SPE 87570 Novel Synergistic Water Soluble Corrosion Inhibitors

William M. McGregor / Lamberti SpA

Copyright 2004, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the 1 Corrosion held in Aberdeen, UK, 28 May 2004.
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Introduction
International Symposium on Oilfield

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 Ever more stringent environmental regulations make it increasingly difficult to obtain satisfactory corrosion inhibitors which are effective while being compatible with marine life. Toxicity towards aquatic organisms is a major concern and environmental constraints have been imposed on the types of compositions used in the North Sea in order to protect marine organisms. Many available inhibitors cannot meet the environmental criteria while maintaining effective corrosion inhibition. For sweet / carbon dioxide corrosion, imidazoline based inhibitors are traditionally effective but they have an imperfect environmental profile. Here we describe how the environmental properties have now been improved by alkoxylation of a traditional inhibitor. This not only improves the environmental aspects but also increases the hydrophilicity of the inhibitor making it more suitable for water based applications and increasing its solubility in the water phase where corrosion usually takes place. Organic phosphate esters are also effective corrosion inhibitors with a broad field of application in sweet and sour corrosion. Here we describe laboratory-based corrosion testing on an innovative range of mixed imidazoline / oligophosphate ester inhibitors which show synergy in corrosion inhibition ability, especially at low dosages. The alkoxyimidazoline protects the cathode of the electrochemical cell and the oligophosphate protects the anode - this dual mechanism promotes synergy and increases confidence that the inhibitor will continue to give corrosion protection even in extreme situations where one of the components might have failed. These mixed corrosion inhibitors are therefore applicable to a wide range of water based systems used in the oil and gas industry.

Corrosion of metal parts and surfaces exposed to aqueous media has always been a difficult problem. The necessity of effectively inhibiting corrosion is particularly felt in oil exploration, production and refining, onshore and off-shore, where corrosion inhibitors need to be used to inhibit corrosion of metal surfaces in contact with water or oil industry fluids containing oil or water. The corrosive environments normally encountered in oil wells may be anaerobic or aerobic and may contain sour (hydrogen sulphide) or sweet (carbon dioxide) corrosive components. Although many effective corrosion inhibitors are known the choice of corrosion inhibitors used varies according to the nature of the corrosive environment. Inhibitor compositions are often based on amines, amides or imidazolines, often in combination with other types of inhibitor, including alkoxylated phosphate esters. In fact, for sweet corrosion, inhibitor compositions are often based on amines, amides or imidazolines, often in combination with other types of inhibitor. For example corrosion inhibitor compositions are known1,2 which are based on the combination of ethoxylated imidazolines with ethoxylated straight chain linear alcohol phosphates. These patents1,2 lays claim to these compositions as inhibitors suitable to meet the demanding environmental criteria in sensitive environments such as the North Sea. Nonetheless these phosphate esters derived from linear monoalcohols are rather less sophisticated as corrosion inhibitors than the phosphate esters of oxyalkylated branched polyols3 (which interestingly had not been previously combined with imidazolines). The combination of imidazoline derivatives with phosphate esters can be considered to be particularly desirable as this should promote a synergistic increase in corrosion protection because imidazolines are generally considered to protect the cathode of the electrochemical cell associated with the corrosion process whereas phosphate esters are generally considered to protect the anode. Environmental concerns make it more difficult to obtain satisfactory corrosion inhibitors which are effective while being compatible with the sensitive life forms indigenous to the local environment.. In the North Sea especially, toxicity towards aquatic organisms is a serious concern and stringent environmental constraints have been agreed for the types of compositions used in the North Sea in order to protect these organisms. Many commercially available inhibitors cannot meet the environmental criteria while maintaining very

