Paper No.

00016

CORROSION

2000

Evaluation of Commercial Corrosion Inhibitors for CO2 Corrosion of API-13Cr Tubing Y. Tomoe, M. Shimizu Technical Research Center, Teikoku Oil Co., 9-23-30 Kitakarasuyama, Setagaya-ku, Tokyo 157, Japan R. H. Hausler Corro-Consulta 7804 Pencross Lane Dallas, TX 75248

ABSTRACT The Minaminagaoka field in Japan produces gas containing 6% CO2 and a light condensate. Some wells are completed with 13% Cr-steel tubing. The useful life of these tubulars was less than 6 years with failures occurring mainly due to what appeared to be flow induced localized corrosion. A program was initiated to evaluate commercial inhibitors for the protection of 13% Cr-steel production tubing. Various products from several suppliers were tested under constant contact and filming conditions. The optimum inhibitor was subsequently evaluated in the field. Through an unusual approach to the laboratory test methodology it was established that for waterdispersible as well as non-water-dispersible corrosion inhibitors a distinct hydrocarbon phase is required for good effectiveness. This was at first considered a problem for wells with a hydrocarbon dew point downstream of the choke. It was also concluded that the treatment life observed in the laboratory is many times shorter than the treatment life that could be established by field measurements. A new proposed model for batch treatment applications attempts to reconcile these observations. Keywords: API-13Cr Tubing, 13%Cr stainless steel, gas condensate well, CO2 corrosion, flow induced localized corrosion, erosion corrosion, corrosion inhibition, batch treatment, treatment life, inhibitor testing, inhibitor effectiveness.

Copyright
2000 by NACE International.Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE International, Conferences Division, RO. Box 218340, Houston, Texas 77218-8340. The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarily endorsed by the Association. Printed in U.S.A.
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INTRODUCTION The inner surfaces of API-13Cr tubing experienced localized corrosion at around 100 - 1,600m (300 to 4800 ft) from the well head in deep, hot Minaminagaoka gas-condensate wells. The causes of this corrosion were attributed to the higher downhole temperatures exceeding the safe operating limits of 13Cr in a CO2 environment and the presence of condensed water film with enough thickness to promote the development of corrosion (1,2). Based on these experiences with 13Cr, commercial corrosion inhibitors were recommended by several chemical companies. However, all the recommended inhibitors had been demonstrated to be effective against high temperature CO2 corrosion of carbon and low alloy steels rather than for 13Cr. Therefore, a series of inhibitor evaluation tests were carried out for 13Cr using high pressure, high temperature autoclaves simulating the downhote corrosive conditions. It should be kept in mind that classical corrosion inhibitor studies tend to relate the inhibitor molecular structure to its inhibition efficiency. However, commercial inhibitors, exhibiting high corrosion inhibition efficiency in actual oil and gas wells, are proprietary, complex mixtures of inhibitor ingredients, dispersants, and often demulsifiers in an oil solvent, and their precise molecular structures are generally not disclosed. Furthermore, oilfield operators prefer to select corrosion inhibitors for field use on the basis of case histories obtained for similar well conditions, in order increase the probability of success, and to avoid the occurrence of side effects such as emulsions and foaming. An interesting, not generally recognized phenomenon observed during routine evaluation tests of several commercial inhibitors in the laboratory led to a much more complex selection scheme than was originally anticipated. Because the nature of the production is such that hydrocarbons condense only at sufficiently low temperatures in the production separators, the inhibitor evaluation tests were carried out in an aqueous environment at first without a hydrocarbon phase. It was observed that inhibitors, when added to the aqueous test solution resulted in very, poor effectiveness. The addition of a small amount of xylene to the aqueous test solution in many cases, however, led to excellent protection (see also ref. 3). Therefore, only marginal effectiveness would have been expected in the field. Nevertheless, field measurements did not confirm this. Rather, reasonably good effectiveness was established in extensive field measurements, which also demonstrated that the treatment life was much longer than anticipated from the laboratory data. An effort was, therefore, made to reconcile these apparent discrepancies by presenting a model for the inhibitor movement in production tubing following batch treatment. This rudimentary concept defined the test methodology applied in this laboratory. The test results and field observations for selected inhibitors are discussed in light of this model.

