SPE 87453

A New Class of Green Mineral Scale Inhibitors for Squeeze Treatments

B. Bazin, N. Kohler, A. Zaitoun (Institut Franais du Ptrole), T. Johnson (Solutia Europe SA) and
H. Raaijmakers (Royal Cosun).

Copyright 2004, Society of Petroleum Engineers Inc.

th
This paper was prepared for presentation at the 6 International Symposium on Olfield Scale
held in Aberdeen, UK, 26-27 May 2004.

This paper was selected for presentation by an SPE Program Committee following review of
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Abstract
The oil industry is currently facing severe restrictions
concerning the discharge of oilfield chemicals into the
environment. For most of the actual widely used mineral scale
inhibitors, the future will depend on the possibility of their reinjection into disposal wells. Another alternative could be the
deployment of biodegradable chemicals. For this purpose a
new class of "green" scale inhibitors, the Carboxy Methyl
Inulins (CMI), has been evaluated in its ability to prevent
carbonate and sulfate scale deposition by squeeze treatments.
Jar Tests and Tube Blocking Tests, performed on actual
reconstructed injection and production waters show that the
CMI inhibitors exhibit competitive inhibiting performances
compared to currently used scale inhibitors. Core tests for the
determination of CMI adsorption / desorption properties in
static and dynamic conditions help to predict inhibitor squeeze
lifetime and to design its implementation in future
squeeze applications.
It is finally concluded that the Carboxy Methyl Inulins may
already be considered as viable alternate mineral scale
inhibitors to currently used but not biodegradable chemicals.

Introduction
The discharge into the environment of oil-field chemicals
becomes more and more scrutinized and legislated. The oil
offshore industry is particularly concerned by the severe
restrictive regulations concerning the environmental impact of
the products used. In the field of the mineral scale inhibition,
chemicals are usually squeezed directly into the reservoir
section surrounding the production well and back produced
with the formation fluids. The only alternative for the

produced water seems to lie between the re-injection on site or

the use for the squeeze treatment of biodegradable chemicals.
Poly (amino-acids) and in particular polyaspartates have
recently been evaluated1-3 as environmental safe "green"
mineral scale and corrosion inhibitors. They have been also
field tested4,5 in down-hole squeeze operations.
In the present paper a new class of biodegradable chemicals,
the Carboxy Methyl Inulins (CMI)6, has been evaluated in its
ability to prevent carbonate and sulfate scale deposition during
topside or squeeze treatments. Their efficiency as scale
inhibitors has been checked comparatively to that of the
currently used phosphonates or polyacrylates by conducting
Jar tests and Tube blocking tests. Their possible application in
squeeze operations has been investigated by performing
adsorption/desorption measurements on model limestones in
static and dynamic conditions. In particular the influence of
the composition of the production brine, used in the desorption
step of the core-flood experiment, on the inhibitor return
concentration was investigated. An experiment using Sea
water as production brine was compared to an experiment
using Forties water, which has a higher TDS and in particular
a higher calcium content.
These tests seek to establish an evaluation of two different
products but of very comparable structure. We tested the CMI
and the polyacrylate. Both are polymers with carboxylic
groups but with a very different structure of their
polymeric chains.

Products.
Carboxy Methyl Inulins (CMI) are derivatives from Inulin.
Inulin is a natural (2-1) polyfructoside with a glucose unit at
the reducing end7. It is extracted from Chicory roots and used
mainly in food applications. Carboxylate groups are
introduced into the polysaccharide by carboxymethylation
with Sodium monochloro acetate as reagent in alkaline
medium (Figure 1).
Carboxymethyl Inulin is made at different degrees of
substitution (DS:average amount of carboxymethyl groups /
monosaccharide unit) and products are commercially available
with a DS of 1.5, 2.0 and 2.5. The average degree of
polymerization (DP) of the commercial product is DP =10.

SPE 87453

The Carboxy Methyl Inulin based product (DS 2.5 and DP

10), is inherently biodegradable with more than 20%
biodegradation according to the OECD 306 test method and
has a very low ecotoxicity.