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SPE 87570

effective corrosion inhibition. One particular problem of note is that of the ecotoxicity of the products used as corrosion inhibitors. Therefore it is essential to use corrosion inhibitors which are active at very low concentrations and which will not harm the living organisms present in the natural environment in which they are used. Experimental techniques Corrosion wheel-testing was performed with 200ml sealed bottles, containing 150ml of 10% aq. sodium chloride, saturated with carbon dioxide and dosed with the anticorrosive composition under test, and containing a mild steel test coupon. Before use, each coupon was washed with acetone, then 3% hydrochloric acid, then 10% aq. sodium bicarbonate, then acetone, dried and accurately weighed. Some bottles contained no anticorrosive composition to give a reference measure of the average uninhibited corrosion rate. The bottles containing the test materials were mechanically rotated inside a suitably equipped oven at 70C for 16 hours. Afterwards, the coupons were cleaned with steel wool, washed with acetone, dried and weighed again. The percentage of weight lost allowed the calculation of weight loss according to Equation 1. (1) % protection = 100 (100 x A/B) where, A = % weight loss with anticorrosive B = % weight loss without anticorrosive For each simultaneous set of tests, a reference commercial corrosion inhibitor was dosed at 300ppm in several bottles and the average % protection for this reference product was mathematically normalised to 100 nominal protection units by multiplication with an experimentally determined conversion factor. All the simultaneous corrosion tests were multiplied by this conversion factor to normalise the results, giving Nominal Protection values for the anticorrosive compositions at varying dosages. The corrosion tests were performed at 8 different dosages from 6 to 1500 ppm of active components. Then the curves of Nominal Protection against Dosage were smoothed by a logarithmic method (in MS Excel) to give best-fit corrosion protection-dosage curves. Toxicity testing was performed using a short term toxicity test following procedure devised by the Laboratory of Biological Research in Aquatic Pollution of Ghent University and adopting the salt water crustacean Artemia salina as test organism. Biodegradability tests were performed in seawater following the OECD 306 guidelines (closed bottle method). Bioaccumulation potential was studied by obtaining log pow (octanol-water partition coefficient) from an interactive website4 and considering that a log pow < 3 indicates low potential for bioaccumulation in fatty tissues.

Corrosion Test Results In the following tests, various compositions were prepared and tested each containing 30% by weight of active material in water (Test 1) or water/isopropanol 1:1 (Tests 2-6). In Tests 2-6 the number of molar equivalents of the active components was based on acid-base titration measurements. Test 1 (for comparison only) This is a reference test without imidazoline. Primary Compositions containing LAPS and another containing PPS were prepared and tested, each containing 30% by weight of active material in water. From the experimental results displayed in Graph 1 it is clear, for the Primary Compositions, that LAPS gives better corrosion protection than PPS and it should be expected that the same trend will be found for a Binary Composition of a given FI xEO with LAPS or PPS. This led us to expect that the Binary Composition of FI xEO with LAP should always give better protection than the Binary Composition of FI xEO with PP. Test 2 (for comparison only) This is a reference test with a non-ethoxylated imidazoline. A Binary Composition containing FI / LAP and another containing FI / PP were prepared and tested, each containing 30% by weight of active materials in water/isopropanol (1:1), the combination being in 1:1 stoichiometric ratio between the imidazoline, FI, and the acid phosphate, PP or LAP.

Graph 1: Corrosion Test PPS against LAPS Nominal Protection

100 80 60 40 20 0 0 20 40 60 80 100 120 140 160 dose (ppm of active content)

LAPS PPS
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We expected the Binary Composition of FI with LAP to give better protection than the Binary Composition of FI with PP and this is confirmed by the experimental results displayed in Graph 2.
Graph 2: Corrosion Te st FI / PP against FI / LAP

Nominal Protection

100 80 60 40 20 0 0 20 40 60 80 100 120 140 160 dose (ppm of active content)

