cu») United States ‘US 20160010217 1 cz) Patent Application Publication co) Pub. No.: US 2016/0010217 A1 Hughes et al. (54) CORROSION INIIBITION (71) Applicant: SCHLUMBERGI (72) Inventors (21) Appl. No. (22). PCT Filed: (86) PCT No, §371 (6,0), (2) Date Related US. Application Data (60) Provisional application No. 61/772.477, filed on Ma. 4.2013. Weight loss (Ib/ft?) in 3 hours O14 0.08 0.06 0.04 0.02 Trevor Hughes, Cambridge (GB); :geny Barmatov, Cambridge (GB) Bruno Drochon, llouston, TX (US) Feb. 21, 2014 PCTTB2014/059164 215. 0.4 TECHNOLOGY and, TX (US) 0.2 (43) Pub. Date: Jan. 14, 2016 Publication Classification (2006.01) (2006.01), CEE 1104 2013.01); C25C 3000 (201301) ABSTRACT Corrosion of tel by agueous acidic solution when treating a wellbore sith acid is inhibited by a procedure in which the Steels initially exposed to fist aqueous solution containing ‘ne oF more comtsion inhibiting constituents which provide both corrsion inhibitor and hydrophobic liquid and deposita corms inhibiting lm on the stl surface and then exposed to an acidic sooond agueotis solution containing one oF more such corrosion inhibiting constituents at a lower concentra tion. During this socond peri, the lower concentration of corrosion inhibiting eonsitaents in the seond agusnus sol ‘ion maintains the film already established on the steel sur face. Weight loss through corrosion in the second stage is lower than the weight loss which otherwise would. be ‘observed, Overall there can he reduction of both weight loss ‘and consumption of corrosion inhibitor, N80 steel ~4— No first film forming stage ~a- Ci/S in first stage ~o- Cl/fa in first stage 0.3 04 0.5 Cl/4 concentration (wt%)Patent Application Publication Jan, 14, 2016 Sheet 1 of 9 US 2016/0010217 AI Weight loss (Ib/ft?) in 3 hours 2 3 z 8 2 3 © 8 © g 8 8 HS80 steel + No first stage 9 Preceded by 0.2wt% PA for 1 hour Fig 1 0 004 008 012 016 02 PA concentration (wt%) H80 stee!: no first film forming stage g + PA in second stage 2 ~o~ Cli in second stage 2 0.4 (sg @ 0.01 S : = i S 2 0.001 O.0001 fener mp Qe ey en a cs PA or Cli concentration (wt%)Patent Applicatiot ot oot Weight loss (Ibift?) in 3 hours 0.0001 in Publication —_Jan. 14, 2016 Sheet 2 of 9 US 2016/0010217 AI N80 stee! + Without first stage after 0.201% Cl for thour Fig 3 0 005 Of 015 O02 025 03 0.35 PA concentration (wt) 1 NBO steel g —+-Without fist stage 3 eater 0.200% CIM for thr = 04 5 & #001 2 3 Fig 4 —. FO pp 0 aor 0.02 003004) 0050.08 CVA concentration (wt)Patent Application Publication Jan, 14, 2016 Sheet 3 of 9 US 2016/0010217 AI N80 stee! e 0.10. —a-No first stage 3 chatter 0.5wt% CW/4 for thr = 0.08. ; a ~o~after twi% C4 for thr < = a 2 Fig 5 z s 3s = 0 04 02 03 o4 05 CWA concentration (wt%) N80 stee! 0.4 ~*~ No first film forming stage 3 ine 2 CIS in first stage 2° o- Cl/Sa in first stage | 0.08 a g 0.04 = Fig 6 2 0.02 a = “Se 0 01 02 03 04 05 Cil4 concentration (wt%)Patent Application Publication Jan. 14, 2016 Sheet 4 of 9 US 2016/0010217 AI 13C180 steel -¢ No first film forming stage g 2 « 0.2% CW in first stage s € on 3 —— B oot S Fig 7 a.001 | 0 005 01 015 02 025 08 PA concentration (wt%) 1 13Cr80 steel £ ~%* No first fim forming stage 2 1B 0.2% CIM in 15 min first stage a @ 0.2% CIM in 1 hour first stage € o4 a a 8 o 8 Boo ° Fig 8 3 = 0.001 02 03 04 05 CIM concentration (wi%)Patent Application Publication Jan, 14, 2016 Sheet 5 of 9 US 2016/0010217 AI -0.30 0.33 3 2 3 E 5 -0.36 | E : : £ € B 039 s : 6 9 9.42 0 60 120 180 240 «300-360, Time (min) Fig 9 1000 : = 100 = 2 £ g 8 g 10 5 6 | Fig 10 60 = 120-180-240 300360 Time (min)Patent Application Publication Jan, 14, 2016 Sheet 6 of 9 US 2016/0010217 AI 1000 100 & E —& 2 5 8 6S 8 © 60 120 180 240 300 360 420 Time (min) 0.2% cus 0.01% cus 034 ! 3 = 2.0.36 g 2 E 5 —& 2 2 = 038 = 8 & 5 & 2 8 o 0.40 0 60 120 180 240 Fig 12 Time (min)Patent Application Publication Jan, 14, 2016 Sheet 7 of 9 US 2016/0010217 AI w 0,003wt% CH/3 1 0.0065t% CUS 400 =e © 0.01m#% cus Ss ‘E 300 E é £200 s$ g E 100 6 0 0 60 120 180 Time (min) Fig 13 60 @ 0.01mt% CI/1, Spm © 0.011% Cl/1, 6000 rpm 2 0.04wt% CI/1, after 0.2% 4 hour, Sprm © 0.04wt% CW/4, after 0.2% 1 hour, 6000 rpm = i 7 a = a a 2 a ® a 3 —— 3 20, —E 5 é 0 60 120 180 240 300 Time (min) Fig 14Patent Application Publication Jan, 14, 2016 Sheet 8 of 9 US 2016/0010217 AI ‘Control © After 1 hour, 0.201% CW © After 1 hour, 0.5wt% CI 4 After 1 hour, twt% Cit 1.0 g 3 3 2 o 04 = s 8 g B 001 3 s Fig 15 | 0.001 0.001 0.01 0.1 1 10 CIM concentration (wt%) 104 @ Contra 2 A After 1 hour, 1wt% CIM 3 1 After 1 hour, 1.511% Ci 2 = 04 = 001 3 = Fig 16 0.004 - - L 0.001 0.04 o4 1 10 CIM concentration (wt%)Patent Application Publication Jan. 14, 2016 Sheet 9 of 9 ‘US 2016/0010217 AL 3 5 J SS SN ES 2 ES aS SS SS RRR y SS NA 5S SEE x Ss XE “SN ES x RR SS KES Ge RGR SES wy SS x. x wn LR SS XE BS, ES EV ys Sd 58: Fig 17US 2016/0010217 AI CORROSION INHIBITION BACKGROUND 10001] There are numerous circumstances where it is desig o protect steel fom corrosion by aeidie material (© which itis exposed. These include the protection of steel ‘exposed to an aqueous acide Tiguid such as when steel tubing Js used to convey a low of agueous liquid. 10002] "One industy which has a nea for protection of stool ‘against cormsion is il and gos exploration and production, Steel tubulars used in a borehole may be exposed to an acidic liguid mixture and so also may stce pipelines used to carry produced oil and 238. 10003] The technique of matrix acdising in which the pro- «ducing formation is treated with acid o stimulate production involves deliberate exposure of borehole steel to acid. This ‘operation maybe performed with coiled tobing whieh is run Jno a borehole and then used o convey aeidl don the Bore- hole othe formation. When the operation comes to an end, the steel casing in the borehole and the exterior ofthe coiled tubing can he exposed to so-called unspent aed owing back with formation Nui towards the surface, {0004} A conventional approsch to the protection of steel ‘against corrosion by’ an acide liguid is 10 contact the steel ith corrosion inhibitor. For example, when conveying an fic iguid through stel tubing. its conventional to add ‘corrosion inhibitor tthe How of liquid as mentioned in many ‘documents including for example U.S. Pat, Nos. 3.773.468, 4498,997 and 5.120.471, 10005] Organic inhibitors adsorb on the metal sures. Adsorbed inhibitor(s) may influence the rate of earrosion by ‘oneor more of several mechanisms: () by forming a physical barrier film which resiriets the diffsion of species ofom the metal surface, (i) by blocking anodic and/or cathodic reac- tion sites dined, (i) by interacting with corrosion reat Jnlermediates adsorbed on the surface and (iv) by influencing the electrical double layer that forms atthe metalsolution imerace [0006] Adsorption may be physi-sorption which is the result of electrostatic attractive foroes between inhibiting ‘organic ions or dipoles andthe electrically charged surface of the metal The surface charge ofthe metal isdue tothe electric field at the outer Helmholtz plane of the electrical double Jayer existing atthe metal/soluion interfeee [0007] Another possibilty is that adsorption is by chemi- somption, which takes place more slowly than electrostatic ‘adsorption and with a higher activation enerpy. Chemi-somp- tion invalves elect transfer frm clectronerich sites within the structure ofthe inhibitor molecules) to vacant low enerpy “orbitals inthe metal. Typically, such electron-rich sites within ‘an inhibitor molecule are heteroatoms with lone pair(s) of ‘electrons or are multiple bonds and aromatic rings so that ‘covalent bonds have electrons in r-orbitals, Because setiva- tion enemy is required, to bring about chemi-sorpton, the ‘extent of chemi-soeption and therefore the efficacy of corm ‘on inhibition may’ increase with temperature. It known that chemi-sorbed aceiylenie compounds ean react to fon polymeric inhibitor films. Such reaelion/polymerisation is Surface-catalysed. 