These bottle tests already show that the CMI green inhibitors
are effective alternatives to DETPMP for BaSO4 scale
inhibition. CMI with the highest degree of substitution
are preferred.

The main characteristics of the Carboxymethyl Inulins

evaluated throughout this study are presented on Table 1.
They are compared to a polyacrylate (MW=2000), two
phosphonates (DETPMP) and a polyaspartate (MW= 1700).
The Mn (number average molecular weight) and Mw (weight
average molecular weight) determinations of the green
inhibitors were performed by coupling on line size exclusion
chromatography (SEC), multi-angle laser light scattering
(MALLS)
and
differential
refractive
index
measurement (DRI).

Tube Blocking Tests (TBT)

Brine compatibility
The brine compatibility of CMI products with a degree of
substitution (DS) of 2.0 and 2.5 were compared to DETPMP.
The scale inhibitors were added to Sea water at a range of
concentrations between 100 and 50000 ppm. These solutions
were aged for 24 hours at 95C. Brine compatibility was
evaluated both visually and by quantitative determination of
the calcium ions remaining in solution. (Table 2). At 95C the
calcium tolerance of both CMI products is higher than that of
the phosphonate for the different inhibitor concentrations.

Jar tests
The Jar tests or Bottle tests are conducted following the
NACE Standard Test Method 0197-978 for BaSO4 scale
inhibition. According to this method, 50/50 Sea water /
formation water mixtures are stored in an oven during 22
hours at the reservoir temperature. The tests were applied for
different concentrations of the inhibitors. Two test conditions
were evaluated:
Moderate scaling conditions using a 50/50 Forties/Sea
water composition at 70C and pH 6 (Table 3).
- More severe scaling conditions using a 50/50
Miller/Seawater composition at 90C and pH 6 (Table 4).
The remaining soluble Barium concentration was taken as a
measure of the percentage of inhibition attained by the
tested inhibitor.
Figures 2 and 3 show some of the results obtained
comparatively during these jar tests with one phosphonate
(DETPMP) and two carboxymethylated inulins (CMI 2.0 and
2.5, DP 10). It can first be seen that in both test waters the
inhibiting action of any of the 3 inhibitors requires high
inhibitor concentrations to reach sufficient BaSO4
inhibition levels:
- In the moderate sulfate scaling conditions BaSO4 scale
inhibition (based on remaining soluble Ba++ ions) is reached
by 10 to 50 ppm of DETPMP, 50 ppm of CMI 2.5 and 100
ppm of CMI 2.0;
- In the more severe sulfate scaling water mixture BaSO4
scale inhibition is reached only by 50-100 ppm of CMI 2.5,
while both DETPMP and the CMI 2.0 fail to fully protect the
water from scale deposition.

CaCO3 Inhibition.
The experimental set-up, previously described2,3 is a pressureand temperature- controlled capillary device in which the fluid
composition is adjusted by means of 2 pumps (one for each
anion-rich and cation-rich fluid). The total injection rate is 30
ml/h for the carbonate scaling test at 60C.
Capillary (7.6 meter stainless steel with 0.25 mm I.D.)
blocking time is first determined for the 50/50 water mixture
(Table 5) without inhibitor (blank test) and then with twice
the final concentration of the tested inhibitor added to the
anion-rich solution. The Minimum Inhibitor Concentration
(MIC) for a given inhibitor is taken as the blocking time
corresponding at least to 5 times the blank value.
At 10 ppm a.m., it is shown that all three CMI with a degree of
polymerization of 10 perform satisfactorily, with the two
products with the highest degree of substitution (DS = 2.0 and
2.5) about two times more active than the CMI 1.5 (Figure 4).
Therefore, increasing the number of carboxylate groups in the
molecule improves the inhibitor performance.
Figure 5 shows that with the experimental product CMI 2.0
DP 24 it is even possible to reach a slightly better efficiency.
Table 6 gives the summary of the MIC (Minimal Inhibitor
Concentration) values reached for the carbonate scaling water
by the different CMI green inhibitors comparatively to a
polyacrylate (PAA), a phosphonate (HEDP) and a
polyaspartate (PASP). Taking into account that the two former
products, although slightly more efficient at low
concentrations, precipitate nevertheless in this water mixture
at higher concentrations and thus present at least a risk of
formation damage, Carboxy Methyl Inulins, seem to be viable
competitive inhibitors for this type of CaCO3 scaling water.
BaSO4 Inhibition .
Some preliminary results of the TBT tests performed with the
moderate BaSO4 scaling test water (Table 3) at 90C have
also been obtained. Both CMI with DS 2.0 and 2.5 have been
compared to DETPMP and a polyaspartate inhibitor. The TBT
tests were performed on a capillary of 1 meter length, with an
I.D. of 1.1 mm and total injection rate of 14 ml/min.
(Figure 6)
Table 7 presents the MIC values obtained for this moderate
sulfate scale inhibition case. The MIC of the tested products
are quite similar and range between 3 and 5 ppm of active
matter for each product. Compared to the bottle tests, this
result is even more favourable for the CMI products. It is
nevertheless not surprising taking into account that TBT tests,
with short contact times, are usually in favour of the higher
molecular weight products9. Thus comparatively to the jar

