm inhibitor concentration level;
ACKNOWLEDGEMENTS
The authors would like to thank the following companies for
funding the work of the Heriot-Watt University OWield Scale
Research Group (OSRG): Agip, Baker Performance

618
SPE 29002 M.M. JORDAN, K.S. SORBIE, M.D. YUAN, K. TAYLOR, K. E. HOURSTON, K. RAMSTAD AND P. GRIFFIN 7

Chemicals, BP Exploration, Chevron, Elf, Exxon Chemicals, onto Consolidated and Crushed Sandstone”, SPE26605,
Kerr-McGee, Marathon, Shell, Statoii, Texaco and Total. Presented at the SPE Annual Fall Conference, Houston,
Particular thanks are extended to Shell UK, Norsk Hydro, TX, 3-6 October 1993.
Enterprise 011 and Total Oil Marine for their permission to use
-–-J—--*-l UaW
fleid andlor exprmmcuku ~-.-= ,,1
:- *~~cfimwr
.lll. ~e~-.. The ~~nnort
~r .- of
-. 11. Breen, P.J. and Downs, H. H.: “The Use of Adsorption
colleagues in the OSRG is also gratefully acknowledged. Thermodynamics in the Development of Scale Inhibitors
for High Barium Content Oilfield Brines”, Royal Society
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Pet. Tech., pp. 339-353, March 1973. 12. Graham, G. M. and Sorbic, K. S.: “The Effect of
Molecular Weight on the Adsorption/Desorption
2. King, G.E. and Warden, S.L.: “Introductory Work in Characteristics of Polymeric Scale Inhibitors on Silica
Scale Inhibitor Squeeze Performance: Core Test and Sand and in Sandstone Cores”, Presented at the NACE
Field Results”, SPE1 8485, Presented at the SPE Annual Conference, Baltimore, Maryland, 28 February -
International Symposium on Oilfield Chemistry, 4 March 1994.
Houston, TX, 8-10 February 1989.
13. Sorbic, K. S., Wat, R. M. S. and Todd, A. C.:
3. Pardue, J.E.: “A New Inhibitor for Scale Squeeze “Interpretation and Theoretical Modelling of Scale-
Applications”, SPE2 1023, Presented at the SPE Inhibitor/Tracer Corefloods”, SPE (Production
International Symposium on Oilfield Chemistry, Engineering), pp. 307-312, August 1992.
Arlaiilelrn,
c.1:4 -:.lllCI, 4-
&alllGl
%1 O? Eahmwwu
-z. . ““. “... J
~~~!.

14. Sotile, K.S., Wat, R.M.S., Todd, A.C and McClosky, T.:
4. Meyers, K. O., Skillman, H.L. and Herring, G.D.: “Derivation of Scale Inhibitor Isotherms for Sandstone
“Control of Formation Damage at Prudhoe Bay, Alaska, Reservoirs”, Royal Society of Chemistry Publication -
by Inhibitor Squeeze Treatment”, J. Pet. Tech., pp. 1019- Chemicals in the Oil Industry: Developments and
,. _____ m~:...~
1034, June 1985. Appucarionx, UJILCUby..nun-~ - 1001
K.LL ~5ueL8, .. . ..

5. Przybylinski, J. L.: “Adsorption and Desorption 15. Sorbic, K.S.: “The Improved Design of Scale Inhibitor
Characteristics of Mineral Scale Inhibitors as Related to Squeeze Treatments”, Presented at the Water
the Design of Squeeze Treatment”, SPE 18486, Management Offshore Conference, Organised by IBC
Presented at the SPE International Symposium on Ltd., Aberdeen, 22-23 October 1991.
Oilfield Chemistry , Houston, TX, 8-10 February 1989.
16. -Hong, S.A. and Shuler, P.J.: “A Mathematical Model
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M., Riley, H. and Gurden, S.: “The Modelling of Presented at the SPE International Symposium on
Adsorption and Precipitation Scale Inhibitor Squeeze OMield Chemistry, San Antonio,TX, 4-6 Februasy 1987.