10008] As illustrated by the US patents mentioned above, ‘corrosion inhibitors are frequently marketed as a mixture ‘containing materials which inhibit corrosion and other mate ‘nls which enbance inhibition, even though these other mate- Fials do not Tunetion as corrosion inhibitors (orate less efli- Jan. 14, 2016 cacious) if used alone. In some cases these mixtures are Proprietary and their exact composition is aot made publi [0009] A mixture which contains chemisorbing eoero- sion inhibitor may also include non-ionic or cationic surfae- ‘ants to assist deposition on steel, quaternary nitrogen com- pounds, amines (which wil protonate to quaterary nitrogen “under acidic conditions) and organie solvent. Some vilfeld ‘corrosion inhibitor prodets considered wo provide good inhi- bition performance st high temperatures are mixtures which make use of a syneristic combination of an amine and an acetylenic aleobol, [0010] Materials used in a corrosion inhibiting. mixture ‘may include materials which are considered to damage an cil reservoirby depositing onthe reservoir formation. Inparticw- lr surfactants in a corrosion inhibiting mixtare may assist ‘deposition of corrosion ihibitoron see, Yet be regarded as potentially reducing production from a reservoir. Conse- ‘quently there is conllict beoween a desire wo protect steel Tubing by means of inbibitor compositions and a desire to protet the reservoir fom exposure to such inhibitor compe 0011} ‘Te corrosion inhibiting effect of an inhibitor or ‘corrosion inhibiting mixture can be tested in various ways (One direet method of testing isto use a test piece whieh isa sample ofthe steel o be protected, customarily referred 10 as “coupon”. This coupon is exposed fora measured length of time t an dedie solution containing a known concentration ‘of corrosion inhibitor. The loss in weight of the coupon is measured and expressed as weight los pee unit surface area. The coupon is also examined for localised pitting and the extent of piting may be expressed asa numerical value: the so-called pitting index [0012] There are « number of ber ways to measure cor ‘sion by anaciie solution, These inchude neat polarization resistance measurement which was fist poposod by M Stera fand.A L. Geary in “Flectrochemical Polarization: A Taco- retical Analysis of the Shape of Polarization Curves” in J Electrochem. Soe. Vol 104 pp 56-63 (1957) and followed by Stem: "A Method For Determining Corrosion Rates From Linear Polarization Data in Corrosion Vol. 14, No. 9, 1958, pages 4401-444, In such ests piece ofthe see is used as an electrode and this electrode may be kept moving as a rotating dis, cylinder or eage to simulate flow ofthe corosive sol tion over the ste. [0013] When sie! is going tbe exposed to flow of an ‘acidic composition, itis normal practioeto est eoupons of the steel with various concentrations of corrosion inhibitor in samples of the acidic composition. A concentration of inhi torsihich produces an acceptably low weight loss and pitting index is deattied and this concentration of inhibitor i thea ‘maintained in the flow of acidic composition to which the steel is exposed. SUMMARY, [0014] This summary is provided to introduces selection of ‘cncepts that are further deseribed below, This smmary is ‘ot intended toe used as an ad in Himiting the seope ofthe subject matter claimed [015] We have now found that with certain corrosion inhibitors and corrosion inhibiting mixtures, iis not nee sary o maintain a uniform concentration in the acidic solu- tion thoughout the period of exposure, an that a better reslt wan be achieved by employing at least two stages with aUS 2016/0010217 AI ‘quantitative or qualitativechangeto the nibitoror inhibiting mixture and/or the concentration thereof between one stage ‘andthe next. [0016] Ina fistaspect ofthis disclosure method of inhib- Sting cmmosion of steel when exposed to aqueous aid in the ‘course of acide treatment of a Wellbore comprises exposing the ste! fora fist period of ime to frst aqueots soliton ‘containing atleast one corrosion inhibitor or corrosion inhib iting mixture which deposits « hydrophobic comrosion ihib- iting film on the stel surface, then ding a subsequent sec- ‘ond period of time exposing the steel to an acidic second solution containing at least one comrosion inhibitor oF inhibi tor mixture witha lower concentration of comroson inhibitor ‘or inhibiting mixture inthe second solution than inthe fist solution. 0017) By formulating the composition used in the first Solution such that it establishes a hydrophobic film whieh persists on the ste! surface, it becomes possible to use 2 ‘concentration of corosion inhibitor or iahibiting mixture in the acidic second soltion which is less than in the first soht- tion but which maintains the film of inhibitor on the sto! surface. In consequence the weight loss through corrosion ia the second period of time is lower than the weight loss which ‘would be observed with the same second solution ifthe treat- ‘ment withthe frst solution during the frst period of time had not taken place. [0018] "The overall los of weight from steel or the overall ‘consumption of corosion inhibiting compounds or both of these, can be less than the corrosion aking compounds) ate kop ata constant concentration throughout [0019] The erm “corrosion inhibitor” is used here wo refer tochemieal compounds which reduce the rate of corrosion of steel when aided! to a solution of a mineral acid, such as hydrochloric acid, with no other earosion inhibitor present. ach solution may contain a corrosion inhibiting mixture in ‘which at east one corrosion inhibitor is accompanied by one ‘or more iaterials which is not ise eoeeosion inhibitor but ‘eahaaces the action of the corrosion inhibitor. Corrosia inhibitors may be water soluble or example propangylaleo- hol) or water-insoluble (for example a long chain acetylenic ‘alcoho!). Organic materials which enhance the ation of & ‘corrosion inhibitor may be water-insoluble. More spectl- cally, a corrosion inhibiting mixture may contain a water: insoluble amine or cationic surfactant (both of which may be aromatic) ora water-insoluble liguid which may be a hydro- ‘carbon oil or a ester 10020] The frst aqueous solution may’ contain a corrosion Shbitor ands separate water-insoluble hydrophobic liquid whieh is not itself a corrosion inhibitor. Alternatively, the Junetion of such materials may be met by compound which js corrosion inhibitor and is a water-insoluble liquid. 10021] -Thecoerosion inhibitors inthe firstand second sl ions may be different compounds but both may have @ ‘molecular stracture with cavalent -bonds or with Tone pait ‘electrons, so that they can chem-sorb toa steel surface 10022] | Water-nsofuble materials in the first and second solutions may be suspended inthe aqucots solution, may be accompanied by emulsifier or surfactant, which may’ be eat onic or non-ionic sa as tobe preset in dispersed droplets oF sutfactant micelles, or may be aecompanied by an organic solvent which is water soluble, 10023] In some embodiments, a corrosion inhibiting mix- ture may contain nitrogen-free corrosion inhibitor and nitto- en-ffee water-insoluble hydrophobic liquid in Jan. 14, 2016 rcater than (possibly mone than three times the ‘of any cationie surfactants and organic amines. It may also be possible to avoid completely any cationic surfae- ‘anls ao organic amines. BRIEF DESCRIPTION OF THE DRAWINGS. [0024] FIG. 1 isa praph showing weight-loss from HS80 steel plotted (on a Tinea sele) agaist concentration of pro- pargyl alcohol, without any fist stage as refered 10 in Example 1 and also after first stage with propargyl alcohol as in Example 2 [002S] FIG. 2s a praph showing weight-loss fom HS80 steel without any first stage treatment plotted (on logarth- ‘ic scale) against concentrations of propargyl alcohol as ‘erred to in Example | and inhibitor CVI as tofered tin Example 4 [0026) FIG. 3 is @ graph showing weight-loss from N80 steel, with and without a frst stage of treatment with CVL plotted (on logarithmic scale) against concentration of pro- pargylalcobiol as refered to in Example 8: [0027] FIG. 4 is graph showing weight-loss from N8O steel, with and without a fist stage of treatment with CW, plotted (on a logarithmic seale) against concenteation of Jnhibitor CV as referred to in Example 9: (0028) FIG. 3 is @ graph showing weight-loss from N8O steel, with and without a frst stage of treatment with CUS plotted (on a logarithmic scale) against concentration of Jahibitor CV as referred to in Example 10; [0029} FIG. 6 is graph showing weight-loss from NSO steel, with and without fst stage of treatment, plotted (on logarithmic scale) against concentration of inhibitor CU as relerred o in Example 11; [0030) FIG. Tis graph showing weight-4ss from 13Cr80 steel, with and without a fist stage of treatment with CVI, plotted on a logarithmic sale) against concentration of pro pargyl alcohol as referred o in Example 12; [0031] FIG. 8is2 graph showing weight-loss fom 13Cr80 steel, with and without a first stage of treatment with CUI for 1S minutes oF I hour plotted (ona logarithmic sale) against ceoncentetion of inhibitor V1 a reerred to in Example 13; [0032] FIG. 9 shows the results of an electrochemical experiment described in Example | [0033] FIGS. 10and 11 show the results ofelectrochemical ‘experiments deserbed in Examples 16 and 17: [0034] FIG. 12 shows the results of an electrochemical experiment with a rotating eylinder electtode, using inhi tors CI/1, CU2 and C13, a describe in Example 18 [0035] FIG. 13 shows te results ofa similar experiment, as Leseribed ia Example 19: [0036] FIG. 14 shows the sults ofa further electrochemi cal experiment with rotating cylinder electrode, as ‘scribed ia Example 20: [0037] FIG. 15 is set of graphs (on logarithmic scales) showing weight-loss from