CORROSION INHIBITION

Abstract

A method of inhibiting corrosion of duplex stainless steel by aqueous acidic solution, comprises carrying out a preliminary treatment which is passivation of the steel while exposing the steel to a first aqueous acidic solution containing at least one organic corrosion inhibitor able to adsorb to a steel surface, so as to deposit a passivating and corrosion inhibiting film on the steel surface; and thereafter during a second period of time exposing the steel to a second aqueous acidic solution different from the first aqueous acidic solution and also containing at least one organic corrosion inhibitor able to adsorb to a steel. The second aqueous acidic solution maintains the film on the steel surface, such that weight loss through corrosion in the second period of time is lower than the weight loss which would be observed with the same second aqueous acidic solution but without carrying out the preliminary treatment.

Claims

1. A method of inhibiting corrosion of duplex stainless steel by aqueous acidic solution, the method comprising: during a first period of time, carrying out a preliminary treatment which is passivation of the steel while exposing the steel to a first aqueous acidic solution containing at least one organic corrosion inhibitor able to adsorb to a steel surface, so as to deposit a passivating and corrosion inhibiting film on the steel surface; and thereafter during a second period of time exposing the steel to a second aqueous acidic solution different from the first aqueous acidic solution and also containing at least one organic corrosion inhibitor able to adsorb to a steel surface; wherein the second aqueous acidic solution is less effective than the first aqueous acidic solution for inhibiting corrosion of an uncorroded sample of the steel, and wherein the second aqueous acidic solution maintains the film on the steel surface, such that weight loss through corrosion in the second period of time is lower than the weight loss which would be observed with the same second aqueous acidic solution but without carrying out the preliminary treatment.

2. The method according to claim 1 wherein passivation is self-passivation of the steel in contact with the first aqueous acidic solution.

3. The method according to claim 1 wherein passivation includes application of anodic electrical potential to the steel.

4. The method according to claim 1 wherein the concentration of the at least one corrosion inhibitor able to adsorb to a steel surface is less in the second aqueous solution than in the first aqueous solution.

5. The method according to claim 4 wherein the concentration in the second aqueous solution is not more than half the concentration of the at least one corrosion inhibitor in the first aqueous solution.

6. The method according to claim 1 wherein at least one corrosion inhibitor able to adsorb to a steel surface is selected from compounds with aromatic groups and compounds with triple bonds.

7. The method according to claim 1 wherein the first aqueous solution contains at least one corrosion inhibitor which is polymerisable on the steel surface.

8. The method according to claim 1 wherein at least one of the first and second aqueous acidic solutions comprises water-insoluble hydrophobic liquid.

9. The method according to claim 8 wherein corrosion inhibitor and hydrophobic liquid are provided by at least one corrosion inhibitor which is able to adsorb to a steel surface and which is a water-insoluble hydrophobic liquid.

10. The method according to claim 1 wherein the first aqueous solution comprises at least one corrosion inhibitor able to adsorb to a steel surface and a separate water-insoluble hydrophobic oil.

11. The method according to claim 1 wherein the first period of time is not more than one hour and the second period of time is at least three times as long as the first period of time.

12. The method according to claim 1 wherein the duplex stainless steel is wellbore casing.

13. A method of protecting duplex stainless steel wellbore tubing during a matrix acidizing operation in which matrix acidizing aqueous acid containing corrosion inhibitor is pumped down coiled tubing into a reservoir formation, the method comprising subsequently pumping an aqueous acidic protective solution down the tubing, so as to flow back to the surface ahead of spent matrix acidizing aqueous acid flowing back from the reservoir formation, wherein the protective solution contains at least one organic corrosion inhibitor able to adsorb to a steel surface at a greater concentration than in the matrix acidizing acid solution.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0053] FIG. 1 is a graph showing weight-loss from samples of four types of steel plotted (on a linear scale) against concentration of hydrochloric acid, in tests without any pretreatment stage, as described in Example 1;

[0054] FIG. 2 is a graph showing weight loss from samples of three batches of duplex stainless steel plotted (on a linear scale) against concentration of hydrochloric acid, in tests without any pretreatment stage, as described in Example 3;

[0055] FIG. 3 is a corresponding graph to FIG. 2 showing weight loss when corrosion inhibitor was included in the acid;