Treatments in North Sea Fields”, SPE25165, Presented
at the SPE International Symposium on Oilfield 17. Sorbic, K. S., Yuan, M..D. and Todd, A.C.: “The
Chemistry, New Orleans, LA, 3-5 March 1993. Modelling and Design of Scale Inhibitor Squeeze
Treatments in Complex Reservoirs,” SPE2 1024,
7. Kan, A., Yan, P. B., Oddo, J.E. and Tomson, M. B.: Presented at the SPE International Symposium on
“Sorption and Fate of Phosphonate Scale Inhibitor in the Oilfield Chemistry, Anaheim, CA., 20-22 February
Sandstone Reservoic Studied
——. - by
. . Laboratory Apparatus 1991.
With Core Material”, SPE217 14, presented at the SPE
Production Operations Symposium, OK, 7-9 April 1991. 18. Yuan, M, D., Sorbic, K. S. and Todd, A. C.: “A Near-
Well Simulator for Modelling Scale Inhibitor Squeeze
8. Kan, A. T., Cao, X., Yan, X., Oddo, J.E. and Tomson, Treatments,” Paper No.24 at the NACE Annual
M.B.: “The Transport of Chemical Scale Inhibitors and Conference, Nashville, TN, 27 April-l May 1992.
Its Importance to the Squeeze Procedure”, Paper No. 33
~— Control
presented at the NALH Annuai Conference and :9. Qal lUGIS, u. b.: ~~p.acimjtation
m . ...l”a.” R T %neeze
. ..,w.y .. .. .. km- - Qg!

Corrosion Show, Nashville, TN, 27 April -1 May 1992.
-.-. ..
9. Sorbic, K. S., Yuan, M-.D., ~hen, Y., I oaa, AC. and Wac
R.M.S.: “The Effect of pH on the Adsorption and
Transport of Phosphonate Scale Inhibitor Through
Porous Media”, SPE 25165, Presented at the SPE
International Symposium on Oilfield Chemistry,
Anaheim, CA, 20-22 February 1993.
10. Sorbic, K.S., Jiang, P., Yuan, M.D., Chen, P., Jordan, M.
M. and Todd, A.C.: “The Effect of PH. Calcium and
Temperature on the Adsorption of Phosphonate Inhibitor
Scale in High-Volume Wells” , 011 and Gas Journal,
December 1983.
20. Carlberg, B.L. : “Scale Inhibitor Precipitation Squeeze
for Non-Carbonate Reservoirs”, SPE 17008, Presented at
the SPE Production Technology Symposium, Lubbock,
TX, 16-17 November 1987.
21. Olson, J.B, Moore, D.C and Holland-Jones, N.: “A
Temperature Activated Extended Lifetime Scale
Inhibitor Squeeze System”, Paper No. 25 at the NACE

619
 8 STATIC AND DYNAMIC ADSORPTION OF PHOSPONATE AND POLYMERIC SCALE INHIBITORS SPE 29002
ONTO RESERVOIR CORE FROM LABORATORY TESTS TO FIELD APPLICATION
Annual Conference, Nashville, TN, April 27- May 1
1992. 32. McTeir, M. D. K.: “Modified Methods for the
Determination of Polyacrylic, Phosphinocarboxylate and
22. Wat, R.M.S., Montgomery H.T.R., Maclean, A. F and Polysulphonic Acid Scale Inhibitors in Oilfield Brines”,
Bland, I.D.: “Squeeze Application Using a Polymer SPE25 160, Presented at the SPE International
Scale Inhibitor - A Case History”, Presented at the 4th Symposium on Oilfield Chemistry, New Orleans, LA, 2-
1-.-.- ..:--.1 n:lc-1~ Pt. —-:--l c.. —--.:..- fl-..:l - C 1X.-L s (IO9
lllLC1lliiLIU1lill U1lllCIU &IICI1llVill =yllltJUSIU1ll, WG1lU, J lVIUU1l 177.7.

Norway, 18-21 April 1993

33. Graham, G. M., Sorlie,K. S., Beak, L. S., Taylor, K. and
-i~
&J, n.. L-:-1: n.D allu
milualull,
-.. A Lu&KIlal
1 -- I. L”+ T
1, A ..
. $t@-l.. k.:l:...
Ouluulllty
. . ...4 ml.’....
allu r Ila>c
Dl:l:..
D1lllG,
T
L.,.
. ,,ma., a,-.._
A/c vG1uplllG1l
a.. ● .-.-,4
L allu
A --1:,...
Appllbxluvll
+:-- -C
U1
A . . . . . . ..-
AVGU1 aLG