BASIC C O N C E P T OF INHIBITOR E V A L U A T I O N

The ~pical corrosive environment of Minaminagaoka wells is summarized in Table 1. Although the length of tubing strings is about 4,500m, water begins to condense at around 4,000m from the well head (1). Hydrocarbons do not condense upstream of the wellhead, but are found in the surface equipment. Judging from the well conditions shown in Table 1, the pH value of the corroded areas is

considered to be low, lower than 3.5, in spite of the high temperature, due to high partial pressure of C02 (4). The corroded areas (Figure 1) were originally covered with chromium enriched corrosion products. It has always been questioned whether inhibitors in CO2 corrosion will be effective if adsorbed on the corrosion product layer ~, or whether the inhibitor has to penetrate the iron carbonate scale layer in order to inhibit the corrosion reaction occurring on the bare metal surface. Because of this uncertainty, all commercial inhibitors were evaluated on both bare and corroded 13Cr surfaces. The wells were completed with packers. Because of this limitation it was not possible to treat the wells continuously in the Minaminagaoka field. Rather, the corrosion inhibitors were applied by a specially designed full tubing displacement batch treatment methodology. The corrosion inhibitor as received (usually 1.5 drums) was dissolved in 13 drums of diesel and injected into the tubing. This inhibitor batch was then displaced with a sufficient volume of a heavy diesel solvent in order to effect a full tubing displacement. Subsequent to this treatment the wells were then shut in for two hours prior to slowly produce back all the fluids. Normal production rates were then resumed. Upon resumption of production after the above described batch treatment, most of the solvent oil and a part of the inhibitor return to the surface within a short period of time. Clearly only the inhibitor and the heavy hydrocarbons remaining deep in the well are responsible for the mitigation of corrosion over time at shallower depths. The concept of inhibitor migration up the tubing string over time is illustrated in Figure 2, After resumption of production, it is visualized that the inhibitor and the remaining heavy hydrocarbon solvent return to the surface by repetitive adsorption and desorption on the surface of the tubing. In this sense the tubing resembles a giant gas chromatographic column. The inhibitor due to its lower volatility and higher affinity to the corrosion product covered tubing surface is expected to migrate slower than the hydrocarbon components. Recognizing this relationship will have special significance relative to the length of the treatment life. Once the tubing is regarded to be a chromatographic separation column, the length of the effective inhibitor treatment term can be discussed as follows. Assume that the produced gas flows up the inside of the tubing at a rate of Vg, whereas the condensed water flow rate up along the inner surface is much slower and defined as Vw. Inhibitor probably mixed with hydrocarbon move up the tubing carried by the condensed water while repeatedly adsorbing and desorbing on the tubing surface. Effective inhibition occurs only when the inhibitor molecules are adsorbed on the tubing surface. Let the time to desorption be ta, and the time to t,. The rate of migration of the inhibitor, V~, can then be expressed by the following simple equation (see also Figure 1):

~) For sour corrosion it was established that nitrogen type inhibitors become effective when adsorbed on the iron sulfide scale (see also Re 3)

Vi = Vw'ta ta + td
where: Vi : rate of inhibitor migration V~,: flow rate of condensed water t~ : time to adsorption after desorption ta : time to desorption after adsorption

The effectiveness of batch treatments is usually evaluated in the terms of the length of the treatment life. Clearly a longer treatment life would require slower movement of the inhibitor up the production string. The flow rate of the water (Vw) may be assumed constant under constant production conditions. Therefore, in order to make Vi smaller, inhibitors would have to be selected which adsorb fast and/or desorb slowly (t,,>>td). This rational was lbllowed in the evaluation of the recommended commercial inhibitors for bare and corroded 13Cr surfaces. The adsorption behavior of the inhibitors was monitored by means of the rate of decrease of the corrosion rate, and also the film persistency was assessed by means of weight loss tests on filmed test specimens. The inhibitors selected by this laboratory methodology were then tested in the field. The field test results were again verified by additional laboratory investigations.