SPE 87453

tests, with a far longer contact time, a levelling effect in

inhibiting performance is observed.

Hach method for the polyacrylate and by the hyamine

turbidimetric method9 for the polysaccharide.

Although complementary comparative tests have to be

performed and particularly with other scaling conditions, it
can be preliminary concluded that the CMI "green inhibitors"
are good biodegradable BaSO4 scale inhibitors.

Before the inhibitor adsorption step, a Sea water solution of a

non-adsorbing tracer (50 ppm KI) was first injected through
each limestone core for an accurate definition of the pore
volume available to the inhibitor solution. The inhibitor also in
Sea water was then injected at q = 10 ml/h and the core
effluent concentration was measured. Figure 8 shows
comparatively the dynamic adsorption front for the tracer, the
polyacrylate (PAA) and the CMI respectively. It is shown that
the delay of the inhibitor front to the tracer is very low,
meaning that only a small amount of each inhibitor is retained
in the porous medium during the injection at a pH of 6.

Static Adsorption Tests

Comparative static adsorption tests were performed on a
crushed Lavoux limestone (99.6% calcite) with a polyacrylate
and a CMI (DS = 2.5, DP = 10) . Various concentrations (up
to 10 g/L) of each inhibitor were contacted with the crushed
core material (16 hours at 60C) at a solid/liquid ratio of 1.
The amount of non adsorbed inhibitor remaining in solution
was analyzed after separation from the solid material by
sedimentation, centrifugation and filtration.
The static adsorption test results are given on Figure 7 for
both inhibitors at pH6. It can be seen that the adsorbed amount
is more than two times higher for the CMI than for the
polyacrylate (adsorption plateau at about 1.7 mg/g for the CMI
compared to 0.6 mg/g for the PAA).

Dynamic adsorption/desorption tests

In general, the scale inhibitor squeeze process consists in
pumping a preflush solution, followed by the main treatment
where the inhibitor is usually dissolved in Sea Water, followed
by a shut-in period to complete the adsorption. Then, the well
is flowed back and the inhibitor is desorbed in the
production water.
Dynamic adsorption-desorption tests presented below are
performed with the scale inhibitor dissolved in Sea Water. The
chase water, simulating the production water, is either the Sea
Water, in the first experiment, or the Forties type water in the
second experiment. The first conditions are considered as
reference conditions for further comparisons of squeeze life
times when various products are tested. The second
experiment is performed in more realistic conditions and
provides some insight into the effect of a salinity gradient,
which will always occur during the treatment (Table 8).
These tests seek to establish an evaluation of two different
products but of very comparative structure. We tested the CMI
and the polyacrylate. Both are polymers with carboxylic
groups but with a very different structure of their
polymeric chains.
Dynamic adsorption / desorption tests were performed on
consolidated Lavoux limestone cores at 60C. The main
characteristics of the cores used were quite similar : L (7-7.5
cm), (2.25 cm), (21.5-28 %), kbrine (1.6 and 2.7 mD).
Dynamic adsorption tests
In the first experiment (reconstructed Sea water, pH 6, 60C)
both a polyacrylate and CMI 2.5 DP 10 were comparatively
tested. Concentration measurements are performed by the