FI / LAP FI / PP
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SPE 87570

Nominal Protection

Test 3 A Binary Composition containing FI 3EO / LAP and another containing FI 3EO / PP were prepared and tested, each containing 30% by weight of active materials in water/isopropanol (1:1), the combination being in 1:1 stoichiometric ratio between the imidazoline, FI 3EO, and the acid phosphate, PP or LAP. We expected the Binary Composition of FI 3EO with LAP to give better protection than the Binary Composition of FI 3EO with PP. Strangely, the experimental results displayed in Graph 3 confirm this only at higher dosages; at lower dosages the trend is inverted and the Binary Composition of FI 3EO with PP gives better protection than the Binary Composition of FI 3EO with LAP.
Graph 3: Corrosion Test FI 3EO / PP against FI 3EO / LAP

stoichiometric ratio between the imidazoline, FI 7EO, and the acid phosphate, PP or LAP. We expected the Binary Composition of FI 7EO with LAP to give better protection than the Binary Composition of FI 7EO with PP. Strangely, the experimental results displayed in Graph 5 shows the trend to be inverted and the Binary Composition of FI 7EO with PP unexpectedly gives better protection than the Binary Composition of FI 7EO with LAP over the full range of dosages displayed.
Graph 5: Corrosion Test FI 7EO / PP against FI 7EO / LAP

100 80 60 40 20 0 0 20 40 60 80 100 120 140 160 dose (ppm of active content)

FI 7EO / LAP FI 7EO / PP
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Nominal Protection

100 80 60 40 20 0 0 20 40 60 80 100 120 140 160 dose (ppm of active content)

FI 3EO / LAP FI 3EO / PP
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Test 4 A Binary Composition containing FI 5EO / LAP and another containing FI 5EO / PP were prepared and tested, each containing 30% by weight of active materials in water/isopropanol (1:1), the combination being in 1:1 stoichiometric ratio between the imidazoline, FI 5EO, and the acid phosphate, PP or LAP. We expected the Binary Composition of FI 5EO with LAP to give better protection than the Binary Composition of FI 5EO with PP. Strangely, the experimental results displayed in Graph 4 shows the trend to be inverted and the Binary Composition of FI 5EO with PP unexpectedly gives better protection than the Binary Composition of FI 5EO with LAP over the full range of dosages.
Graph 4: Corrosion Te st FI 5EO / PP against FI 5EO / LAP

Test 6 A Binary Composition containing FI 17EO / LAP and another containing FI 17EO / PP were prepared and tested, each containing 30% by weight of active materials in water/isopropanol (1:1), the combination being in 1:1 stoichiometric ratio between the imidazoline, FI 17EO, and the acid phosphate, PP or LAP. We expected the Binary Composition of FI 17EO with LAP to give better protection than the Binary Composition of FI 17EO with PP. Strangely, the experimental results displayed in Graph 6 shows the trend to be inverted and the Binary Composition of FI 17EO with PP unexpectedly gives roughly equivalent protection to the Binary Composition of FI 17EO with LAP over most of the range of dosages displayed, except for lower dosages where the Composition with PP is slightly better.
Graph 6: Corrosion Te st FI 17EO / PP against FI 17EO / LAP

Nominal Protection

100 80 60 40 20
FI 17EO / LAP FI 17EO / PP
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Nominal Protection

100 80 60 40 20 0 0 20 40 60 80 100 120 140 160 dose (ppm of active content)

FI 5EO / LAP FI 5EO / PP
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0 0 20 40 60 80 100 120 140 160 dose (ppm of active content)

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Test 5 A Binary Composition containing FI 7EO / LAP and another containing FI 7EO / PP were prepared and tested, each containing 30% by weight of active materials in water/isopropanol (1:1), the combination being in 1:1

Discussion of corrosion test results Overall it is clear, for the Primary Compositions, that LAPS gives better corrosion protection than PPS and it should be expected that the same trend will be found for a Binary Composition of a given FI xEO with LAP or PP. In fact we expected the Binary Composition of FI xEO with LAP to