[0056] FIG. 4 is a graph showing weight loss from samples of one batch of duplex stainless steel with differing corrosion inhibitor included in the acid plotted (on a linear scale) against concentration of hydrochloric acid, as described in Examples 3 and 4;

[0057] FIG. 5 is a graph showing weight loss from samples of one batch of duplex stainless steel, in a weight loss test after a pretreatment stage, plotted (on a linear scale) against concentration of hydrochloric acid, as described in Example 6;

[0058] FIG. 6 shows current densities recorded during a pretreatment stage with applied electrical potential, plotted (on a logarithmic scale) against time, as described in Example 8; and

[0059] FIG. 7 shows diagrammatically the use of coiled tubing in a matrix acidizing job, with a portion of the wellbore shown enlarged as FIG. 7a.

DETAILED DESCRIPTION AND EXAMPLES

[0060] As mentioned above, the present disclosure provides a method of protecting an article of duplex stainless steel using an initial pretreatment stage in which there is exposure to acid 4prior to a longer period (which may be use of the steel article) in which there is again exposure to acid. Organic corrosion inhibitor is present in both stages, but the pretreatment allows the concentration of corrosion inhibitor in the second stage to be less than would otherwise be required. The method may be employed in a wide variety of circumstances where duplex stainless steel is exposed to acid. More specific possibilities are duplex steel tubing exposed to acid. Duplex steel tubing may be wellbore casing.

[0061] The experimental examples below investigate the weight loss resulting from acidic corrosion, with and without corrosion inhibitor and then go on to examine weight loss when a two stage procedure is used.

[0062] The general procedure for measuring loss of weight from steel test pieces (referred to as coupons) was that coupons with surface area of 25-30 cm.sup.2 were glass bead blasted to ensure a clean surface, measured to determine their exact surface area, weighed and then exposed to 100 mL of an acidic solution at 78° C. for a period of three hours.

[0063] After this period of exposure to acid each test coupon was washed with demineralized water and allowed to dry. It was then weighed to determine the weight loss and a value for weight loss per unit area was calculated. The results in the following examples are each an average of two replicate tests.

[0064] In these examples, hydrochloric acid was used at various concentrations. The correspondence between percentage by weight and molarity is given in the following table:

TABLE-US-00002 Concentration (wt %) Molarity 5% 1.4M 10% 2.8M 14%   4M 17% 4.75M  20% 5.6M 28%   8M 37% 10.3M 

EXAMPLE 1 Experiments were carried out with test pieces (coupons) of the following steels:

[0065] HS80, a low carbon steel used to fabricate coiled tubing. [0066] N80, a medium carbon steel used to fabricate casing. [0067] 13Cr80, an alloy steel containing chromium without nickel, also used to fabricate casing. [0068] 22Cr125, a duplex alloy steel, also used to fabricate casing.

[0069] Elemental compositions of these steels are set out in the table below. Phosphorus and sulphur are not shown but are required to be at very low levels (below 0.1%) or entirely absent.

TABLE-US-00003 C N Fe Cr Ni Cu Mo Mn Si HS80 0.10-0.15 — 97.07-97.87 0.45-0.70 0.25 0.40 0 0.60-0.90 0.3-0.5 (max) (max) N80 0.24-0.33 — 97.33-98.26 0.04-0.16 0.012-0.028 0.010-0.019 0.018-0.05 1.19-1.66 0.22-0.39 13Cr80 0.15 — 83.11-86.11 11.5-14.5 0.16 0.01 0 1.0 1.00 22Cr125 0.14-0.20 0.08-0.20 64.55-69.73 21.0-23.0 4.5-6.5 —  2.5-3.5 1.0 1.0 (max) (max)

[0070] Weight loss tests, in acid without inhibitor, were carried out in accordance with the procedure above. The period of exposure to acid was three hours. The results obtained are plotted in FIG. 1 as a graph of weight loss against acid strength. It can be seen that for the HS80, N80 and 13Cr80 steels, the weight loss increased progressively with concentration of the acid. However, different behaviour was observed with 22Cr125. The weight loss values increase as the hydrochloric acid concentration increases from 0 to 14 wt % but a decreasing trend is observed at higher acid concentrations. This is due to self-passivation, i.e. passivation due to the formation of a stable oxide film under freely corroding conditions.