Regarding the low adsorption behaviour of the inhibitors at

pH=6, it was decided to decrease the pH to 4.5 in the second
experiment. At low pH, carboxylic groups are less negatively
charged, which may increase the adsorption level by reducing
the electrostatic repulsion forces between the surface and the
adsorbing chemicals. The composition of the solutions for the
adsorption step in the second experiment differs only by the
nature of the pH of the make-up water (Table 8).
Figure 9 shows the adsorption profile of the CMI in the
second experiment (10 g/L, Sea water, pH 4.5, 60C).
Contrary to the previous experience at pH 6, the delay of the
inhibitor breakthrough versus the tracer is relatively
consequent (about 0.42 PV) pointing to a high CMI adsorption
(0.516 mg/g of rock material). This confirms the role of
electrostatic forces in the adsorption mechanism as pointed
out before.
Dynamic desorption tests
In the first experiment, the desorption profiles for the
polyacrylate and the CMI are compared in the same conditions
(Sea water, 60C) in Figure 10. It can be seen that the CMI
and polyacrylate performances are comparable. A level of 3 to
5 ppm effluent concentration, corresponding to the possible
MIC lower limit, is already reached for both inhibitors after
about 50 PV of Sea water injection. The reduced squeeze
lifetime is consistent with the low adsorption values of
Figure 8.
First, it is striking that polyacrylate and CMI have the same
adsorption and desorption profiles. In these experiments these
products behave in an almost identical manner, probably
owing to the nature of their adsorbing functions, i.e.
carboxylates. However, further experiments are required to
clarify this conclusion. The optimal conditions for adsorption
of CMI on limestone would need to be studied and this for the
different degrees of substitution and for different degrees
of polymerisation .
Second, the squeeze life time for the polyacrylate in a
limestone core, i.e. 50 PV, is very low as found in similar
salinity and temperature conditions but with a Forties core, i.e.
a sandstone10. This confirms that the polyacrylate is
definitively less performing than products like phosphonates.

The lifetime obtained with a phosphonate in similar

conditions11, i.e. limestone mineralogy, temperature, water
composition, was more than 5 times longer than the result
obtained here for the polyacrylate. It was nevertheless shown
that the phosphonate was retained by a precipitation
mechanism and this may explain its relatively longer lifetime.
As CMI is less sensitive to precipitation with divalent ions,
retention by precipitation is not expected to occur as readily
with CMI.

SPE 87453

resulted in a low CMI concentration return curve over an

extended period of time.
Additional experiments, by varying for example the degree of
substitution or polymerisation of the CMI and also the rock
mineralogy, are still required before down-hole field
implementation of these inhibitors in squeeze applications .

References
Figure 11 shows comparatively the inhibitor desorption
profiles with Forties type water versus Sea water elution
(previous experiment, Figure 10). Undoubtedly, the
conjunction of the increased inhibitor adsorption, due to the
low pH of the injection brine, and the chemistry of postflush
brine, Forties water, has a beneficial effect on inhibitor
squeeze lifetime: the 10 ppm inhibitor effluent concentration
is reached after 50 PV of elution while the 1 ppm level is
attained after about 250 PV.
Figure 10 shows that the length of time required for the CMI
to fall below 1 ppm active was 7 times longer in Forties
conditions than in Sea water conditions. This should be related
to the differences in the calcium content of the brines used for
the desorption: 400 ppm in the Sea water against 3100 ppm in
the Forties water. This would indicate that higher levels of
calcium could potentially improve the retention profile12. This
would require a more detailed study.
Moreover inhibitor injection in more acidic conditions
improved somewhat the permeability of the carbonate core :
kw increases from 1.6 mD to 6.1 mD at the end of the
elution step.

1.

I.R.Collins, B.Hedges, L.M.Harris, J.C.Fan, L.D.G.Fan:

"The Development of a Novel Environmentally Friendly
Dual Function Corrosion and Scale Inhibitor", SPE
65005, SPE International Symposium on Oilfield
Chemistry, Houston TX, 13-16 February 2001.

2.