EXPERIMENTAL

Materials

Rectangular specimens (2 x I0 x 50 mm) and cylindrical electrodes (20 x 6 mm) were cut from actual API-13Cr tubing the chemical composition of which is given in Table 2. All specimens and the electrodes were abraded with emery paper up to No. 600, ultrasonically degreased in acetone, washed with deionized water, dried, and weighed before use. The test brine was made up to a chloride concentration of 1000 ppm and slightly buffered with a bicarbonate concentration of 100 ppm. The chemicals were analytical grade reagents. The pH of this solution was adjusted to 6.8 with a small amount of dilute hydrochloric acid. In the corrosion tests, the solution alter deaeration with nitrogen was saturated with carbon dioxide (CO2) at a predetermined CO2 partial pressure Eight inhibitors recommended by three chemical suppliers for the oil and gas industry were used in the evaluations. All the jnhibitors were said to be of the filming amine type. However, as shown in Table 3, their solubility in oil and their dispersibility in water were significantly different

Experimental procedure
Evaluation of adsorption behavior of inhibitors 1.7 liters of the test solution were filled into a Hastelloy C-276 lined 2.3 liter autoclave (26% gas space), which was equipped with devices for electrochemical measurements. The 13Cr electrodes were used as working and reference electrodes. A platinum bar (6 nun in diameter and 110 mm in length) was used as the counter electrode. The autoclave was deaerated to less than 1/10,000 of the original oxygen by repeated pressurization with ultra-pure N2 while stirring at 350rpm. This should have resulted in less than 1 ppb of dissolved oxygen in the solution. The autoclave was then pressurized to 4 MPa (.-- 580 psi) with ultra-pure CO2. The corrosion rate of the working electrode was recorded every 5-6 minutes by a commercial corrosion rate meter based on the linear polarization resistance technique (5). The autoclave was heated up at 150 C~C (302 ~F). The corrosion rate became stabilized after about 15 hours. At this point a 10% inhibitor solution in ethanol was injected into the autoclave through a chemical injection valve on the autoclave so as to bring the concentration of the inhibitor to 200 ppm.. Two hours later, 20 rnL of xylene were similarly injected into the autoclave in order to simulate the effect of a hydrocarbon solvent on the inhibition efficiency of the corrosion inhibitor. A series of similar experiments were carried out with 13Cr electrodes which had been pre-corroded at 180 C~C(356 ~F) for 75 hours prior to injection of the inhibitor. Inhibitor film persistency test Twenty milliliter of a 10% inhibitor solution in xylene was poured into a 25mL test tube, A rectangular specimen was subsequently immersed in the solution for filming. After one hour, the specimen was retrieved and washed with ethanol to remove the excess inhibitor solution from the surface. A filmed test specimen was put into 20 mL of the test solution contained in a 25 rnL test tube. The test tube was capped with a permeable silicone rubber stopper to allow breathing. These test tubes containing both the test solutions and the filmed test specimens were put into a 7.8 liter stainless steel (SUS 316) autoclave. After the deaeration in the same manner as described above, the autoclave was similarly pressurized with CO2, heated up to 150 C (302 ~F) and was then allowed to stand for three days. After cooling, the specimens were retrieved, de-scaled with an inhibited dilute hydrochloric acid solution, washed with deionized water, dried, and weighed. The corrosion rates were calculated based on the weight losses. A non-filmed test specimen was also tested and the result was used to calculate the percent inhibition. Such film consistency tests were also carried out on pre-corroded specimens. In this case, the precorrosion occurred in the same test solution under the identical CO2 partial pressure over 220 hours at 160 C (320 ~JF). Inhibition tests in actual wells