[0071] The results shown in FIG. 3 were influenced by consumption of acid (so-called acid spending) during the 3 hour test period. When the weight loss from test coupons was large, the consumption of acid reduced the acid concentration. Thus the higher values of weight loss recorded in FIG. 1 might have been even higher if the acid concentration had been maintained at constant strength. However, this does not affect the observation that the duplex steel showed self-passivation and falling corrosion rates when the acid concentration was 17 wt % or above.

EXAMPLE 2

[0072] When 22Cr125 steel was exposed to hydrochloric acid, a black layer formed on the metal surface. A sample of this black layer was obtained by repeatedly exposing a test coupon to acid until the coupon had been dissolved away. The acid-insoluble black solid residue was then separated by filtration (glass microfiber filter paper) and washed with fresh aliquots of 14 wt % acid.. After drying, the residue was analysed by X-ray Photoelectron Spectroscopy (XPS) and the major components were found to be molybdenum and oxygen, (Mo+O)=53 atomic %. Thus self passivation of duplex alloy steel can be attributed to formation of an insoluble protective layer of molybdenum oxides.

EXAMPLE 3

[0073] Weight loss tests were carried out on coupons of 22Cr125 steel from three manufacturing batches. These tests were carried out in acid without inhibitor and also in acid containing 0.2 wt % of a liquid corrosion inhibitor which contained which is 7% propargyl alcohol, 60% hydrocarbon oily phase and 33% methanol. The results are plotted in FIGS. 2 and 3. These show that this concentration of corrosion inhibitor gave some reduction in corrosion, and also show that the acid strength associated with peak corrosion varied from one manufacturing batch to another. This variation between batches was attributed to small differences in composition between manufacturing batches. Analysis of the steels showed molybdenum content varying between 2.82 and 3.05 wt %, and the Ni/Cr ratio varying between 0.213 and 0.248.

[0074] The surfaces of the coupons corroded in the weight loss tests were brushed to remove loose corrosion products and analysed for their elemental composition by X-ray fluorescence (XRF) spectrometry. Relative to XRF analyses of the uncorroded surface, several trends could be observed with increasing concentration of hydrochloric acid: [0075] No significant change in wt % Mn as acid concentration increased.. [0076] As acid concentration increased from 2.5 to 28 wt %,there was a 1-2 wt % increase in Fe and 2-3 wt % decrease in Cr. [0077] As acid concentration increased from 2.5 to 14 wt % there was a 2 wt % increase in Ni but Ni concentration declined as acid concentration increased further. [0078] Significant Mo enrichment at the surface when the coupons are exposed to 10-28 wt % HCl and, in particular, strong Mo enrichment on exposure to 28 wt % HCl+0.2 wt % A264.

[0079] It was observed that much of the molybdenum rich solid formed at the metal surfaces was loosely held but some was adhering securely to the surface. In view of this surfaces were analysed by XRF both before cleaning and after an ultrasonic cleaning. This led to a finding that in the absence of corrosion inhibitor, corrosion by acid of 5 to 14 wt % concentration caused preferential dissolution of the Mo-rich ferrite phase (indicated by changes in the Ni/Cr ratio). However, when acid concentration was in the range 17-28 wt %, a persistent molybdenum enrichment of the surface was observed (even after cleaning). This was attributed to formation of a more adherent molybdenum-rich film on the metal when exposed to hydrochloric acid in the concentration range 17-28 wt %.

[0080] Coupons of one batch of 22Cr125 were exposed to 14% hydrochloric acid for three hours in the presence of varying concentrations of the corrosion inhibitor. After this exposure the surfaces were surfaces were examined by XRF both before and after ultrasonic cleaning. Ni/Cr ratios were calculated. The observed values of Ni/Cr ratio and Mo content are given in the following table

TABLE-US-00004 Corrosion inhibitor Before cleaning After cleaning (wt %) Ni/Cr ratio Mo (%) Ni/Cr ratio Mo (%)   0% 0.36 3.46% 0.33 2.95% 0.2% 0.345 3.45% 0.33 3.02% 0.6% 0.29 3.35% 0.285 3.18% 1.0% 0.28 3.36% 0.28 3.18%