Behaviour of Polyacrylate Scale Inhibitors and their Detection and Assay Techniques for Oilfield Scale
Implications for Precipitation Squeeze Treatments”, Inhibitors in Produced Water Samples”, SPE 28997,
SPE28998, Presented at the SPE International Presented at the SPE International Symposium on
Symposium on Oilfield Chemistry, San Antonio, TX, Oilfield Chemistry, San Antonio, TX, 14-17 February
14-17 February 1995. 1995.

24. Malandrino, A., Yuan, M. D., Sorbie,K.S. and Jordan, 34. Jordan, M.M., Sorbic, K.S., Jiang, P., Yuan, M.D., Todd,
M. M.: “Mechanistic Study and Modelling of A. C., Taylor, K., Hourston, K.E. and Ramstad, K.
n-.. -:-:.-.:--
rlG&lpl LCIL1ull
C?”..l-
O&alc
T- L.:&:.-.
111111
c . . . -------
UILU1
D.,...”..”-.**
oyucGLG Ilvuc>scs ,
~,aa:..a-..lm,:..,.l
lvllllclaluglua
P,...
QU1l
*-al.
LIUIS m
T_l.:l.: .. .
111111UILU1
A ,4...
Auaulpuullr
-,:....1

SPE29001, Presented at the SPE International Desorption in Brent Group Sandstone and Their
Symposium on Oilfield Chemistry, San Antonio, TX, Importance in Predicting and Extending Field Squeeze
1A 17 E.-._.-...._.10CIA
1--1 I l-Guluiily 177-?.
T :ca*:-.M**
JA1GLIIIIG3 ,
cDc~7(a-17
or~z Juu J,
D.-. --,...4
r IGSGIILGU
.-..
aL
Cnlz
orL2
?2...,.......
fiuiupau

Production and Operation Conference, Aberdeen, UK,

25< Jordan, M.M., Sorbie,K.S. Jiang,P., Yuan,M.D., Todd 15-17 March 1994.
A.C. and Thiery, L.: “The Effect of Clay Minerals, pH,
Calcium and Temperature on the Adsorption of 35. Yuan, M. D., Sorbic. K. S.. Jiarm, P., Chen, P., Jordan,
Phosphonate Scale Inhibitor onto Reservoir Core and M. M~,Todd, A. C., Hourston, K.E. and Ramstad, K.:
Mineral Separates”, Presented at NACE Annual “Phosphonate Inhibitor Adsorption on Outcrop and
Conference, Baltimore, Maryland, 28 February - 4 Reservoir Rock Substrates: The Static and Dynamic
March 1994. Adsorption Isotherms”, Presented at the Fifth
International Symposium on Chemistry in the Oil
26. Sorbic, K. S., Yuan, M. D, Jordan, M. M. and Hourston, Industry, Royal Society of Chemistry, Lancaster
K. E.: “Application of a Scale Inhibitor Squeeze Model University, Ambleside, England, 12-15 April 1994.
to Improve Field Squeeze Treatment Design”,
SPE28885, Presented at SPE EUROPEC94, London, Appendix A: Mineralogy of the Sandstones Used
UK, 25-27 October 1994. A brief summary of the sandstones used in this study is
presented below. A fuller account has been published
27. Jordan, M. M., Sorbie,K.S. Jiang,P., Yuan,M.D., Todd elsewhere. 10)25,27
A.C. and HourstonK.E. : “Phosphonate Scale Inhibitor ● Brent Group Sandstone, Tarbert Formation (North Sea):
Adsorption/Desorption and the Potential for Formation From examination of the cored samples, this sub-arkosic
Damage in Reconditioned Field Core”, SPE27389, arenite is subrounded to subangular, well sorted and
Presented at the SPE International Symposium on comprises: 8290 quartz, 7- 9% feldspar, 8-10% kaolinite, 1%
.~nr-.~i-. name-a f=fim~pfil
“. ,,,-., ”,, “6Un&u~-Wu,,., v’,
T af..,afta
Mm-, w..-,
~~, a-in
7 -,”
—....-....
lllUXWVILC
- —:--
Illlud
*m. .--I ----- Ulu
1 -m Uli WIUILG
.-a U.
n cm. 1:.k:-
J-m llUIIG
r-- —.-..
11 ilglllcllm.
.m_
1 llC

February 1994. main pore filling materials are quartz overgrowths, kaolinite,
chlorite and illite.