Selected inhibitors were field tested by the method described elsewhere (6). The inhibition efficiency was monitored by the change in iron counts in the produced water. The determination of iron count was made by the o-phenanthoroline method. Electrochemical study of inhibition efficiency of the selected inhibitor and the influence of xylene on the inhibition efficiency Using the 2.3L autoclave for electrochemical measurement cathodic and anodic polarization curves were measured, following the similar method as described above. However, in these measurements, a pressure balanced Ag/AgC! (0.1mol/L KCI ) reference electrode was employed in stead of a 13Cr electrode (7). Using a commercial potentiostat, a cathodic polarization curve was obtained at a scanning rate of 20mV/min. After the corrosion potential returned to its original value, an anodic polarization curve was obtained at the same scanning rate. After a 10% inhibitor solution of ethanol was injected into the autoclave as to the concentration of the inhibitor becomes 200ppm to the test solution. Cathodic and anodic polarization curves were measured in the same manner as written above. After the injection of 20mL of xylene into the autoclave, the polarization curves were obtained again.

RESULTS AND DISCUSSION

Evaluation of Laboratory Results

Corrosion inhibitors, particularly oil soluble/water dispersible ones, are not generally tested in the absence of a hydrocarbon phase. It is therefore interesting to note that in Table 3 that injection of the inhibitors into a water phase only corrosion medium led with one exception (C-8) to rather poor results. The presence of a small hydrocarbon phase (20 ml xylene in 1.7 liters of brine) led in almost all cases to high degrees of protectiveness (with the exception of A-l). This effect, although not generally known, had previously been described for sour corrosion (3). It appears, therefore, that for good inhibition a distinct oil phase may be required. This observation was the reason for the design of the batch treatment, which included full tubing displacement of the inhibitor "pill" with a heavy diesel hydrocarbon. Pre-corrosion of the test specimens leads in the constant contact test (CCT) sometimes to lower effectiveness. In three instances this decrease is quite noticeable while for the other inhibitors there was either no effect or a marginal one. Tile fihn persistency test (FPT) appears to distinguish between the inhibitors much more effectively than the CCT. In general the effectiveness in the FPT is decreased. Indeed, some products even appear to accelerate the corrosion on the pre-corroded specimens. The performance of the products from company A was not convincing, particularly in the absence of a hydrocarbon phase Furthermore, for these compounds, film persistency was essentially non-existent. In

particular, compound A-1 could, on the basis of the available data, be said to be no inhibitor at all. Nevertheless, because of its ready availability and because of the presumably favorable case histories, this inhibitor had been used in the field prior to the studies described here. In view of the fact that the available data from the 6 test procedures do not allow for consistent ranking (see also Figure 3) three products were specifically focused on in more detail. These B-6, C-8 and A-1. B-6 was selected because of its general good performance. C-8 however, performed best in the absence of a hydrocarbon phase. A-I was used as a comparison because it had already been in use in the field. The raw data on adsorption behavior of these three inhibitors against bare and corroded 13Cr are shown in Figure 4 (except for A-1 on pre-corroded 13Cr, because of the negligible effects). The horizontal axis is time and the vertical axis is corrosion rate. In cases for bare 13Cr, the corrosion rates reached steady state in 1.5 hours after the injection of an inhibitor. It is considered that the adsorption of the inhibitors is nearly complete after this period of time and the adsorption equilibrium has been attained. In contrast, in the case of corroded 13Cr, the corrosion rates after 1.5 hours were still decreasing after the injection of the inhibitor and, in one case, also after the injection of the xylene. These results suggest that on corroded 13Cr, it takes longer for inhibitors to reach adsorption equilibrium In the case of A-1 the poor inhibition efficiency of only 3%, when injected by itself, was essentially not affected by the addition of xylene. In general it can be said that when the inhibition efficiency of inhibitor by itself is equal to or higher than 10%, the addition of xylene has a large effect and can raise the inhibitor effectiveness to above 95%. While xylene by itself has negligible inhibitive properties, these results suggests that xylene in the presence of the inhibitor actually contributes more to the overall inhibition efficiency than the inhibitor by itseff. Furthermore, it should not be overlooked that four of the eight inhibitors accelerated corrosion of corroded 13Cr in the FPT, although some effectiveness was observed on bare metal surfaces It is believed that such results have never been observed before, or have not been reported and are not routinely screened for. The phenomenon may, however, be of great importance in certain field situations.
Field Inhibitor evaluations