[0081] The difference between the values at 0.2 wt % inhibitor and 0.6 wt % inhibitor indicates that when the inhibitor was present in the higher concentration range of 0.6-1.0 wt % it promoted a more uniform dissolution of the two phases (lower Ni/Cr ratios, both before and after cleaning) and a higher retention of persistent molybdenum after cleaning (about 3.2% at the surface which is higher than 3.05% determined by elemental analysis of the steel in bulk)

[0082] In summary, XRF analyses of corroded weight loss coupons indicate the following: [0083] in the absence or presence of 0.2 wt % corrosion inhibitor, exposure to HCl concentrations in the range 17-28 wt % promotes formation of a persistent (adherent) molybdenum-rich passivating film. [0084] when the HCl concentration is below the 17-28 wt % range, e.g. 14 wt %, the presence of a higher concentration of the corrosion inhibitor (0.6-1.0 wt %) promotes formation of a persistent (adherent) molybdenum-rich passivating film.

EXAMPLE 4

[0085] The results of weight loss tests in Example 3 showed that corrosion was reduced by the inclusion of 0.2 wt % of the corrosion inhibitor although with the lower acid concentrations, the extent to which corrosion was reduced varied somewhat between the three steel batches. Weight loss tests on coupons from the three manufacturing batches were also carried out in acid containing 0.6 wt % of the liquid corrosion inhibitor. Results, which also include results from the previous example without corrosion inhibitor and with only 0.2 wt % corrosion inhibitor are set out in the following table. Results for one of the three batches of steel are also shown in FIG. 4.

TABLE-US-00005 Corrosion Weight loss Inhibitor. Batch A Batch B Batch C Acid (wt %) (wt %) lbs/ft.sup.2 gm/m.sup.2 lbs/ft.sup.2 gm/m.sup.2 lbs/ft.sup.2 gm/m.sup.2  5% none 0.35 1709 0.2 977 0.10 490  5% 0.2 0.33 1611 0.13 635 0.07 342  5% 0.6 0.18 879 0.04 1953  5% 1.0 0.02 98 10 none 0.88 4297 0.6 2930 0.4 2344 10 0.2 0.69 3369 0.24 1172 0.12 586 10 0.6 0.09 439 0.01 49 10 1.0 0.02 98 14 none 0.78 3808 0.8 3906 0.21 1025 14 0.2 0.28 1367 0.38 1855 0.6 2930 14 0.6 0.0 0 0.01 49 14 1.0 0.01 49 17% none 0.51 2490 0.5 2441 17 0.2 0.17 830 0.19 928 0.6 0.10 488 1.0% 0.01 49 20 none 0.39 1904 0.46 2246 0.2 0.12 586 0.07 342 0.6 0.08 391 20% 1.0% 0.04 195 28% none 0.44 2148 0.48 2344 0.5 2441 28% 0.2 0.02 977 0.01 49 0.03 146 28% 0.6 0.00 0 0.00 0 28% 1.0% 0.00 0

[0086] These results are consistent with the XRF results in the previous example, and show progressive reduction of corrosion with increasing concentrations of the corrosion inhibitor. Results with the other two batches of 22Cr125 steel also showed progressive reduction of corrosion with increasing concentrations of the corrosion inhibitor.

EXAMPLE 5

[0087] In this example a pretreatment step is carried out before a longer period in which steel is exposed to an acidic solution.

[0088] Weight loss tests were carried out by a modified procedure. In a first stage the coupons are exposed to a composition intended to deposit a protective film on the test coupons. This pretreatment stage, referred to in the drawings as the film-forming stage (FFS), lasted 1 hour after which the test coupon was washed with demineralized water, allowed to dry and weighed again. The weight loss test was then carried out as set out above, using an acidic solution for 3 hours. This second stage is referred to in the drawings as the film maintenance (FM) stage.