S&Osteel, wth and without lage of treatment with CVI, plotted against concentration of inhiitor CU, at higher temperetureand pressure, as refered toin Example 21: [0038] FIG. 16 isa comesponding set of graphs (on loga- rithmic scales) showing weight-loss irom N80 steel, with and ‘without a first stage of treatment with CU, plotted wgainst cconcentetion of inhibitor CVI at higher temperatare and pressure as referred to in Example 22; and [0039] FIG. 17 shows diagrammatically the use of coiled tubing in a matrix aeidizing job.US 2016/0010217 AI DETAILED DESCRIPTION 10040) In some aspects ofthe method disclosed hers, tel to be protectad from corrosion is exposed, during ist Period of ime to first aqueous solution containing oe or tore eonosin inhibiting constituent selected from coro ‘oa inhibitors able to adsorb to ste! surlace, waleria- nes, cationic surfctants, non-ionic sfactants soluble hydrophobic ligeids such that te ern sion inibitng consitvents provide atleast omosin inhibi torand ydrophobic iid nd deposit a cormoion iaibiting film on the steel surfice and then exposed during a second period of time to an acidic second aguoons soltion conte fg one or more corrosion inhibiting consttuens also selected from corrosion inhibitors able to adsorb to a stel surface, water-soluble amines, cationic surictaats, aon- Jonienrfictant, ad Water esol hydrophobic liquids. {0041} “Thisfirstsotutionmay possibly be acidic. contains atleast one corosion inhibitor which chemi-sorbs othe stot Surface and contains hydophobic iid which deposits on the ste strfooe. Howser the cormsioniabtorand hyo phobic liquid may possibly be both provided by a corosion Inhibitor which s hydrophobic and liquid 10042] 1 the hydrophobic liguid isnot ite eorosion inhibitor it may be ai sich asa hydrocarbon olor water insoluble este sch ya ester ofan aid contsining at east Searbon atoms or of an alcohol containing at least 8 earbon ons. This hydrophobie guid may haves boiling tempera ture, at atmosphere presse, of atlas 100" C 10043], Thecomosion inhibitor may havea molecular stre- {ure wit at east one unsaturated group so that tas at east ‘one covalent a-bond enabling the inhibitor molecule 10 ‘homsorb othe steel surface The aibitor my then Be an ‘nsiturated compound which polymerises om tel surface. ‘Compounds which can polymerise on a tee surface inelode ‘imamaldeiyde and homologues (in which an oleic ‘double bond is conjugated with both an aroma ing and an aldchyde group, aalkens! phesones (in which the keto troup is conjugated with an aoasatie sing and an olefinic ‘ouble bond in the alkenyl group and acetylenic alcool the corsion inhibiting consents include separate hydrophobic liquid, the corovon inhibitor may he Water Soluble, for instance propangyaleohol. If the corosion inhibitors tselfhydrophobi,tmay bean aceslenic alcool ‘which Figo at atmespherc pressure and as a structure ‘contain at least 6 carbons atoms, al possibly from Gor 8 to T8 carbon atoms. When acetylenic eompounds form» ‘ormosion pret flo a ste surface, the wple bond ‘cables them to chemi-sorh, after which thy polymerise on the surface 10044} Another posibiity is thatthe eoeosion iaibitor may have sritire which incorporates fone pir electrons ‘on nitrogen, able to partipate in chemisorption, or may incomorate quatemary nite. 10045} Corrosion inhibit which chemi-soebs to the stel surface ay be ineladed in the ist solution a conceit ‘fat least 0.1 wi % and possibly inhigheramounts such up to 5 wes, 10 wi % or even 1S wi Ye ofan aqueots solution, ‘specially wen being taed a high temperstres. In some ‘embodiments the concentration may be not more than 3 6% fand possibly not more than | wt %. A hydrophobic ligsid hich i 01 sets eomosion ibibitor my be incl at 9 ‘concentration of at east 0.1,0.20¢0 51 Poup © 5 wt, 10 ‘weor 15 w(% although possibly notmore dan oF? WI% Jan. 14, 2016 [0046] This fist solution may contain surfactant, which may be water insoluble cationic surfsctant and the concer ‘ration of cationic surfactant (present) may Tie in a range fom O1 upto Lor 2Wt%, [0047] Exposure of the steel to the first solution may be carried out as part of process which is more than an ant corrosion treatment, The duration of exposure to the fist solution (Le. the fist time period) may be detennined by requirements of the overall process, lowever it may well be ‘thatthe ist period of time is at least S min and not Tonger than 90 min, During this first period of ime the first solution may be made to low over the sec, for exampleif the fist solution js being pumped through stel tubing, oF it may be allowed t0 ‘become stationary in contact with the steel for example by ‘pumping the solution into contact with the stl and then Stopping the pump fora time, so thatthe solution remains ia Stationary contact withthe ste! [048] After the first period of time, dhe ste! is exposed {during a second peri of time toa second solution which is ‘acid. This also contains at least one corrosion inhibiting ‘constituent, This may bea corrosion inhibitor that is able to adsorb onto steel. Iso, this corrosion inhi lower concentration then in the fist solution. We have fond thataflera protective flm hasbeen established during the frst period time, a much lower concentration of corrosion inhibi {or of ihibiting mixture can maintain the persistence of the protective flim. [0049] The corrosion inhibitor used during the second period of time may bea compound with lone pair electrons oF ‘teovalent a bond, so that it too ean chemi-sorb to see. Iimay >bea compound which is able to polymerise on ste! sch as nacetylenic alcohol sis possible in the first period a time, ‘hut it doesnot need to be the sme as the corrbson inhibitor cused during te fist period of time. For example, i'a water- insoluble hydrophobic corrosion iahibitor is used during the first period oftime, tis possible thatthe corrsion inhibitor in ‘his second solution will bea water soluble corrosion jah tor such as propa! aloo [0050] Concentration of eomosion inhibitor in the second solution may be very low, and it may possibly Tie in a range from D02 wt % up to 0.1 wt %, [0051] ‘The corrosion inhibitor or inhibiting constineents ‘sed in the second solution may be qualitatively the same as inthe fist solution, but ata lower concentration. However, it isalso possible that the composition use inthe second period is qualitatively diferent fom that in the frst period. The ‘ortosion inhibiting constituents included in the secoudaque- ‘ots solution may ormay not contain hydophobie igud. We ‘hae found that tis not necessary to include a hydrophobic ol in thie second aquedus solution, but there i lso no necessity {w exclude hydrophobic oll from second solution. Somewhat similarly, the sosond solution may contain some surfactant bt it does not need wo do so [0052] It will dus be appreciated thatthe second solution ‘may contain lower concentration of corrosion inhibiting ‘mixture than the fist solution and a lower conceateation of corrosion inhibitor than the first solution, However, its also possible thatthe first and second solutions contain similar ‘concentrations of eortsion inhibitor but the second solution tconiins a lower concentmtion of other corrosion iaibiting fcnstitvens than the fist solution, Such a situation eo arse if the frst solution contains & corrosion inhUS 2016/0010217 AI ‘ure in which there is a high proportion of hydrophobic oil ‘while the second solution eontsis corrosion inbitor with File oF no oil 10053] _In some embodiments, the concentration of eoero- soa inhibiting costinvents which are comsion inhibitors oF hydrophobic liquids present inthe second solutionmay be not ‘more than half or not more than ane quarter the concentration ‘of such materials in the first solution, 10053] Ifthe second solution isa matex aeidising solution, ‘ts envisaged that the second solution may not contain sure factant. The quantity of cation surfactant(s) in the second Solution may well Beles than wt % and possibly less than Ow %. 10055] The second solution may be brought into contact ith the steel directly alter the contact with the first solution Which took place during the fist period of time. Indeed, it may be convenient for the second solution 10 be used 10 displace the fist solution. However, itis possible that there will bean intermediate period as an interval between the frst second periods of time and during this interval the steel ‘could possibly be contacted by an acide solution which does not contain corrosion inhibitor. Plainly during soch an inter= val there would be nothing t© maintain the film whieh has been established on stool, but we have observed that film ‘established on stel does not disappear immediately even in the absence of any maintenance concentration of corrosion inhibitor. 