28. Jordan, M.M, Sorbic, K.S, Yuan, M.D , Taylor, K, K. Etive Formation, moderate to well sorted sub arkosic arenite
Hourston, K. E. and Ramstad, K. and Griffin, P. “The sub angular and comprises: 78% Qtz, 11% feldspar, 5%
Adsorption of Phosphonate and Polymeric Scale kaolinite + illite, 290 muscovite, I% carbonate, 290 pyrite.
Inhibitors onto Reservoir Mineral Separates”. Presented Oseberg Formation poorly to moderately sorted, sub arkosic
at the 5th International Oilfield Chemicals Symposium, arenite, angular to sub angular and comprises: Qtz 76&, 8%
Geilo, Norway, 21-23 March 1994. feldspar, 6% muscovite, 2% carbonate and 8% kaolinite +
illite.
29. Walters , G.L (Chief Editor) : Hach Water Analysis ● Hopeman Sana%tone(Permo-Triassic): This is also known
Handbook, Hach Company, Colorado, p.5 16, 1989. as Clashach sandstone. The rock is an arenite and the
Hopeman sandstone can be classified as a quartz arenite, with
30. Murphy, J and Riley,J.P.: “A Modified Single Solution about 5% feldspar and > 94% quartz.
Method for the Determination of Phosphate in Natural ●Forties Member Sele Formation (North Sea): From
Water”, Anal Chim. Acts, 27, pp.31-36, 1962. examination of the cored samples, the sub-arkose is
subrounded to subangular, moderately to poorly sorted and
31. Pennington, J. “An Overview of Alternative Approaches comprises: 67% quartz, 11% feldspar, 8% lithic fragments,
to the Development of Monitoring Methods for Scale 5% clay matrix, 2-5% authigenic clay (kaolinite, chlorite and
Inhibitors in Oil-Field Produced Waters”, Proceedings of illite), 1% muscovite mica and 2-5% carbonate (calcite,
the 3rd International Symposium Chemicals in the Oil siderite). Quartz overgrowths, kaolinite, chlorite and illite are
Industry, University of Manchester, 19-20 April 1988. the main pore-filling minerals.

620
 Table 1: Summary of Reservoir (Condition Inhibitor Corefkmds.

1 —~ I 1
Description of the rock
w Rock
NO. type huwclogy
(IoMco)
(%)
*.82 , Fdd.lols,
& Tcrbat MOCc.1-3,m 0.%2!
FOnOcuaPyr.o.la3,3h0L S-13
F4 all. 1-3,InL u.
Fs Ck3mch QQ..>94034J65,
Pyr. &clcytmce \ ‘\ 20.8 1252 171 195 110 31.4 42.6 P33428 \\ 118 SS8S0 7.4 2.m m 19 110 Sw 850 73(3
F7 Ocd!ag QIZ76.3W. 8,==.~ 3990m 106
FOrmuimc9b. zKcoL&lui.8 — ... 29.7 MS KM 152 106 47.8 33.5 N \\ [lb 40s18 6.8 2.3s m 21 1(K Fw 350 892
Ifa EliW Qla7s, FckLll, Mo9c2 3953m 106
FOtmcliollcib.1,Fyn2?--.5 -. —--- 27.9 7s3 317 341 106 52.5 23.8 \ \ Ilb 42A92 6.3 2.3s m m 106 m 160 Iloa
no ‘hbe$t COmpdkmnfocmcodiu >7STm 1112 23.7 36 16 19 1lC) 4s.9 29.(JI 0.1%22 \\ Ilc 57951 6.1 S.48 m 17 110 Sw 1350 1273
—— . @l 4.2s
1127 18.4 2.42 0.33 1.55 lu~ 41.8 34.5 0.06%S3 N Ilb 40643 8.6 2.m m la 127 Fw 1064 55
@l 5.3s
0.1%95
12190ft ‘1O7 26.7 439 265 268 1~1 3s.7 24.11 pHS.PO \\ 14b 451527 9.62 6.45 m 18 107 Fw 43 40
0.1%32
12222n la) 25.2 136 31.5 58 KY7 42.5 39.”1 @i 3.68 N Ilc 51456.9 9.09 6.00 m 20 107 Fw 618 320(
0.1%S6
12190t? 107 26.6 356 154 164 107 37.8 21.4 p313.78 N MC 30s27 9.63 4.50 m 17 107 m 44 620
0.1%S2
S616ft 107 23.8 213 4s.s \ 10V 36.2 19.8 pH3.6S N llC 5202s 10.03 6.00 m 19 m7 m 960 424s
— —— —

10s42R .107 23.4 34.7 16.1 21.1 law 46.2 2s.,3 -gal \\ NC 34472 10.9 4.50 20.00 1s 107 Fw 445 149

8516fi 107 22.5 209 36 50.5 m7 36.1 m.7 Um \\ Ilc 54164 11. 3 6.00 m.00 18 10’7 Fw 1094 39s
2.s%S3