Based on the laboratory results and product availability, field tests of selected inhibitors were considered for the purpose of verifying the laboratory methodology and to identify the most effective product. Among three inhibitors of interest C-8, which had shown excellent adsorption behavior, could not be used for a field test, because it caused severe foaming the gas processing plant downstream. Therefore only the results from field tests on inhibitors A- 1 and B-6 can be described below. The change in iron count of produced water after a batch treatment for well X using inhibitor A-I is shown in Figure 5. The horizontal axis is date, and the vertical axes are the production rate of gas and the iron count. A corrosion inhibitor was continuously injected at the wellhead of this well to protect the gathering line. The water samples were taken from a stainless steel sampling pot which was located

just downstream of the choke about 50 meters (150 r ) from the wellhead. If the batch treatment for the well had been effective, a clear decrease in iron count from the base line of 30 ppm ought to have been observed. No such decrease in iron count was observed. In fact, the trend of the iron counts is opposite the trend in the production rates which is in agreement with the COPRA correlation (Ref. 8) The inhibitor A-l, it was concluded, was not effective tbr 13Cr tubing in a typical Minaminagaoka well which was in agreement with the laboratory data. The test results for inhibitor B-6 obtained in a similar well (Y) are shown in Figure 6. In this test the continuous inhibition for the gathering line was stopped. After the increase in iron count and the value reached a steady state, a batch treatment for the well was conducted. After the batch treatment, the iron count apparently dropped below 20 ppm, which had been the base line during continuous inhibition for the gathering line, and prior to the batch treatment. The lowest value measured was a little less than 10ppm 83% inhibition, in apparent agreement with the laboratory results. However, the iron count began to increase about two weeks after the batch treatment, reached 20ppm about three weeks after the treatment and was still increasing thereafter. The inhibitor B-6 was concluded to be effective for 13Cr tubing with probably limited treatment life. Although the effective inhibitor treatment time using inhibitor B-6 was on the order of three weeks, considering the severity of the well conditions, this treatment life was judged to be acceptable. Similar film lives following batch treatment of wells with comparable production rates and flowing bottom hole temperature had been observed previously (8). Conventional film life theory holds that once an inhibitor molecule desorbs from a metal surface under dynamic conditions, this inhibitor molecule is carried by produced fluids without contributing further to inhibition. The reason for this is that desorbing the inhibitor results in a very low concentration in the streaming fluids. Indeed, film lives determined in laboratory tests at elevated temperatures seldom exceed a few days (see also ref. 3), and are more likely of the order of a few hours. It appears, therefore, reasonable to explain the observed long film lives in the field in terms of the above model of a chromatographic column. Electrochemical investigation on the inhibition efficiency of B-6 and the effect of xylene Figure 7 shows the results of polarization measurements under downhole conditions simulated in the autoclave. The injection of the inhibitor in an ethanol solution resulted in only a small inhibition effect. However, the injection of xylene greatly decreased both anodic and cathodic currents, thus confirming the results obtained earlier by means of continuous LPR measurements (Fig 3). Similar results were also obtained with a water soluble corrosion inhibitor, sodium laurylate. These observation indicate that hydrocarbons have a great affinity to a surthce already covered with an adsorbed layer of a hydrophobic polar compound such as a carboxylic acid, an imidazoline, or a phosphate ester. The effect is interpreted in terms of the hydrocarbon much more effectively excluding water from the surface and thereby reducing the corrosion reactions simply be impeding water migration to the electrochemically active sites (anodes and/or cathodes). It had been pointed out in the literature (10,11) that in treating hot deep gas wells attention should be given to the phase behavior of the inhibitor carrier oil. The idea was that without a hydrocarbon phase the inhibitor would not move up the tubing string, or might evaporate into the hot gas stream. It now appears more likely that a liquid hydrocarbon phase is required in the tubing in order to enhance the