10056) The concentration of acid in the second solution ‘may well he | molar or more, The first solution may be acidic and it may have an acid concentration of at east. molar oF ‘atleast I molae, The aid concentration in both solutions may Jieina range from 1 10 10 molar. The acid may be hydrochlo- rie, especially when used in subterranean reservoir teatment [0057] Because the present process calls for steel to be ‘exposed to Wo solutions in tuecession, the process likely to betsefil in acontext where the stecl is exposed a flaw of ic aqueous solution, This eoull for example arise when . to provide a pipeline for transport of an 10058) Specifically the invention may be utilised in the ‘context of operations where an acidic solution i passe into ‘wellbore through coiled tubing, as ogcurs in the context of matrix acidising when acid is delivered through coiled tubing to pass out of the wellbore into the surrounding geological ormation In this case the fist solution ean deposit a eorro- sion protecting film on the inside of the coiled tubing t0 protect it during the second period of time during which aeid Js pumped through the tubing to-go out into the formation ‘around the wellbore. In a development, the second period of time is followed by a third period of time during which @ solution with an increased concentration of corrosion inhibi tor of corrosion inhibiting mixture is pumped down through the coiled tubing so that this third solution will deposit a protective film onthe interior the fixed wellbore tubing and the exterior ofthe coiled tubing at the begining of the flow= back stage when these surfaces are contacted by aqueous solution, (which may still be acid) fowing back from the Tormation. 10059] The presence of a film on steet can be checked ‘experimentally using test pisces. After exposure ofa ste test piece toa solution containing one or more corrosion inhibit- {ng constituents the test piece is washed with demineralized allowed to dry. The film is then dissolved by Jan. 14, 2016 immersing the tes piece in an oranie Solvent andthe result ing solution is analysed for corrosion inhibiting materials. [0060] The formation ofa film andi efficacy wen main- tained by a low concentration af inhibitor will now be shown by the following experimental Examples. The frst group of experiments (Fxamples | to 12) were carried out observing ‘weight loss in a manner similar to conventional eorrsion tests, Sloe] eomosion test coupons with surface area of 25-30 cm? were glass bead blasted to ensue a clean surface, men- sired to determine their exaet surface area, weighed and then exposed to acidie solutions in a well sired corrosion cell containing 200 ml. fhid per test coupon. The temperature was held at 78° C.A numberof these tests involved exposure {0 a fist uid solution fora period of time, after which this solution was remaved and replaced with a second Mud sol- ‘ion fora longer time. Care was taken tha the second oid solution was not contaminated with races ofthe first solution. Fr this reason, when a coupon was removed from the frst solution twas washed off wi a small quantity afte second solution (andthe washings discarded) before being paced in the second solution in the corrosion cell [0061] The various stets sed in these tests were: [0062] 1880, a low carbon stew] used to fabricate coiled ‘obing [0063] NSO, « medium carbon steel used fo Lsbricate eas- ing. [0064] 13C+80,acommon metal alloy slso used to fabricate casing. All tree of these steels have yield strength of about 80 kp [0065] A number of these examples demonstrate that, in some embodiments, the to stage approach diselosed here can lead to 2 weight loss per unit area in the second stage ‘which i atleast 10 times less aftera ist stage pretreatment ‘han the weight lss per unit aren ifthe frst stage pretreatment is omilted. ln some instances the weight loss per unit arca is Tower by at least 20, 40 and even 100 times, Example 1 [0066] A frst series of tests was carried out exposing the Jow carbon HS80 steel to 4 molar hydrochloric acid eontain- ing propargy alcohol (2-propyn-1-l) in concentrations from (0.005-0.20 wt %. In each experiment there was exposure for ‘period of three hours, The resultsare shown i the following fable and are plotted as weight loss against propargy alcohol ‘concentraion in FIG. 1, with the points represented as dia- ‘monds, As will be mentioned ia Example 4 below, the same results are also ploted in FIG. 2, with weight loss on a logarithmic scale TABI Wao verti nas ropa al (wt) sume [067] Most of the above results are an average of two replicate tests tin the case of 0.20 w' % propargy!aleobl, ight replicate tests were caried out and indicate a meanUS 2016/0010217 AI value of 0.0041 Ib/R?, a population standard deviation, 0,0. (000386 Ibi? and a relative standard deviation, RSD-0 4% [0068] As can be seen from the numbers inthe table and from the graph in FIG. 1, the weight loss decreases very ‘considerably from 0.148 Th inthe presence of 0.005 wt % propars! alcohol 0.0041 Ib? inthe presence of 0.201% propargy! alcohol, By reading from FIG. 1 it would be seen that concentration of 0.02 wt (shown by a dashed vertical line) is the minimum propargyl_sleohol concentration rexuired to achieve a cumulative weight loss of wot more than (005 Thif® (24 gin) over throe hours exposure, which is ‘requently regarded as the maximum acceptable in the course ‘of a mttixaviizing job, Example 2 10069] Further tests were also caried out using the same apparatus and temperature and again using coupons of HSS0 steel. Coupons were exposed to aed in tWo exposure stapes The frst Stage was eared out using a fist fd solution which was 4 molar hydrochloric acid containing 0.20 wt % propargy!sleohol with an exposure time of one hour, aer Which weight loss was measured. In second stage, the cou- Pons were exposed to a sacond Mud solution which was 4 ‘molarhydroehlori acd containing various concentrations of propargy alco, for three hours [0070] The Weightloss observed inthe one hour first stage s¥a8 0.002720.0001 Ibs/R? (1340.5 mim). Weight losses ‘observed in the three hour second stage are given in the {ollowing table: TABLE 2 Trepwialcobolssassration Welton or ds tue inseous ge 0) et eu 10071] These results are plotted as open squares in FIG. 1 and, when compared with those from Example 1, show that the weight loss during the second stage in Example 2 is very similar t the weight loss with the same propargyl alcohol ‘concentration in Example 1. Thus this Example 2 shows tat 2 first stage of one hour with 2 higher concentration of prop- ‘rgyl alcohol has ao appreciable elfeet on corrosion in the second stage, Pxample 3 10072] Another series of tests was carried out, using the same procedure and the same HS80 grade tel 2s in Example 2, The first fluid solution was 4 molue hydrochloric acid ‘containing various corrosion inhibiting constituents. The ‘olution used forthe three hour second stage was 4 molar hydrochlorie acid containing propargy! aleohol ata eoncen- teaion of either 0,005 wt 9% oF 001 wt %. 10073] | Materils used in the fist stage (and abbrevi fortem) were 0074} Propargy aleohol PA) 10075] Dodecyl pyridinium chloride (DPC) which isa cat- fonie surfactant [0076] | Meth! oleate(MO) which ester, watersinsoluble ily Jan. 14, 2016 [0077] ‘The results are given inthe following table which repeals some figures from Example 2 to facilitate comparison TABLES —Ffintasge ic) Sonata (om Weslo PA Ws Meri yng?) ami? tamer owne 49 ig 86 A Sodus G02 $9 ame a2 1897 WWO2Ms Lend: GO 12 OHS SL 28 Molsoats om toms 17 Mo 2 O2M Fey 000-49 OMS 0004 Ma NO [0078] | Comparison of ros 6 with row 2 and row 7 with row 53 shows that ielusion of 0.1 9% DPC and 0.1 wt % MO in the first staze fd leads to litle or no reduction of corrosion inthe second stage. However, comparison of rows 10 and 12 ‘with ows Gand 2 and likewise comparison of ows 1] and 13 with rows 7 and 3 shows that changing from propargyl aleo- bol whichis water solubleto I-octyn-3-0l or 4-ethyl -oetyn- 3a, both of which are water insoluble, leads toa dramatic ‘ednetion inthe amount of eorrsion during the second stage provid that 0. wt % DPC and 0.1 wt % MO are incladed in the fist stage. This demonsrates that the low concentration of propargy! alcohol present during the second stage is main- faining a corrosion protecting film established in the first stage. Example ¢ [0079] series of tests was eatied our using similar pro- ‘cadure to Example | above. The steel was ain HS 80. The steel coupons were exposed fr three hours to 4 molar ydro- chlorie acid containing various concentrations of a corrosion ‘hibiting mixture denoted CVI which contained 7% propat- aylaleobol, 6% hydrocarbon oily phase and 33% methatl. [0080] The results are shown in the following table and are ploted as weight oss against CVI concentration in FIG. 2, ‘which the weight loss isons logarithmic scale, thedata points {rom this Example ae plotted as open cirles and the data points from Example 1 are plotted as diamonds TABLE 4 —Selossnertise oun cure) se won?US 2016/0010217 AI ‘TABLE 4-continaed Wont oe erie oa crise) a anne a1 Tans » 0081} By ating from tecurveploted ia FIG. 2,itwould be soon thats concentration of abou 0.01 st % (howe by a las veal lines themiaimun concentration ofthe CU mixtre required to achiewe a ctmatve weight loss of not tore tan 0.08 To (244 gs?) over de hours exposure Example S 10082] A series of tests was caried out sing the procedure ‘of Examples 2 and 3, The stel was again HS 80. The fist stage was | hour and the frst uid contained the corrosion rasof02 wt % ‘in hydrochloric aid at concentrations of 14M, 4M. and 88M. As in Example 3 thelud forthe thee hour second stage was 4 molar hydrochloric acid containing propargyl aleohol ata concentration of either 0.008 w1% or 0.01 wt %. [0083] | The results are given in the following table: ae een Se et i a owns seh iinet eee ey ie © nome 44 omms oan 10084) Thefirst1wo ws thetable aboveare copied from Example 1 and show the extent of corrosion if the second stage takes place without the first stage, The subsequeat ows numbered 3 onwards, where there was frst stage using the ‘CII inhibitor composition, show considerable reduction in, the extent of corrosion i the second stage. This demonstrates that a corrosion inhibiting flm established with the CUI mixture inthe first stage is being maintained as an effective ‘corrosion preventing film by 2 naluced concentration of pro- pargyl alcoho in the second stage [0085] When the data points forthe 3 hour second stage ia rows 310 14 are plotted in FIG. 2, they appear inthe region shown by a shaded box, with very low weight loss at low Inhibitor concentration, [0086] | Thecouponsfornws'3t0 14ofthesbovetablewere Inspected visually and seen tobe fre oralmost fee of piting. Jan. 14, 2016 Example 6 [0087] Furher tests were cartied out generally as in Example 5, using 0.2 W% CWI in4 molar hydroehlorie acid ina first stage of one hou, followed by an extended second sage of six hours, using a second Aid containing three concentrations of propargyl alcohol in 4 molar hydrochloric acid [0088] ‘The weightloss observed inthe one hous fis stage was 0.0012 Ibs!" (5.9 n/m") as in Example 5. The follow- ing table shows weight losses observed this six hour second stage and for eomparison also repeats data from Pxample S where the seeond stage was three hours, TABLE 6 Prpuplalaiol Daron Weigh em ung concesraies dig sondage __ sofa econbenge(nt*s) hour) tet? an? 3 hs ‘ bab bs [089] 1: can be seen that the corosion protecting films ‘established in the first stage were sustained! for six hours. ‘Moreover the data forthe second stage solutions containing 0.005 and 0.01 w1 % propargyl aleobol indicate that the ‘Weightloss during the second three hours ofthe second stage ‘was only 00002-0,0008 Thif compared to 0,001-0.0012 Tv? ding the fist three hours. That suggests that tho iahi- bition efficiency of the film increases with time during the second stage. Example 7 [0090] series oftests was carried out using the procedure ‘of Example Te frst stagewas 1 hour and sid used or this fit stage contained 0.2 wt % of the corrosion inhibiting mixture denoted CV in 4 molar hydrochloric acd, giving a eight loss of 0.0012 Ibs/f® (5.9 gmim*) as in Example 5 ‘The Mid forthe three hour second stage was 4 mole Hydeo- ehlori acid containing CUI at several concentrations, [0091] Te results are given in the following table which repeats some results from Example 4 asa comparison: TABLET, sna tte a Wit ow Betase( Inet? ania? [0092] Once again the inital treatment with CV ted to 0 second stage in which a low concentration of CU gave ow corrosion ng te film formed i te fist stage.US 2016/0010217 AI 10093] In his example the steel test piewes were NAO ste! As in Example 1, steel coupons were exposed for 3 hours (ith no preceding frst stage) to 4 molar hydrochloric acid ‘containing various concentrations of propargyl alcohol These results are shown graphically in FIG. 3 withthe data points shown as ciamonds [0094] Asin Example 5, steel coupons were exposed in a first stage of 1 hour toa Mud contaiing 0.2 wt % CWI in 4 molar hydrochloric acid with weight loss of 0.0014 Iyit= (68 gmvim), This was followed by a second stage in which they were exposed to various concentrations of propargyl alcohol in 4 molar hydrochloric acd. These results are also shown in FIG. 3 withthe data points shownas squares, Itean bbescen thatthe frst stage treatment reduced weight loss inthe second stage to ess than anything achieved without de pre= 10095] The results are also given inthe following table TABLES, Pepanot Wei oe Finteage (tour) ack we 6) thet? gi Ping 3 Oi So 58a 3 Os hone one d Oi oon tone Example 9 10096] _Inthisexample te steel test pieces were again NSO stcel. As in Example 4, stool coupons were exposed for 3 hours (ith no preceding first stage) to 4 molar hydrochloric i containing various concentrations of the CU inhibitor mixture. These results are plotted in FIG. 4 with the points shown as diamonds, 10097] Following the procedure in Example 7, tee] ou- pons were also exposed toa sid containing 02 wt % CUI in ‘molar iydrochlarie acid fora first sfage of one hour, with 3 ‘weight loss of 0.0014 Ib (6.8 gmim), followed by a sco ‘ond stage in which they were exposed to various concent tions of CU in 4 molar hydrochloric acid, These results are plted in FIG. 4 withthe data points shown as squares Itean readily be seen thatthe weight loss daring this second stage is very Tow, 10098] ‘The results are also given inthe following table TABLED Secon ou Cul Went ee Finraage(t bow) (0006) _ he? gm —_Phing Jan. 14, 2016 TABLE 9-continved Sess sags ates (Uw) (018) og Pig 5 Os enor7 88 te Example 10 [099] The procedure of the preceding Example 9 was repeated using N8O steel with a proprietary corrosion inhi {oF componition denoted C4 which contained « haloalky] heteropolyeyeic sat, an aromatic aldehyde, a quaternary ‘ammonium compound, an oxyalkylated fatty eid and formic acid [0100] In the first stage, the N8O steel coupons were ‘exposed 10a Muid containing ether 0.5 w1% or L wt % CL in molar hydrochloric aid for one hour, with a weight loss ‘f0.001 Ibs! (4.9 grin’) in both cases. This was Followed by a second stage in which the coupons were exposed 10 Various concentrations of C14 in 4 molar hydrochloric acid for three hours. Comparative experiments Were carried aut with no fst tape [0101] The results are given in the following table and also shown in FIG. 5. Ascan be seen, cormsion protection achiev- able using 0.4 oF 0-8 wt % Ci throughout was matched oF bettered by using 0.5 wt % CW4 initially and then dropping the concentration of C14 100.08 38, TABLE 10 Sees sage tum oe ee Tne Ton ae ba Ooo Rs sone hs ome 78 sone aM BCL 003 0.0008 29 ae fine Samos 39 sone ht” Samos 39 Sone ba Ooo RN ane rarvecsia ht Gages 39 sone ba Ooo 34 ae Example 11 [0102] ‘The procedure of preceding Fxamples was repeated ‘using N80 steo! with two diferent compositions i the 1 hon first stage followed by sing the CU4 comosion inhibitor composition at several concenteations in the 3 hour second stage. [0103] One composition, designated CUS, used in the fst stage provided [0104] naphihy! methyl quinolinium chloride (NMQCH ‘which isa water-soluble corrosion inhibitor, 0.34 wt% [0105] methyl oleate (MO), which is an oily ester, 0.1 wt 96, andUS 2016/0010217 AI soluble non-ioie surfactant (ND), 0 wt [0106] water % ind molarhydrochlorc acid {0107} Weight ss during this fst stage was 0.0099 bs? (39 gaa") Nophihy! metiyl quinoinium corde aque ternary ite compound and therefore is organic cal jon, btit doesnot frm suefatan cells in Wate {0108} An altemative composition ws in the fit stage ‘vas designated CVS, Teontainedthe same materialsas CUS burt kdtionalyiacioded eingamoniteile,s0 as 1 provide (065 wt einnamonitie in the 4 molar hydeochlee acid ‘Weight lost during the fet stage was 0.0015 Iba? (7.5 ni {0109} Asshowaby the results sctoutin the fllowingtable and which ae also pote in FIG, 6, buh ofthe ist stage trestments made it possible to get low ight Joss in the 3 hour second sage with only 0.2 wt 9% of CUA Including ‘nttarmonitile which has benzene ring conjugated to ‘lefnie group anda earbon-nitrogentriple bond inproved the ‘elfctvence ofthe corrosion protecting fils deposited inthe 1 howe ist stage and persisting during the second stage ADI 1 ond ms 14 waist oe Finraage(t bo) __(@t94)_h? gm? Ping 10110] Some sxditonal tests were carried out replacing ‘Clin the second stage with ether dhe nuphihyl methyl ‘quinolinium chloride lone ora combination of methyl oleate ‘and water insoluble non-ionic surfeetant (Without naphthyl meth quinolinium chloride). These tess were carried out ironed CU/Sa combination of material, ‘inching cinnamonitile, in the first stage and also without & fist stage, The results are show in the following table: ARI p12 Send age Oh) It ioe Tinw NWO oy bits NOeDswe%NI 91S 18 ceusainancnicl Hi mneNWOG! fon te [0111] These results show thatthe