S464ft 107 22.9 S6 27.4 107 47.s 23.1 pll4.01 N 11c. 54640 10.1 6.00 20.00 1s 107 Fw 9s0 400
Na4w
l) MhldOgycbbddaW . Qzqz ~.*@NL MIIX*+IC mka IJ131.*Mc fmsmcmLCar.=Ccrbmut%Pyr.=pyrite,CICy SCCOI.=KCOliritq
C16.dkrI@ IIKd13itc.
aSl@Wmti~ti_A*mxdb=ti_u.
3) Ila [lb ad IIccm threetypa ofpk#onctc Mdk4torsmpp3kdby scrvicccomcoics.
4) w cd 14bsmw of p- bud 00POUCC@C~d
$A31dulioossmdtwccd beforeinjection.M him dutimn od for mtumdoo and plWfMl ccc adjwttd to pH of 5.5.
 “TABLE3. OSRG scale inhibitor code%generic chemkal types
I 1
and the codes of the floods where these chemicalswere teated

TABLE 2 Composition of synthetic North Sea brine I OSRG Code I Chemical Type I Used in OSRG C(~[
and Formation water used in this study

Synthetic seawater Formation water for Floods El to E7

orryposition ( mg/t) _l@tion ~mti)
Na+ 10,890. 31,275 I I
ca2+ 428 5,038 13 Phosphinopoly +
Mg2+
K+
1,368. 739 I carboxylicacid I
1
460 654
so42- 2,960. mm 14 Poty acrytic acid
cl- 19,766 60,848 14a CsrboxyticCopolylncr El, E5
sr2+ Zero 771 14b POIYacrvlicacid E3 +
Ba2+ Zero 269

pH of synthetic seawater brine and formatiomwater after degassing were adjusted to pH 5.5 15a Poly vinylsulphonate
15a Subhonate acrylicacid

TAIBLE 4. Static adsorption onto crushed reservdir core (mg/g) measured over the pH range of
the reservoir examined. The pore volume values reflect the volume of posfflushfluid required
to reduce the inhibitor concentration to the threshold values. For flaws F3, F4, F5, W, ~ and
F25 the threshold value is 5ppm active and for ft&ds El to E4 the threshold value is 1 ppm
active inhibitor.

code adsorptiontests Coretloodpostflush pore volume I Core Type

mg (inhibitory@(Crushedcore) to inhibitor threshold concentration

1= F3
F4
.“
,...
1.5
1.6
..7
I 1
(
‘!%=
<. -—-—

E
F7 1.7 995 ~
Pa 1.78 975 ~.s_- ~
Xlve Frn.
F25 1.82 1055 m
El 1.2 m-t =

1 -.”-
1 -.

1= ii 3.8 275
 .

4
---

3 E~=Esi3im 1.2

1
\/” 0.9

0.8
—
11 adsorption at 25°C
11 adsorption at 95*C
13 adsorption at 25°C
13 adsorption at 95-C
I I

0.7 1 Seawater 25°C

‘“i
0
2 3 pH[--> 4 5 6
0.6 i =
Seawater 95*C
, ,
I
, I
2 3 pH --> 4 5 6
F@re 1: Penta phosphonate and PPCALitilbitor adsorption onto crushed Figure 2: Calcium release data from penta phosphonate and PPCA
Tarbcrt Formation core as a fimction of pH at 25*C and 95*C. inhibitor adsorption onto crushed Tarbert Formation Core
as a function of pH at 25°C and 95-C.
4.0 —
4

L-
~ Ila penta phosphonate adsorption at 95°C
~ Ilb penta phosphonate adsorption at 95*C 3.5

3 3.0
Tarbert Fm. T=95°C
2.5
‘~ Hexa-phosphonate Hc
2.0 ‘~ Sulphonated acrylic acid 15b
2
‘~ PVS 15a
\ 1.5

\ 1.0
1
\
0.5

0.0
01 2 3 pH --> 4 5
2 3 pH --> 4 5 6
Figure 4: Inhibitor adsorption data from Tarbert Formation core at 95°C as
Figure 3: Two penta-phosphonate inhibitors (Ha and Ilb) adsorption a function of pH for hexa-phosphonate and sulphonated co-polymers
onto crushed Tarbert Formation core as a function of pH at 95”C.
 ————

I ‘hrbt Fo!7iMItioIIcOIt?]hds, ~r= 110C

‘—-–1
l— FId F1O (hexa-plhosphonate,Ilc, IpH=:5.41) I
_ ~ood F3: (penta-phosphonate,lla, IpH==2.00) I
————

0 200 400
-----

Postflush pore volume -->

1 pprn active inhibitor

600
-- L,
=-- -~---= --a-

8CI0 lVUU
~:,

L~::F:
.... ..... ..
., .
0 150 300 450 600 750
Postflush pore:vobtle
.!-------