inhibitor action by forming a hydrophobic layer as described above. This does of course pose some practical problems in (oil)-dry production strings that have to be treated batchwise. The treatment life is limited by the period of feed back of the inhibitor carrier oil during production. Similar thoughts had been expressed earlier (Ref. 12) where it was pointed out that overall effectiveness was greatly enhanced in wells that had a demonstrated self-squeezing behavior whereby an inhibitor reservoir could be established in the formation during shut-in following a batch treatment.

SUMMARY

AND CONCLUSIONS

A series of laboratory tests were conducted in order to selects the most appropriate corrosion inhibitor for 13% chromium tubing used in the completion of the Minaminagaoka hot, deep gas condensate wells. Although the wells do produce hydrocarbons, the hydrocarbon dew point is in the surface equipment while water starts to condense out at 4000 m (12,000 feet). It was, therefore, necessary to establish that the corrosion inhibitor would be effective in a high temperature water-only environment, or design the batch treatment such that an acceptable treatment life would be achieved since the wells were packed off and could not be treated continuously. The major results of this work are summarized as follows: Laboratory tests established that with one exception a hydrocarbon phase is necessary for good inhibition of all proposed commercial inhibitors. One inhibitor (C-8) results in excellent protection in the adsorption test, however, it could not be used in the field because of poor secondary properties. Tests conducted on pre-corroded specimens showed good performance in the constant contact test, while pre-corrosion was detrimental for half the inhibitors in the film persistency test. The inhibitors used for the field tests were one (A-1) which did not perform well in the laboratory, and one (B-6) which gave excellent results in both the adsorption and the constant contact test. The field results essentially confirmed the laboratory conclusions. The treatment life in the field was about three weeks, or substantially longer than generally anticipated from laboratory experience. This was rationalized with a model treating the tubing as a large gas chromatographic column in which compounds move by ever-repeated adsorption and desorption. The eluent in this case was condensed water ensuring that adsorption was fast and desorption was slow. This would result in a minimal migration rate of the inhibitor up the tubing.

REFERENCES
1) 2) 3) M. Kaseya, Journal of the Japanese Association for Petroleum Technology, 58, No.6, 524, ( i 993 ) J. Murali, 13 Cr Tests high against CO2 Corrosion, Oil and Gas Journal, July 23, 1984, p 66 R.lt. l-lausler, L.A. Goeller, R.H. Rosenwald, Contribution to the Mechanism of Hydrogen Sulfide Corrosion Inhibition, 3 rd European Symposiurn on Corrosion Inhibitors, Ferrara, Italy,

4) 5)

6)

7)

8)

9)

10) 11) 12)

13)