N.Kohler, B.Bazin, C.Lemaire, D.Pasquier: "Selection of

Green Inhibitors for Squeeze Treatments", paper n16,
14th International Oil Field Chemistry Symposium, Geilo,
Norway, 23-26 March 2003.

3.

N.Kohler, B.Bazin, A.Zaitoun, T.Johnson, "Green

Inhibitors for Squeeze Treatments : A Promising
Alternative", Corrosion/2004, paper 537, NACE 2004.

4.

R.Wat, O.M.Selle, H.Boerstad, O.Vikane, T.Hagen,

P.Chen, A.MacLean: "Scale Inhibitor Squeeze Treatment
Strategy on Heidrun", SPE 68944, SPE European
Formation Damage Conference, The Hague, The
Netherlands, 21-22 May 2001.

Adsorption/desorption mechanisms being very dependent on

experimental conditions (pH of the injected solution, degree of
substitution or polymerisation of the CMI, rock
mineralogy), other experiments are required before drawing
general conclusions on lifetime performance of the inhibitor.

5.

P.Chen, T.Hagen, A.MacLean, O.M.Selle, K.Stene,

R.Wat: "Meeting the Challenges of Downhole Scale
Inhibitor Selection for an Environmentally Sensitive Part
of the Norwegian North Sea", SPE 74652, SPE Oilfield
Scale Symposium, Aberdeen, UK, 30-31 January 2002.

Conclusions

6.

H.C. Kuzee, H.W.C. Raaijmakers: Methods for

preventing deposits in oil extraction, publication NWO
9964716.

7.

D.L.Verraest, J.Peters, H.van Bekkum, G.M. van

Rosmalen: "Carboxymethyl Inulin: A New Inhibitor for
Calcium Carbonate Precipitation", J. Am. Oil Chem. Soc.,
vol.73, n1 p. 55-62, 1996.

8.

NACE Standard Test Method TM 0197-97 : "Laboratory

Screening Test to Determine the Ability of Scale
Inhibitors to prevent the precipitation of Barium Sulfate
and/or Strontium Sulfate from Solution (for Oil and Gas
Production Systems).

9.

G.M.Graham, K.S.Sorbie, L.S.Boak, K.Taylor, L.Billie:

"Development and Application of Accurate Detection and
Assay Techniques for Oilfield Scale Inhibitors in
Produced Water Samples", SPE 28997, SPE International
Oilfield Chemistry Symposium, San Antonio,TX, 14-17
February 1995.

Carboxy Methyl Inulins (CMI) have been compared to

Phosphonates and Polyacrylates as "green inhibitors" of
mineral scale deposition of reservoir production brines.
Comparative Jar and Tube Blocking Tests show that these new
class of green inhibitors are good biodegradable scale
inhibitors for both carbonate and sulfate scale deposition.
Preliminary static and dynamic adsorption / desorption
experiments performed on limestone core material with the
CMI inhibitor dispersed in Sea water show that its behaviour
is quite similar to that of a polyacrylate with nevertheless
superior adsorbing properties. It has also been shown that
improved inhibitor adsorption can already be reached by
performing inhibitor injection in slightly acidic conditions.
Finally, the importance of the chemistry of the production
brine on the CMI return concentration was pointed out by a
comparison of desorption profiles with Sea water and Forties
water. The high calcium concentration in the Forties water

SPE 87453

10. Jordan, M.M. et al: Static and Dynamic Adsorption of

Phosphonate and Polymeric Scale Inhibitors Onto
Reservoir Core from Laboratory Tests to Field
Application: SPE 29002 presented at the SPE
International Symposium on oil Field Chemistry held in
san Antonio, Texas, 14-17 February 1995.
11. B.Bazin, N.Kohler, D.Broseta, Y.Le Gallo, P.Delaplace
and D.Longeron: An Integrated
Approach for the
Design of Squeeze of Mineral Scale Inhibitors SPE
78544, presented at the SPE International Petroleum

Exhibition &
October 2002.

Conference

Abu

Dhabi,

12. Jordan M.M. et al: The Design of Polymer and

Phosphonate Scale Inhibitor Precipitation Treatments and
the Importance of Precipitate Solubility in Extending
Squeeze Lifetime, SPE 37275 presented at the SPE
International Symposium on Oilfield Chemistry held in
Houston, Texas, 18-21 February 1997.