combination of NMQCI, rmethy! oleate, surfactant and cinnamonitrle can create a per sistent film which ean be maintained by NMQCTalone, butt js destabilise by the combination of methyl oleate and non- ‘onie surfactant Jan. 14, 2016 Example 12 [0112] In this example the ste! test pieves were 13Cr80 steel. Asin Examples | and8, steel coupons were exposes for hours (with no preceding firs stage} to 4 molarhydrochlorie ‘cid containing various concentrations of propangy aleobl [0113] Asin FxampleSstcel coupons werealso exposedin 41 hour frst stage toa fil containing 002 wt CLT ind ‘molar hydrocsloric acid with a weight loss of 0.0012 Ibi? (5 gmim* followed by a second stage in which they were ‘exposed to various concentrations of propargyl alcohol in 4 ‘molar hydrochloric acid. [0114] Theresuttsare plotted graphically sven in the following table: FIG. Tandalso TABLE 13 Second gs Propane int tuge (bos) oot? ane? [0118] Asean be seen from the table and FIG. 7, with no Tit stage, 0.2 w1% PA in the second stage did inhibit coero- sion considerably, but increasing to 0.3 wt % PA had very Tile addtional benefit. By contrat after the frst stage with 02,W1% CVI to deposit il, amuch lowerconcentration of A in the second stage gave a much superior result Example 13, [0116] In this example the steel test pieces were again T3C¥80 stel. As in Example 4, steet coupons were exposed {or3 hours (with no preceding first stage) to 4 molar hydeo- chloric acid containing various concentrations of the C11 inhibitor mixture. Asin Example 7, stel coupons were also exposed 1 first uid containing 0.02 wt % CVT in 4 molar Ihydrochlorie acid followed by a second stage in which they were exposed to various concentrations of CUT in 4 molar Ihydroehlori acid, The frst stage lsted for either 15 minutes ‘orone hour. The second sage was three hours in each ease [0117] The results are plotted graphically in FIG. 8 and are given in the following table: TABLE 14 Tas ‘Sonleine ha Tine _Weintoss CU _Wistlos in) the? _ ymin? mt)? _PiingUS 2016/0010217 AI TABLE 14-continued Tass ‘Sscnd ge Gh Tine Waist ee CU _ Wi oe (ei) ew) teas ws - Sor face 3) tone Chin fii ik 186 toe Gor Ook "seme fim tase 38 hoe Example 14 10118] _ series of tess were caried out exposing HS80 ste coupons to 4 molar bydroclorie acid containing 02 wt Seproparasslohol asin xample I, forperiodsof minut, Sainte, 30 minutes an 180 inst. 10119} Thepresense of prosctive films on thecoupons was then examined After exposure, each coupon was washed in deionised water to rimove anyexoess ack. Aer drying, the ‘upon was thea immersed in 50 mt dichloromethane and the inhibitor films prodits wore exacted int the ganic solvent duriog 30 mints immersion and agitation ina ‘ltrsoni ath, The dichlorometbane sation ws he ras Ferre to 100m Petr dishand3 mi of an aqueous soltion ‘of? moll KBr wa add. The dichloromethane and water ‘components wer allowed to completly evaporate ina fune hod overnight and subsequently na oven (140° C.) over night yielding a solid mixture of inhibitor film products and Potasiom bromide. This reside was then” completely Femoved from the dish, remixed and ground and its neared. spccrum was collected relative wo # pure KBr background Prepared bythe same dying and grinding proces nar od specs Were detennined hy Fourie tnnsfonm iia red spectroscopy [0120] Ic vas observed that a relatively sharp baad in the inf ed specran of peoparg leohol due to C—O stetch- ing (1028-1026 em) was replaced by abroad band (1300- 8$0em")intheeoupondichoromethane extracts This band provides a diagnose of the polymeric film as its peak area Incrensessystmatcally with exporore time Thisexpermeat emoustated a procedite for exabishing whether il is presentona wate coupon. However the weight los expec ‘ents in ample 2above show hat th pratetve im which Tormd in the presence of 0.2 wt % proparyl alcohol did aot provide persistent consion proteton afer the concent tion of propor alcohol was redoced. Blectrochemical Measures [0121] Examples below made use of electrochemical mea- ‘urements carried out ina corrosion call which was a 0.8 Ktre lass container surrounded by a thermostatic waterjacket 10 ‘maintain temperature at 78 C, The containers pls fp Was fined with a number a items projecting into the figuid in the ‘container. These were a Metrohm Ag/AgCl (3M KCI refer- ‘ence electrode, a graphite counter eloctede, a thermometer and a gas two-way purge tbe. A fine Luggin capillary was placed close to the working electrode to minimize ohmic resistance eflects, Magnetic stirring was nsed to provide an ‘even temperature distribution and good mixing during each ‘experiment Jan. 14, 2016 [0122] Each test was carried out using a static working electrode which consisted of 1-4 mm thick, 16mm diameter, Tat, circular HS80 steel disk with exposed surface area of 10 cm, No crevice eormsion was observed under the Teflon corring used to monnt the disk in a holder. The liquid in the container was de-aerated by bubbling nitrogen through it for 30 minutes prior to each test and throughout the experiment. [0123] An Autolah PGSTAT 302N Poteatiostat combined ‘with Autolab MUX Multi¢ multiplexer was used to apply potential fo the electrodes and record current ow. [0124] Lineae polarization resistance (LPR) measurements ‘were carried out ina potential ange #5 mV’ withrespecttothe ‘pen circuit potential (OCP) and a a sean rate of 0.2 mV The polarization resistance (R) was determined from the slopeof the potential versus the curren lie. The Tafel slopes, 2, and. were determined from potentiodynarnic polar tion tests. The polarization resistance was used to caleulate the cormsion eutrent sing the Stem-Geary equation Web M88 UK, [0128] The corrosion curent was converted to weight loss using Faraday’s Ia. For corrosion of see, a corrosion eur- rent of | miA em” approximates toa eoerosion rate of 11.6 ‘mim per year, Example 15 10126] ‘The working electrode was @ | em* disc of HS8O steel Initially thie was exposed thecorosioneell to4 molar hnydrochlorie acid which didnot contain any corrosion inhibi tor. During an initial 40 min period of equilibration, the open circuit potential reached a near-steady state value around 0.375 volt. This is shown by curve 20 in FIG. 9 in whieh ‘pen ciruit potential is indicated on the left-hand axis. After 40 minutes, a indicated by dashed line 21, some CI/ eoero- sion inhibiting mixture was then introduced to give a concen- ‘tation of.2 wt %, The open circuit potential rose rapidly to 0.315 volt as shown by the continuation 22 of eurve 20, [0127] During the exposure o this concentration of C11, the eomasion mite, indicated by curve 26 fell progressively. This was attributed o the formation ofan inhibitor film onthe steel test piece. [0128] ‘The 4 molar hydrochloric acid was replaced! four {imes at intervals indicated by dashed lines 23, reducing the ‘concentration of corrosion inhibitor each time as set out inthe following table: Tigesltine nie) Cli emceatin (70) [0129] As shown by slope 24, these four successive ‘decreases in the concentration of C1 ia the aed led to only ‘smal eduction in open eircuit potential and did not result in ‘an increase inthe instantaneous eorosion rate. On the con- trary the corrosion ate docreaso rom 17 to 14 mmiye. Thus, ‘team he seen that the efficacy of the corrosion inhibiting fn established by 0.2 wt % CWI was maintained fora total of 4 hours by successively lower concentrations of CVUS 2016/0010217 AI 10 Example 16 10130] _Ineach experiment the working electrode was adise ‘ofTIS80stel ut in the previous example. This tee electrode ‘a ist exposed to 4 molar hydrochloric acid containing 0.2 \WO% CV inhibitor mixture fora period of 110 mia. LPR was rasured at intervals and used to caleulte the corrosion rate which is plotted in FIG. 10. er 110 min, indicated in FIG. 10 by a dotted vertical linc, the acd in the corrosion cell was replaced with fesh 4 molar hydrochloric aeid. LPR measure- ments were continved and used to calculate corrosion rates. [O11] Tn one experiment this replacemeat acid contained ro corrosion inhibitor and the corrosion rate rose progres- sively as shown by curve 30 in FIG. 8, In the second experi- mnt the replacement acid contained C1/I corrosion inhibitor ‘ata concentration of 0.0036 wt % and the corrosion rate ‘calculated from LPR measurements is shown by curve 32. Ib ‘can be seen thatthe corrosion rate rose somewhat, but the reached an almost constant plateau value, Tis was alow rate ‘of about 90 mavyr equivalent toa weight loss of 05 Ib jn 3 hours, eventhough the concentration of CUI was much lower than the 0.2 wt % used initially. 