14th to 17th September 1970, p 399. A. Miyasaka, K. Denpo, H. Ogawa, Tetsu-to-Hagane, 74, No. 10, _ _ (1988) Y. Tomoe, M. Tezuka, The Influence of CO2 on the Corrosion Behavior of Oil Country Tubular Goods in Hot, High Density Brines, CORROSION/87, paper No. 50, (Houston, TX, NACE 1987) Y. Tomoe, H. Takeda, K Yamashita, Journal of the Japanese Association for Petroleum Technology, 47, No. 6, 63 (1982) K. Taehibana, T. Masuda, H. Shimizu, S. Miyazaki, M. Yokoi, A New Pressure- Balanced Outer Reference Electrode Made of Zicaloy Tube Sheath for Corrosion Studies of Metals in High Temperature Aqueous Solutions, and its Application, 4 th Asian-Pacific Corrosion Control Conference, Vol. 2 (Tokyo, Japan: JSCE, 1985), p 1275 L.K, Gatzke, R.H. Hausler, The COPRA Conelation - A Quantitative Assessment of Deep Hot Gas Well Corrosion and its Control, CORROSION/83, Anaheim, California, April 1983, paper No 48 N. Nakamura, M. Tezuka, Y. Tomoe; Proceedings of the Pacific Corrosion Conference held in November 1987 (Parkville, Victoria, Australia: Australasian Corrosion Association Inc., 1987), last page in session 1 Y. Tomoe, M. Tezuka, Proceedings of the Fall Meeting of Sekiyu-Gakkai, held October 1988 (Tokyo, Japan: Sekiyu-Gakkai, 1988, p, 21 R.N. Tuttle, T.W. Hambi Jr,, Materials Performance, 16, 10, p. 9 (1977) M . C . Place, Jr. Corrosion Control in Deep Sour Gas Production, published in H2S Corrosion in Oil and Gas Production: a compilation of Classic Papers, eds R.N Tuttle, R.D. Kane (Houston,TX: NACE, 1981), p. 829 R.H. Hausler, S.G. Weeks, Low Cost, Low Volume, Continuous Inhibition of Gas Production Tubulars; Materials Perlbnnance, June 1986, p.28 (i 986) NACE

Table 1 Typical Minaminagaoka Well Conditions

Depth Bottom-hole Temperature Bottom-hole Pressure Gas Composition COz

4800 m
180 C

15740 fi 356 OF 8250 psi

560 bar

6% 2 ppm 25,000 Nm3/KI 6500 Nm3/Ki 10 - 30 ppm

7.1 bbl Water/MMscf

HzS Gas/Water Ratio Gas/Oil Ratio

Chloride Content in Water

14.3 bbl Oil/N,~/lscf

Table 2
Chemical Composition API 13% Cr Steel for Test Coupons

Si

Mn

Chemical Corn >osition (wt%) P S Cr Ni

Mo

A!

Fe

13%Cr

0+2 ' 0.51

0.67 10.022

0.002

13.0 I 0.08 ] 0.02

0.005 I bal

Table 3 S u m m a r y of Inhibitor Evaluation Results from L a b o r a t o r y Tests (data are in % protection) Constant Contact Tests Inhibitors Company A
B Dispersive Prop. I~

-Film Persistency Tests

Ba re Surface

Product 1

Pre-corroded Surface 2) -~-- w/Xylene ~ -N-ea-t -:~- w/Xylene ~-- ~-N-~a-t 3 21 27 38 25 88 16 23

11

Bare Surface

Pre-corroded Surface 3) 36 61 41 73 -30 -26 -1 -23

na

20 99 98 98 99 99 98 96 97
. . . . . . .

-12 57 24 53 4 20 11 27
na

V C A
D

7 9 11 22 57 6 3 11
. . . . . . . . .

89 96 99 99 96 99 65 71

Legend:

~) dispersible O non-d~ispersible V poorly dispersible ~ Pre-corroded for 75 hrs at 180 ~:~C(356 F) ?~ Pre-corroded for 220 hrs at 160 C (320 F) 4~ Inhibitor was added "as received" dissolved in small amount of ethanol ~ Xylene was added after a certain time into the corrosion test (see texU

Figure 1 Typical Examples of API 13 % Cr Tubing Corrosion at Pin Ends

Figure 2

Model of Inhibitor Movement in Tubing String

Vi V w

v/
Vg

V .ta
ta + td

V i = velocity of inhibitor V i = velocity of water

ta =

time to adsorption after desorption

t o = time to desorption after adsorption

Figure 3

Ranking of Inhibitors over Various Test Procedures

100I"" 80~
|ts~d[

u,,ae

i 2

0 40
20 ~

l
t

'

~,
L ~

rII .....

a.

0 -20
/ /

-40 ~.... A1

B4

B5
. . . . . . . . . . .

B6
. . .

C7

C8

Inhibitor I
!. i. . . . . . .