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SPE 87570

always give better protection than the Binary Composition of FI xEO with PP. Instead, as shown in the graphs, only the FI and FI 3EO based compositions follow the expected trend. For FI 5EO and 7EO the trend is unexpectedly reversed and the Binary Compositions with PP perform better than the Binary Compositions with LAP. Even for the FI 17EO the PP and LAP Binary Compositions strangely are equivalent in performance and do not follow the expected trend. Moreover, the unexpectedly better FI 5EO / PP and FI / PP compositions have very high corrosion protection, especially at low dosages this is a particularly interesting and welcome surprise as the high protection at low dosages is ideal for treating high throughput systems where very large quantities of fluid can then be treated with limited quantities of corrosion inhibitor. Compatibility The corrosion test results are and important factor in optimising the corrosion inhibitor performance. For field use other factors are also important, including cost, production feasibility, and compatibility with the application system. Since this type of corrosion inhibitor is particularly suitable for use in completion fluids as well as in other simpler aqueous systems, Table 1 shows the water and brine solubility characteristics for a preferred finished composition containing the preferred imidazoline, phosphate and appropriate environmentally compatible solvent(s). As can be seen from this table, the preferred composition exhibits a broad range of solubility, ideal for use in fresh water and all brines tested. Environmental considerations Ecotoxicology results on the active ingredients of the preferred anticorrosive composition are shown in Table 2. The excellent toxicity results suggest that these components be considered as environmentally compatible materials especially since the intermediate values obtained for biodegradation are less important for components with a low bioaccumulation potential as observed for each component. In summary these chemical products may be considered to be stable, low-toxicity components with good environmental properties. Conclusions Selected compositions combining ethoxylated imidazoline and phosphate ester have synergistically enhanced corrosion

protection, especially at low dosages - high protection at low dosages is ideal for treating high throughput systems where very large quantities of fluid can then be treated with limited quantities of corrosion inhibitor. These compositions are highly water soluble and are compatible with a wide variety of brine systems. The active components of these compositions are stable, low-toxicity materials with good environmental properties. Acknowledgements Thanks to the management of Lamberti SpA for granting permission to publish this paper. Thanks also to the staff in Lamberti SpA who helped this project and for discussions with special thanks to the staff of the ecotoxicology laboratory for collaboration. Nomenclature In the corrosion inhibitors presented the active materials are substituted imidazoline in combination with phosphate esters of ethoxylated polyol. The following abbreviations are used in the text to represent the active components under scrutiny: FI = long chain imidazoline FI xEO = FI, ethoxylated with x equivalents of ethylene oxide PP = ethoxylated polyol, phosphate ester, acid form PPS = ethoxylated polyol, phosphate ester, potassium salt LAP = ethoxylated long chain alcohol, phosphate ester, acid form LAPS = sodium salt of LAP References
[1] Braga, T.G. et al, Combinations of Imidazolines and Wetting Agents as Environmentally Acceptable Corrosion Inhibitors, World Patent WO 0049204, filed 16.02.00 [2] Martin, R. L., Biodegradable Corrosion Inhibitors of Low Toxicity, European Patent EP0651074, filed 10.10.94 [3] Bellos, T. J., Corrosion Inhibitor for Highly Oxygenated Systems, United States Patent US4311662, filed 19.01.82

[4] http://esc.syrres.com/interkow/kowdemo.htm

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SPE 87570

Table 1: Solubility of a Preferred Anticorrosion Composion in Selected Brines

Acquous Phase Fresh water Saturated NaCl Saturated KCl 30% w/w NaBr 38% w/w CaCl2 Solubility (1% w/w) complete complete complete complete complete

Table 2: Ecotoxicology of a Preferred Anticorrosion Composion

Imidazoline derivative

Phosphate ester

LC50 (mg/l) Artemia salina Biodegradability in Sea Water OECD 306 Bioaccumulation Potential (log pow)

2170 40% <3

> 10000 42% <3

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