10132] "In the third experiment the replacement acid eon- tained 0.01 wt 9% ofthe CU/T mixture. The corrosion rate is shown by curve 34 and it can be sce thatthe corrosion rate ‘continued to fall. This shows that a corrosion inhibiting film ‘established with 0.2 wt9%6CI/1 was notonly maintained bythe lower concentration of 0.01 wt % but became more efi Ex 10133]. ‘The procedure was similar to that of the previous ‘example, LPR measurements al itervuls wer te comrsion rates which are plated in FIG. ‘erent corrosion inhibitor mixtures Were used, including the ‘CHI mixture refered to above. These mixtures contained: 0134] CH: 7% proparyyl aleobol, 60% hydrocarbon (oily phase), 339% methanol [0135] C12: 7.5% propanyy alcoho, 3% 4-ethyl 1-08- tyn-3-ol, 15% ally] quaternary ammonium surfactants, 6% non-ionic surfictan, 7.5% hydrocarbon, 61% water- soluble organic solvents 0136] CU: 11% s-lkenyIphenones. 24% haloalkyl hheteropoiyeyeic salt, 27% formie acid, 10% non-ionic strfaclanl, balance i a mixture of Water and Water- soluble onganie solvents 10137] For each experiment there was an inital equiibea- tion in 4 molar hydrochloric acid without aay eortosion Inhibitor. After 30 minutes one of the corrosion inhibitor mixtures was added to give a concentration of 0.2 w % fara further 80 min after which the aeid was replaced with more 4 molar hydrochloric acid containing the same corrosion ‘inhibitor ata concentration of 0.01 wt %. 10138] The coreosion rates during exposure 10 0.2 wt % CU, 02 4% CVI and 0.2% CLS were similar. When the acid was replaced to reduce the inhibitor concentration 10 0.01 wt %, the corrosion rates with CU2 and CV3 rose but reached a steady plateau value Which is @ corosion rte of ‘about 90 mmyear, With CVI the result was even better bocatse the eortsion rate continued ofall ople 17 Example 18 10139] Plectrochemical measurements akin to those in Example 15 were carried out using rotating eylinderelec- Jan. 14, 2016 £6000 rpm, the Wal shear stress was 5OKPa whichis similarto the wall shear stress in coed tubing with a 1 inch (2.5 em) internal diameter when thero is a Mow rate of 1 bblimin ‘through i Calculation of Reynolds number showed that ow adjacent fo the rotating electrode was turbulent when the clectmode was rotating a this spec. [0140] Experiments were carried out using the CVS eorro- sion iahiitor mixture mentioned above, In a fst stage of slightly over 1 hour, the electrode was exposed to 4 molar hydrochloric seid at 78° C. containing 0.2 wt % CV while rotating at 6000 rpm. As shown in FIG. 12, the open cireit potential rose From ~0.375 volt o =0.35 vot during this time. Ina throe hour second stage the cylinder was exposed to the sume strength acid containing 0.01 wt % CU. Open circuit potential and linear polarisation resistance (LPR) measure- ‘ienls Were contined andthe measurements of LPR were ‘ed to calculate the rate of eormsion. As ean he sen at the suht hand portion of FIG. 12 the erosion rate remained low, showing once again that «comrosion protecting film is estab- Tished inthe fist stage and remains effective in the second stage. Example 19 [0141] The procedure of the previous example was fol- lowed. Inthe second stage the aeid contained C1/3 at different concentrations in three separate experiments. The results rom the second stage are shown in FIG, 13 [ts apparent that the concentration of 0.0065 wt % was suficient to maintain the protective film established inthe fist tage, but the lower concentration of 0.003 wr % was not suficient to do tis Example 20 [0142] Further experiments were carried out using 9 rotat= ing eylinder electrode made of HS8O steel in procedures similar to those of Example 18. The CVI corrosion inhibitor ‘ientioned above as used, [0143] Ina fist stage of 1 hour, the electrode was exposed {0 4 molar hydrochlori acid at 78° C. containing 0.2 wt % CUI while rotating at GOO rpm so that flow adjacent the clectmde vas turbulent as mentioned in Example 18, la a thre hour second ste the cylinder was exposed to the same strength acid containing 0.01 wt % CU while rotating at the sme speed of 6000 rpm. Linear polarisation resistance (LPR) ‘measurements were mde and Used to calculate the rate of corrosion, which is shown graphically in FIG. 14, Another experiment was similar, except thatthe electrode was rotated at only 5 rom. Calculation of Reynolds number showed that How adjacent wo the electrode was laminae. The res shown i FIC. 14 ln comparative experiments the ‘sing 0.2 wi % CVI was omitted, [0144] As ean be seen from FIG. 14, with both linear and ‘turbulent few, corrosion protecting film is established inthe firststageand remains effectivein thesecondstage, so that the cortosion rate observed in the second stage is low. Example 21 [0145] Experiments similar to those in Examples 5 and 7 "Were caried out at a temperature of 121° C. and pressure of 3000 psi (20.7 MPa) representing conditions which might be encountered dawahole in a wellbore.US 2016/0010217 AI W [0146] | Coupons of HS 80 steel were exposed t0 15 wt % (4.1 Molar) hydrochloric acid foran initial period of onehour uring this initial period theacid contained 0.2,0.5 or l wi% (CU inhibitor Then ina second stage at the same temperature ‘and pressure the coupons were exposed 10 15 wt % hydeo= lorie acid containing various concentrations of U1 iii tor. Weight loss was determined aftr three hours, Results are showin in FIG. 15 as plots of weight loss in the second stage against theconcentrationof CI. inhibitor inthe second stage. ‘This Figure also shows weight-loss in control experiments ia which inital period was omitted. As ean be seen from FIG. 418, the formation of an intial film in the first stage led to 8 ‘considerable reduction in corrosion in the second stage com= pared to the contro), with CVI concentrations of 0.1 Wt Yeand below in the second stage. 10147] Thus the protective effect ofan inital period with a relatively ised concentration of corrosion inhibitor, prior. Jonger exposure ata lower concentration of corrosion inhibi- tor was observed at the higher temperature used ia these ‘experiments. As shown by these results it was beneficial t0 tise a greater concentration of CVI daring the initial period than was used inthe initial period in Examples Sand 7 where the temperature was 80° C Example 22 [0148] The procedure of Example 21 was repeated using ‘coupons of NSO steel. The reslls are plotted in FIG. 16 ‘Concentrations of we % and 1.5 Wt % C11 were used inthe inal period. As can be seen from FIG, 16, the formation of ‘an intial film in the first stage again led to a considerable reduction in corrosion in the second stage compared to the ‘control, with CV conceatrations of. wi %and below inthe second stage, [0149] FIG. 17 showscoited ubinginuse formate acidiz~ ing. Coiled tubing 54 is inserted into a wellbore so a8 to ‘extend dawn the well tothe vicinity of perforations 58 which ‘extend through the well casing into the surrounding rock formation [0150] Tusiation 1. The coiled wbing $4 made of BS80 steel, Tt has length of 3000 metres and internal diameter of 3 ‘em, so that thas an internal volume of 13.34Bbl (2121 litres) 44 molar hydrochloric acid containing 02 wt % CUI is pumped nto the upper end ofthe bing, a8 shown by arow 52 ata rate of 1 bh/minute for 15 minutes, Thus the 15 bbl (2385 lites) of acd which is pumped in s slightly more tha the tubing volume, Ths is followed by the main acid stage ia whieh acid is pumped down the tubing $4 as indieated by amr §6 to flow out through the perforations S8 into the surrounding formation. Inthis stage the acids 4 molarhydro- cchloric containing 0.01 vt % propangy! alcohol, and itis pumps! at 5 bbUminute (795 hitesmin) foe 3 hours [0151] The amounts of materials and the weight loss (pre- ict from igure in Example 5 above and therefore assum- Jing temperature of 80°C.) are calculated as [0152] First stage: 1 bbYimin (159 Limin) of 4M HCL containing 0.2 w!% CV, pump time 1S min [0153] Total volume-15 bbl (2385 L) which is >1 tubing volume [0154] Total inhibitor (at 2 /L)H4.77 ka, [0155] First stage weight loss-0.0006 Ibis? 2.9 Jan. 14, 2016 [0186] Main acid sage: 5 bbl/nin (795 Linn) of 4M HCl containing 0.01 61% propansyalcobel, pump tine Shours [0157] Totat vokume900 bb! (143100 L) which is >67 tubing volumes [0188] Total propargyaleobol at.) g/L)-14:301 ka 10159] _ Main acid stage weight loss-0.0011 Ib (5.4 anim") [0160] Tota inhibitor"4.77 ka Ct and 14.3 Ke of pro parzy aleohol [0161] Total weight Hoss-0.0017 Ibi (8.3 pin) [0162] _By contrastaconventional approsch woul use over 28 Keg of inhibitor by adding 0.02 wt % CVI oF 0.02 wt % ‘ropargyl alcohol to all the aed in expectation of a weight foss of no more than 005 Ib? (248 givin’) Thus the eon- ventional approach uses more inhibitor to keep the weight Jossdown a value which is many mes higher than that low Joss of weight achieved by the nwo stage approach above. lustration 2 (0163] ‘The coiled tubing $4 is made of HS80 steel. I has Jeng of 6000 meres and intemal diameter of 3. em, so thai thas an intemal volume of 26.68 bbl (4242 lies). [0164] The frst stage is eased out using 4 molar hydro- chilore cid containing 0.2 wt % C11 pumped at 0 bb per ‘minute (79.5 Tites/min) for 1 hour. The main aeid stage is then carried ont using 4 molar acid containing 0.008 wt % ropargyl alate! pumped at3 bbl minnte (477 htresmin for hours. The amotinis of materials and the weight loss (pre- iced from fignres in Example 5 above) are caleulated as [0165] First stage: 05 bblimin (79.5 Limin) of 4M HCI containing 02 % C11, pump tine 1 howe 10166] Total volume30 bbl (4770 L) which is tubing volume [167] Total inhibitor (t 2 w/1.)