Table 1 : Carboxy Methyl Inulins : Main Characteristics

Carboxy Methyl Degree of Substitution
(DS)
Main Characteristics
Inulin
Degree of Polymerization (DP)
Mn
Mw
IP
Phosphonate:
Diethylene- penta (methylene)
206
DETPMP
phosphonic acid.
Polyaspartate:
Maleic anhydride-NH3
PASP
1740
4810
2.8
polycondensation.
Polyacrylate
Carboxylated copolymer
2000
3000
1.5
PAA
Carboxy Methyl Inulin - Degree of Substitution (DS) - Degree of Polymerization (DP)
CMI 2.5
CMI 2.0
CMI 1.5

DS : 2.5
DS : 2.5
DS : 2.0
DS : 2.0
DS : 1.5

DP: 10
DP: 24
DP: 10
DP: 24
DP: 10

13-16th

1730
4900
2160
3400
1760

5300
7300
6130
6000
4810

3.0
1.5
2.8
1.8
2.7

SPE 87453

Table 2 :Brine Compatibility to Sea water at 95C

Ca Tolerance
DETPMP

CMI DS 2.5

Active acid ppm

100
1000
10000
50000
100
1000
10000
50000

24 hours
PP
PP
-

Table 3 : Ionic compositions of the different waters for moderate sulfate scaling conditions
Forties formation water - (ppm)
Ion
Na+
Ca++
Mg++
K+
Ba++
Sr++
ClSO4--

Sea water
10,900
403
1,320
340
19,800
2,480

Formation water
30,200
3,110
480
430
250
660
54,587
-

50/50 Mixture
20,550
1,757
900
385
125
330
37,194
1,240

Table 4 : Ionic compositions of the different waters for high sulfate scaling conditions
Miller formation water (ppm)
Ion
Na+
Ca++
Mg++
K+
Ba++
Sr++
ClSO4--

Sea water
10,900
403
1,320
340
19,800
2,480

Formation water
25,591
500
91
1,100
650
60
41,142
-

50/50 Mixture
18,245
451
705
720
325
30
30,471
1,240

SPE 87453

Table 5 : Ionic compositions of the different waters for carbonate scaling (ppm).
Ions
Na+
Mg++
Ca++
ClHCO3-

Cation-rich Water
27,521
2,048
16,090
77,023
-

Anion-rich Water
28,387
42,479
2,296

50/50 Mixture
27,954
1,024
8,045
59,751
1,148

Table 6: Dynamic CaCO3 Scale Inhibition test

(qtotal = 30 ml/h, capillary 0.25 mm (I.D.) , 60C)
Inhibitors
Phosphonate (HEDP)
Polyacrylate (PAA)
Polyaspartate (PASP)
Polysaccharide (CMI)
2.5 DP 10
"
"
2.5 DP 24
"
"
2.0 DP 10
"
"
2.0 DP 24
"
"
1.5 DP 10

MIC CaCO3 (ppm)

<4
2 < MIC < 5
5
5 < MIC < 10
7.5 < MIC < 10
< 10
7.5
10

Table 7: Dynamic moderate BaSO4 scale inhibition tests

(q = 840 ml/h, capillary : 1.1 mm (I.D.), 90C, pH 6)
Inhibitors
DETPMP
Pasp
CMI DS 2.0 DP 10
CMI DS 2.5 DP 10

MIC BaSO4 (ppm)

3 < MIC < 5
< 5.5
< 4.5
3 < MIC < 4

Table 8: Compositions of solutions for the dynamic experiments.