[0089] In the one hour pretreatment stage, coupons were exposed to acid without corrosion inhibitor. In the three hour second stage of the weight loss test the coupons were exposed to 14 wt % hydrochloric acid containing 0.2 wt % of the corrosion inhibitor. Results are set out in the following table:

TABLE-US-00006 Pretreatment stage. No corrosion inhibitor Acid concentration Weight loss (wt %) Second stage. lbs/ft.sup.2 gm/m.sup.2 NONE 14 wt % hydrochloric acid 0.214 1045  5% and 0.2 wt % inhibitor 0.17 830 10% 0.175 854 14% 0.075 366 20% 0.07 342 28% 0.08 391 37% 0.085 415

[0090] From the table above it can be seen that exposure to uninhibited ac id of 14% strength or more, followed by 14% acid containing inhibitor led to a weight loss of 0.075 lbs/ft.sup.2 during the subsequent three hours. This contrasts with a weight loss of three times as much when there was no pretreatment, thus indicating that self passivation with acid alone establishes a protective film which is then maintained in the second stage. It can also be seen that weaker or stronger acid in the pretreatment stage also established a protective film so that weight loss in the second stage was below the weight loss observed without the pretreatment.

EXAMPLE 6

[0091] In this example, as in the previous example, a one hour pretreatment step was again carried out before a three hour period in which steel was exposed to an acidic solution. The procedure was the same as in the previous example, except that corrosion inhibitor at a concentration of 1 wt % was included in the pretreatment. Results are given in the following table and also shown in FIG. 5.

TABLE-US-00007 Pretreatment stage with 1 wt % corrosion inhibitor Second stage with Acid concentration 0.2 wt % corrosion inhibitor Weight loss (wt %) Acid concentration (wt %) lbs/ft.sup.2 gm/m.sup.2 5% 5% 0.03 146 10% 0.07 342 14% 0.03 146 17% 0.06 293 20% 0.04 195 28% 0.01 49 14% 5% 0.01 49 10% 0.05 244 14% 0.02 98 17% 0.11 537 20% 0.07 342 28% 0.01 49 28% 5% 0.03 146 10% 0.02 98 14% 0.02 98 17% 0.05 244 20% 0.05 244 28% 0.01 49

[0092] The following table brings together results from this example and the one before.

TABLE-US-00008 Pretreatment stage with 1 wt % corrosion inhibitor Second stage with 0.2 wt % Inhibitor corrosion inhibitor Weight loss Acid (wt %) (wt %) Acid concentration (wt %) lbs/ft.sup.2 gm/m.sup.2 5% none 14% 0.17 830 5% 1% 14% 0.03 146 14% none 14% 0.75 3662 14% 1% 14% 0.02 98 28% none 14% 0.08 391 28% 1% 14% 0.02 98

[0093] The results show that when inhibitor at 1 wt % concentration is included in the pretreatment stage, the weight loss in the second stage is reduced even further. Thus it can be seen that the inhibitor in the pretreatment stage is contributing to formation of a protective film which persists into the second stage and is maintained, giving low weight loss in the second stage. Moreover it can be appreciated from the results in Example 4 that the inhibitor in the pretreatment stage will reduce weight loss during that stage.

EXAMPLE 7

[0094] A further experiment, with a different batch of 22Cr125 steel demonstrated the value of including corrosion inhibiitor to maintain the protective film established in the pretreatment stage.

[0095] The procedure was the same as in the previous example, except that there was variation in the concentration of corrosion inhibitor in both stages. The results are shown in the following table

TABLE-US-00009 Pretreatment stage Second stage Inhibitor Inhibitor Weight loss Acid (wt %) (wt %) Acid (wt %) (wt %) lbs/ft.sup.2 gm/m.sup.2 14% none 14% none 0.7 3418 14% none 14% 0.2 wt % 0.3 1465 14% 2% 14% 0.05 wt %  0.4 1953 14% 2% 14% 0.2 wt % 0.02 98

[0096] As can be seen from the last two lines of the table, corrosion inhibitor in the pretreatment stage was effective to provide a protective film for the second stage which was maintained by 0.2 wt % corrosion inhibitor but was not maintained when the corrosion inhibitor in the second stage was at a concentration of 0.05 wt %.

EXAMPLE 8

[0097] This example used a modified form of the procedure of examples 5 to 7 above. An anodic electrical potential was applied to the coupons during the pretreatment stage. The coupons were from the same batch of 22Cr125 steel as those used in Examples 5 and 6. The pretreatment was carried out for only 10 minutes and at room temperature of 21° C., in 14% hydrochloric acid with and without the corrosion inhibitor present at a concentration of 0.2 wt %. A counter electrode and a Ag/AgCl reference electrode were immersed in the acid solution and an electrical potential of +0.6volt, relative to the Ag/AgCl reference electrode, was applied to the coupons during pretreatment. The current flowing was measured and the current density (current per unit surface area) was calculated. The pretreatment was followed by a weight loss test, using 14% acid containing 0.2 wt % of the corrosion inhibitor composition mentioned in Example 3. The following table shows current density at the end of the pretreatment stage and the weight loss in the second stage. The current densities recorded during the pretreatments are shown in FIG. 6 which has a logarithmic vertical axis.

