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.

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.

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 any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

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.

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.

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

www.petroman.ir

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. 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).

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.

Tube Blocking Tests (TBT)

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

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.

www.petroman.ir

SPE 87453

tests, with a far longer contact time, a levelling effect in inhibiting performance is observed. 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.

Hach method for the polyacrylate and by the hyamine turbidimetric method9 for the polysaccharide. 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. 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.

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

www.petroman.ir

SPE 87453

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. 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. 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.

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
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. 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. N.Kohler, B.Bazin, A.Zaitoun, T.Johnson, "Green Inhibitors for Squeeze Treatments : A Promising Alternative", Corrosion/2004, paper 537, NACE 2004. 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. 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. H.C. Kuzee, H.W.C. Raaijmakers: Methods for preventing deposits in oil extraction, publication NWO 9964716. 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. 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). 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.

2.

3.

4.

5.

Conclusions
Carboxy Methyl Inulins (CMI) have been compared to Phosphonates and Polyacrylates as "green inhibitors" of mineral scale deposition of reservoir production brines.

6.

7. 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 8.

9.

www.petroman.ir

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,

13-16th

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 1730 4900 2160 3400 1760 5300 7300 6130 6000 4810 3.0 1.5 2.8 1.8 2.7

www.petroman.ir

SPE 87453

Table 2 :Brine Compatibility to Sea water at 95C Ca Tolerance DETPMP Active acid ppm 100 1000 10000 50000 100 1000 10000 50000 24 hours PP PP -

CMI DS 2.5

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

www.petroman.ir

SPE 87453

Table 5 : Ionic compositions of the different waters for carbonate scaling (ppm). Ions Na+ Mg++ Ca++ ClHCO3Cation-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% Desorption Sea water As it is Forties water As it is

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

www.petroman.ir

SPE 87453

CH 2 OH O OH HO HO HOH 2 C O
OH

CH 2 OH O OH HO HO

Cl-CH2CO2-Na+, H2O, NaOH

CH 2

HO CH 2

O OH

CH 2

OH HOH 2 C O
OH

n
O

OCH 2 CO 2 Na

CH 2 OCH 2 CO 2 - Na +O O OH

CH 2 OH OH
OH

CH 2 OH

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

Sulfate Scaling Inhibition Moderate scaling conditions

DETPMP CMI 2.0 DP 10 CMI 2.5 DP 10
100 90 80 Efficiency % 70 60 50 40 30 20 10 0

Sulfate Scaling Inhibition High scaling conditions 100 ppm 200 ppm

100 90 80 70 60 50 40 30 20 10 0 5 10 50 100 Inhibitor Concentration ppm

Efficiency %

DETPMP

CMI 2.0

CMI 2.5

Scale Inhibitor

Figure 2 : Comparative Jar Tests (Moderate BaSO4 scaling conditions)

Figure 3 : Comparative Jar Tests (High BaSO4 scaling conditions)

www.petroman.ir

SPE 87453

CaCO3 Inhibition
10 9 BLANK 8 CMPS 2.5-DP10 CMPS 1.5-DP10 CMPS 2.0-DP10

Differential Pressure (Bar)

10 ppm

a.m.

2 PAA

0,0

0,5

1,0 Time (hours)

1,5

2,0

2,5

Figure 4 : Comparative CaCO3 inhibition by green inhibitors TBT method (C inh = 10 ppm, 60C).

CaCO3 Inhibition
10 9 8

Blank

5 ppm

7.5 ppm

CMI 2.0-DP24

Differential Pressure (Bar)

7 6 5

10 ppm
4 3 2 1 0
0,0 0,5 1,0 1,5 2,0 2,5

Time (hours)

Figure 5 : CaCO3 inhibition by High Molecular Weight CMI (TBT method, 60C).

www.petroman.ir

10

SPE 87453

5,5

Concentration: 3.4 ppm

4,5

Blank PASP DETPMP CMI DS 2.0

Pressure (psi)

3,5

2,5

CMI DS 2.5
1,5

0,5

-0,5

10

15

20

25

30

35

40

45

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 2,50 2,00 1,50 1,00 0,50 0,00 0 500 1000 1500 2000 2500 Equilibrium Concentration mg/l PAA CMI 2,5

Figure 7 : Static adsorption on crushed Lavoux limestone (pH 6, 60C)

www.petroman.ir

SPE 87453

11

14000 Inhibitor concentration mg/l 12000 10000 8000 6000 4000 2000 0 0 1 2 3 Pore Volume 4 5 CMI 2,5 DP10 polyacrylate tracer

1,4 1,2 1 0,8 0,6 0,4 0,2 0 Tracer

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

1,2

Concentration (C/Cmax)

0,8

0,6

CMI 2.5 DP10 tracer: KI

0,4

0,2

0 0 0,5 1 1,5 2 2,5 3 3,5 4

Pore Volume (V/Vp)

Figure 9 : Dynamic adsorption on Lavoux limestone core reconstructed Sea water, pH 4.5, 60C

www.petroman.ir

12

SPE 87453

Inhibitor concentration mg/l

100000 10000 CMI 2.5 DP10 1000 polyacrylate 100 10 1 0,1 0 50 100 150 Pore Volume 200 250 300

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

100000 10000 1000 100 10 1 0,1 0 100 200

Pore Volume V/VP Desorption Sea Water Desorption Forties Water

300

400

Figure 11 : Dynamic desorption from Lavoux limestone core comparison Sea water/formation water, 60C, pH 6

www.petroman.ir