~~~
-

900
----

-->
1050
--—

1:200 1350 1500

Figure 9: Comparisonof polymer and hexa-phosphonate!etums in the Figure 10: Comparison of penta- and hexa-plhosphmmtereturns in the
during formation water postflush in floods E3 and E4.
effluent effluent during seawater postflush in floods F3 and F1O.

All penta-phosphonates /

> “’‘ >’

❑/’
,, / .
/
,/
● //
/0
,/
—.
o F3
/’
● F4
// /“ ■

.- ------- ----- ----- ----- ------ ----- . .+./ ■ F5

\---- ----- ------ --- ------ ----- -.

.—
~ 1.00
50 100 150 200 250 300 350 400 700 800 900 1000 1100 1200
Postflush pore volume --> Pore volumes of posttlush to threshold concentration

Figure 11. Comparison of inhibitoreffluent profiies for pol:ymeradsorption Figure 12: InhMor (Penta-phosphonate) static adsorption tests onto Brent
coreflood E3 and polymer precipitation coreflood E5. Group (F3, F4, F25) and Clashach (F5)Isandstones vs pore volumes
of postflush required to reach threshold concentration,
 ~
.......... ................ ................ ....... ........ .... .... .....●...... .,
Ld 2.0-
E
.a

4 1.0

0.5-

t).t)~ ~-l
0 510 100 150 200 250 300 350 o 50 250 300
Pom volumes of postfhwh to threshold concemtmtion lnhib& Concen&5$n (ppm~~>
Flglllre13.’ Inhibitor adsorption in static tests on Forties Manbers sandatone Figure 14 Adsorption isotherms for both penta- and hexa-phosphonatcs
vs pore volumes of postflush required to reach threshold concentration km Floods F3, F4 and FIQ Tadxxt ForrnutionCore at 110I”C.

..
7“
,s — Ovedlush volume doubled 3200 bbls
4-””
.-”
..”--.
.......... Base csse overflush volume 1600 bbls I
,/.”
x’
..&” Squeeze operation:
...
Inhibitor - phosphonate
Preflush - 100bbls aeavvater
Main treatment - 1215blbls20% inhibkor
(- 5.8% active contemt)
Treatment interval -13 lft
I Porositv -0.22 1
........... ............... ................................... . . .. . . .. . . .,---
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . --- . --,...-.- .
......................................................

20 25 o 200000 6000110 800000

o 5 10 15
InhibitorConcentration @pm) --> Cumulative Water Production (lMs) -->
Figure 16: Sensitivity of predicted squeeze inhibitor returns to seawater owerflush
Figure 15: Low concentration region of the adsorption isotherms for the penta- volumq Modelled using the Flood F3 isotherm data.
and hexa-phosphonatea in F@ure 14 Tarkt Formation core at 11(YC.
 Four Successive Scale Inhibitor Squeezes in
Alwyn Producer

r Increasing Gvertlush Squeeze 1-->4

[(Squeeze 2 problems - see Ref. 26)

60 ppm
(ss supplied)

10
o 5txKM0 1ooOOOo 1500000 2ooOOOo
tcwnulative Produced Water (bbl) -->
a
N
-1 F@re 17: Field inhibitor returns from repeated penta-phosphonate
treatments to the same Brent Group well, TarbextFormation.