Adsorption
1%

Experiment 1

Experiment 2

Inhibitor
concentration (A.M.)
Brine
Sea water
pH
6 adjusted with HCl
Inhibitor
1%
concentration (A.M.)
Brine
Sea water
pH
4.5 adjusted with HCl

Desorption
Sea water
As it is
Forties water
As it is

SPE 87453

CH 2 OH

CH 2 OH

OH

OH

HO

HO

HO
HOH 2 C

HO

HO CH 2

Cl-CH2CO2-Na+,
H2O, NaOH

OH

O
OH

CH 2

CH 2
-

OH
HOH 2 C

OCH 2 CO 2 Na

CH 2 OCH 2 CO 2 - Na +O
O

OH

OH

CH 2 OH

CH 2 OH

OH

OH

Figure 1 : Carboxymethylation of Inulin (n: polymerisation degree)

Sulfate Scaling Inhibition

Moderate scaling conditions
CMI 2.0 DP 10

100

CMI 2.5 DP 10

90

100
90
80
70
60
50
40
30
20
10
0

80
Efficiency %

Efficiency %

DETPMP

Sulfate Scaling Inhibition

High scaling conditions
100 ppm

200 ppm

70
60
50
40
30
20
10
0

10

50

100

Inhibitor Concentration ppm

Figure 2 : Comparative Jar Tests (Moderate BaSO4

scaling conditions)

DETPMP

CMI 2.0

CMI 2.5

Scale Inhibitor

Figure 3 : Comparative Jar Tests (High BaSO4

scaling conditions)

SPE 87453

CaCO3 Inhibition
10

9
BLANK

CMPS 1.5-DP10

CMPS 2.0-DP10

Differential Pressure (Bar)

CMPS 2.5-DP10
7

10 ppm

a.m.

2
PAA

0,0

0,5

1,0

1,5

2,0

2,5

Time (hours)

Figure 4 : Comparative CaCO3 inhibition by green inhibitors

TBT method (C inh = 10 ppm, 60C).

CaCO3 Inhibition
10

Blank

5 ppm

7.5 ppm

CMI 2.0-DP24

Differential Pressure (Bar)

8
7
6
5

10 ppm
4
3
2
1
0
0,0

0,5

1,0

1,5

2,0

Time (hours)

Figure 5 : CaCO3 inhibition by High Molecular Weight CMI

(TBT method, 60C).

2,5

10

SPE 87453

5,5

Concentration: 3.4 ppm

Blank

4,5

DETPMP

3,5

CMI DS 2.0

2,5

CMI DS 2.5
1,5

0,5

-0,5

10

15

20

25

30

35

Time (min)

:
Figure 6: Comparison of BaSO4 inhibition by TBT method at 90C.
(ID= 1.1 mm; Q=14 ml/mn)
3,00
Adsorption mg/g

Pressure (psi)

PASP

2,50

CMI 2,5

2,00
PAA

1,50
1,00
0,50
0,00
0

500

1000

1500

2000

2500

Equilibrium Concentration mg/l

Figure 7 : Static adsorption on crushed Lavoux limestone

(pH 6, 60C)

40

45

14000

1,4

12000

1,2

10000

8000

0,8

6000

0,6

CMI 2,5 DP10

polyacrylate
tracer

4000
2000

0,4
0,2

0
0

2
3
Pore Volume

Figure 8 : Dynamic adsorption on Lavoux limestone core

(reconstructed Sea water, pH 6, 60C)

Adsorption - Sea Water pH=4.5 - CMI 2.5 DP 10

Concentration (C/Cmax)

1,2

0,8

0,6

CMI 2.5 DP10

0,4

tracer: KI

0,2

0
0

0,5

1,5

2,5

3,5

Pore Volume (V/Vp)

Figure 9 : Dynamic adsorption on Lavoux limestone core

reconstructed Sea water, pH 4.5, 60C

Tracer

11

Inhibitor concentration
mg/l

SPE 87453

SPE 87453

100000
10000
CMI 2.5 DP10
1000
polyacrylate
100
10
1
0,1
0

50

100

150

200

250

Pore Volume

Figure 10 : Dynamic desorption from Lavoux limestone core

reconstructed Sea water, 60C, pH 6

Desorption experiments CMI 2.5 DP 10

CMI Concentration mg/l

Inhibitor concentration mg/l

12

100000
10000

Desorption Sea Water

1000

Desorption Forties Water

100
10
1
0,1
0

100

200

300

400

Pore Volume V/VP

Figure 11 : Dynamic desorption from Lavoux limestone core

comparison Sea water/formation water, 60C, pH 6

300