TABLE-US-00010 Pretreatment Weight loss 14 wt % Current density at 14 wt % acid, acid, 0.6 volt for 10 0.6 volt at end of 0.2 wt % inhibitor minutes pretreatment lb/ft.sup.2 gm/m.sup.2 none 0.214 1045 no inhibitor 6.6 mA 0.0621 303 0.2 wt % inhibitor 4.7 mA 0.0534 261

EXAMPLE 9

[0098] This example used a similar procedure to Example 6, but a different corrosion inhibitor was used. The corrosion inhibitor was a combination of cinnamonitrile (CN) and dodecyl pyridinium chloride (DPC). During the second stage, these materials were used in two ratios. Results are in the following table.

TABLE-US-00011 Second stage Pretreatment stage Second stage weight loss Acid CN DPM Acid CN DPM gm/ (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) lbs/ft.sup.2 m.sup.2 14% none none 14% 0.025% 0.095% 0.6 2930 14% 0.2% 0.095% 14% 0.025% 0.095% 0.15 732 14% none none 14% 0.037% 0.095% 0.3 1465 14% 0.2% 0.095% 14% 0.037% 0.095% 0.05 244

Illustration of Matrix Acidizing

[0099] The following description illustrates the implementation of the present concepts at the end of a matrix acidizing job. The concentrations of acid mentioned here serve as illustrative example only. It will be appreciated that the concentration of acid when carrying out matrix acidizing is chosen for the specific formation and wellbore.

[0100] FIG. 7 schematically illustrates positioning of coiled tubing for matrix acidizing. Flow from the wellbore is halted by closing valve(s) at the wellhead. Coiled tubing 12 is drawn off from a reel 14 and taken over a guide 16 (the so called gooseneck) which turns the tubing to descend vertically into a borehole as seen in FIG. 4. The tubing 12 is lowered into the well through well control equipment 18 as illustrated by FIG. 7 until the downhole end of the tubing reaches the perforations 22 which give access to the formation outside the well casing. The well control equipment 18 includes one or more valves able to prevent flow from the wellbore.

[0101] As shown by the enlarged view FIG. 7a, the casing 24 lines the wellbore and is surrounded by cement 26 in a conventional manner. The perforations 22 extend through the casing and cement into the surrounding geological formation. The casing 24 is made of 22Cr125 steel.

[0102] An inlet 20 to the coiled tubing is provided on the reel axis. In order to treat the formation, 14 wt % hydrochloric acid is pumped into the coiled tubing 12 through its axial inlet as diagrammatically indicated by arrow 32 and down the coiled tubing 12 in the direction of arrow 34 to the formation which is to be treated. During this main pumping stage the acid contains 0.2 wt % of the corrosion inhibitor composition mentioned in Example 3.

[0103] At the end of the main pumping stage several tubing volumes of 5 wt % hydrochloric acid containing 1 wt % of the corrosion inhibitor are pumped in. At the same time the well control equipment 18 is operated to allow a similar volume to flow from the well. Consequently this acid containing 2 wt % corrosion inhibitor begins to flow up the wellbore outside the coiled tubing 12 towards the wellhead. This is followed by spent acid flowing out of the formation and up the well bore outside the coiled tubing 12 as indicated by arrows 36 in FIG. 7. Thus the casing 24 above the perforations 22 receives a pretreatment by the 5 wt % acid containing 2 wt % corrosion inhibitor before it is contacted by the spent acid containing no more than 0.2 wt % of corrosion inhibitor.

[0104] By referring to Example 4 given above will be appreciated that the acid introduced after the main pumping stage could be at the higher concentration of 28% rather than only 5 wt %.

[0105] It will be appreciated that features referred to above or shown in individual examples may be used together in any combination as well as those which have been shown and described specifically. Accordingly, all such modifications are intended to be included within the scope of this disclosure.