A2

A3

D1
I

[] FPT-BM
. . . . . . . . . . .

~ FPT-PCM
. . . . . . . . . . . .

[] CCT-PCM

[] CCT-BM

Inhibition
Inhibitor

Efficiency (%) 13Cr

Description

Bare13Cr 3 (20)

Pre-Corroded

1
;.'.

...; ....
,7:...

. . ,-. . . "

.,-.

'-,~
. ..F.r"
.

7 ....................
;~:.-: '.: ..:.t } .: ,

..[-

I~q

.,...,,

v ....

~Nmnv:,

r-'J

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I

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.t
'
,

i
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-'.

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,
'

,
,~

v~O~ll'l,,....,i
. 1 .

~.

~
"

:\~:.',.'
-

,
" -.'I

,
,

A-1

O,-Solub,e
Water-Dispersible

4(7)

.-

11"t ' t'r ~'rl" ." ~ t T r H"~"il~ " ~ : ~ 1 " H r i ! 4

r .........

"'..; ...... ~ .....

I .......

' ...........

::~

A
B-6
--

Oil-Soluble
(most) Oil-Soluble

38(98)

11 ( 9 8 )

_..~__.._..J~

~....~J I1%

--]

O ~ o /

t/.:.
/0

~-=/ -f--....

Inhibitor ~ .=-

xy~ene
.. 0 m

4:--~---.. ,:: : P
-

"

4. U

:!Ill.. 2, : ~i~--- 7

-'rr:~-=--~

C-8

Water-Dispersible

88(99)

57(95)
of X y l e n e

_._200mg/l, =
~
t
I

FS %
1 0 0 ~
;
I I

1~ i~ r '' ':''~"'':''~''~ "~....

. '
~
I

( ) : After Addition

~ .
L L
4

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~ :
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:
,
I

.
,

,__~_~:._.~

'.'

_~_ZL.3
.]~-,2,~._..J
I__ I

4: .! 1-4 .-4 FS. 5 0 m p y

, , ,

!~t-~
~-rl-'r---t
; I ~ I

F S 5 m p y ~2..~.7_~_~
. . . .
I I

: }:.: F-i:- t-:

-I::T-~F-.,
-; :: ~:::~:~ ~ ;U,~i ~:{,,

!
i
,~i.:..:.ii;T, ........... B~Wtiti(Wt{(tWiii
LI-_L_2.L.LL_.~ ....

!
~

._
dL
L.. L T :

-,
-I--,-LL-CLL--.L-=
'-

iCooiing
J,I
~ " ~.l-

.... ~
~. t I

~
~
'

~'q

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'b~-~.-~ :'.~..".'-~ . . . . .

L.. . . . . . . . . . . . . . . .

: .... :~- ,

i)

~ , , !.1 j

~ i

r I

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,--t

T.~':lPI~

,-,-t

ooo/-~_.~.T.~
.... ;.L.t':e::,=--'

~.,

,_
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Yo;
e

--~I.--~:-~---~-iE-~=~ 11% :?..i....L..i:...i--i9 8 % ~

-.]

('1 - - ' - - , ' - - - ' - - " - " ' - - , ' - . - ' . . . ' - - - ' , v O-.O--O-..o-O--O--o-O-O

-o-~a Io-o--o--o--o

...............

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'- : - -- : c .!-- --'-- -.'.~.'!:[ - . ' 1

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:..,":i:::_~__~

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Figure4 Autoclave LPR Corrosion Tests Trends for Three

Pre-Corroded
lnhibitors in

on B a r e a n d P r e - C o r r o d e d

Test Specimens

80

E ~60.
v

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0

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Figure5

Field Test Results with InhibitorA-1 in W e l I X

80 E 6040 ~
0

20 ]
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Figure 6 Field T e s t Results of Inhibitor B-6 in Well Y

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100

1000

10000

Current Density (,u.A/cm2) Figure 7 Polarization Curves for 13% Cr Steel under Well Conditions in the Autoclave