-9.53 kw {0168} First stage weight loss-0.0011 It? [0169] Main acid stage: 3 bbv'min (477 Limin) of 4M HCI containing 0.008 wt % propargyl ale, pump time 6 hours 10170] Total volume-1080 bb (171720 L) which is 240 tubing volumes [0171] Tota propargy alcohol (at 0.05 g/L)-8.38 ka [0172] Main stage weight loss-0.0014 Init (68 ‘gmin) [0173]. Total Weight Loss-0.0025 tbf* (12.2 em/m*) [0174] By contast in a conventional spproach pumping 3 ‘blimin 477 L/min) of 4 HCl containing 002-003 wt % CVI 0F 0.02-0.08 wt % propargylaleabol for 6 hours [0173] Total volume=1080 bbI (171720 litres which is 40 tubing volumes) 0176] Total CV! or propargy! alcohol (at 02-03 g/L) 3432-5148 ka, 0177] “Total Weight Loss-0.05 h/f? (244 grea?) [0178] ‘The conventional approech ses much more inhi {or to keep weight loss dawn to a value which is 20 times higher than that achieved by the two stage apprcach, [0179] Using the conventional approach, @ C/I concentra tion of 20.06 wt % (total quantity 102.96 kg) would be required to reduce the weigh loss 10 0.01 Ib (49 gm) ‘The latter weight loss is sill 4 times higher than the weight Jos achieved by the two stage approach,US 2016/0010217 AI usteation 3, [0180] _Itis assumed that there will be exposure to tempera- tures of 120° C. The eoiled tubing $4is made of HS80 stet. has length of 4877 metres (16,000 ft) and intemal diameter ‘of 3.5 em (1.4 inch), so that it has an internal volume of 30.5, bbl (4850 lites). One bing volume of 15 wi % hydrochloric acid containing 1.061% CVI is pumped into the upper end of the tubing as the tubing is inserted into a borehole. Ia the subsequent main acid stage the acid pumped down the tubing S4 is 15 wt Sehydrochlorie acid coatsining 0.05 Wt%CV/1. It Js pumpedat 2 bb\iminute(79S lies min) for bowrs so that 530 bb (57240 L) is purpes [0181] "The amounts of materials and the weight loss (pre- dicted ftom FIG. 15) are calelated as [182] First sage: [0183] Volume=30.5 bbl (4850 L) which is 1 tubing voliime [0184] C11 inhibitor (a 10 gL)-48.5 Ka [0185] _ Weightloss approx. 0.001 1b [186] Main acid ste: [0187] Total volume~360 bbl (57240 L) [0188] CVI inhibitor (at 05 w)-28.5 Ke [0189] Weight loss 0.011 Io [0190] Overall toal CV! inbibito-77 Ka CUL [0191] Overall weightloss 0.012 Ibi 10192] By contrast, using a constant 0.15 wt % CU/L while pumping S60bbI (572401) would use 86 Kyof CU iaibitor ‘and total weight loss would be inferior, at around 0.04 Th? 10193] If the steel was N8O, the frst stage could alsa be carried out with 1 61% C/1 in one tbing volume of seid and (0.05 wt 9% CVI in the acid of the main siage so that the total ‘amount of ihibitor would be 77 Kg and the weight Joss ‘would be about 0.013 Ih. By contrast using atleast 0.5 wt ‘% CVI while pumping 360 bb (57240 L) would use 286 Ke, ‘of CI inhibitor and weight loss would be the same. 0104) Ac the end of the main pumping stage spent acid from the formation is conventionally allowed to flow back to the surface, Howing up the annus 60 around the coiled ‘wbing. This exposes the well easing andthe exterior of the ‘oiled tubing to acid, In a Tater development of the proce ‘dure illustrated above, several tubing volumes of acid con- twining 0.2 wi % CU) are pumped in atthe end of the main stage. This acid which contains the higher concentration of ‘inhibitor leads the flow back tothe surface, thus contacting the exterior ofthe coiled tubing and the wel easing with @ ‘concentration of hibitormixture which i quantitatively and ‘qualitatively able w create a persistent film al thebeginningot the flow back period. 10195] Ic is also possible that matvix acidizing could be ‘carried out without using coiled tubing. aad pumping the acid directly into the wellbore tubing. In this event the fist stage ‘would place a protective film ot the wellbore tubing before the main sage in whieh aeid is pumped through the wellbore to flow out into the formation, Materials aad concentrations might be simile 1 those in the illustrations above although ‘witha larger volume i the fist stage to match the volume of the wellbore. 10196] Iewillbeappreciated thatthe example embodiments described in detail above can be modified and varied within the scope of the concepts which they exemplify. Features referred to above or show in individual embodiments above may be used together in any combination as well as those Which have been shown and described specially. Aecord- Jan. 14, 2016 12 ingly, all such modifications are intended to be included ‘within the scopeof this disclosure as defined in the following claims, 1. A method of inhibiting corrosion of ste! by aqueous acidic solution whea the stel is exposed to aqueous ci solution inthe course of ace treatment ofa wellbore the srthod comprising during a frst period of time, carrying out a preliminary treatment by exposing the steel to first aqueous sot tion containing one or more corrosion inhibiting con- stituents selected from corrosion inhibitors abl wo adsorb toa see surface, and ‘water-insoluble hydrophobic materials stich thatthe corrosion inhibiting constituents provide both cortosion inhibitor and hydrophobi liquid and deposit a cor- ‘sion inhibiting film on the stel surface; and thereafter during « second period of time exposing the steel to aa acidic sevond aqueous solution also containing one or more corrosion inhibiting constituents selected from corrosion inhibitors abl wo adsorb toa see surfiee, and ‘water-insoluble hydrophobic materials ‘wherein the concentration of said corrosion inhibiting con- stituents in the second aqueous solution sess than inthe first aqueous solution but maintains the film onthe steel surface, such that weightloss through corrosion inthe second period of time is lower than the weight loss ‘which would be observed withthe same acide second ‘aqueous solution but without carrying out the prelimi- nary treatment 2. A method according to claim 1 wherein the second aqueous solution contains eorosion inhibitor able to adsor toa steel surface and the concentration of said cortsion inhibitor inthe second aqueous solution isles than in the frst aqueous solution, '3.A method according to claim 1 wherein the fist aqueous solution contains at least one corrosion inhibitor which is polymerisable on the steel surface 4.\ method according claim 3 wherein the corrosion inhibitor which is polymerisable on the stel surfooe is an acetylenic aleobol, '. A mothod according to claim 1 wherein the water-in- soluble hydrophobic materials are selected from water-in- soluble amines, cationic surfectants and. water-insoluble lydrophobie liquids. 6.A method according 1 claim 1 whereincorosioninhibi- {or and hydrophobic liquid inthe fist aqueous solution are provided by'at least one eotrosion inhibitor which is able to adsorb toa steel surfice and which isa water-insoluble hydeo- phobic liu 7A method according 1 claim 1 wherein the coerosion inhibiting continents in the fist aqueous solution comprise atleastoneeoerosion inhibitorable to adsorb toa steel surface ‘anda separate wate isoluble hydrophobic ol 8. A method according to claim 7 wherein the oil is a hydrocarbon or an ester 9. \ method according to claim 1 wherein the eotrosion| ‘nhibiting constituents in the first aqueous solution comprise: 2 10 25 wt % of al least one corrosion inhibitor able to chemisorb oa steel surface, 010 109% of waterinsoluble eationie surfctant, and 15 to 98 wt % of uncharged water-insoluble hydrophobic “il.US 2016/0010217 AI 1B 10..A method acconting o claim 1 wherein the eoncentra- tion of said corosion inhibiting constitvents i the ist aque= ‘us solution is atleast 0.1 st % but not more than 10 wt % 11. A meshod according o claim I wherein the concentns- tion of said corrosion inhibiting constituents in the second ‘aqueous solution is not more than half the concentration of said corrosion inhibiting constituents in the first aqueous solution 12. A method according to claim 1 wherein the firs period ‘of time isnot more than one bour and the second period of time is at least trae times as long asthe frst period of time. 13..A method aocording to claim 1 wherein the fist and second agusous solutions are both pumped through steel ‘coiled tubing inserted into a wellbore. 14, A method according to claim 13 further comprising ‘during a thir period of time after the second period of time pumping theovgh the coiled tubing thre aqueous solution also containing one or more corrosion inhibiting constituents selected from ‘corrosion inkibitos able o adsorb toa steel surface, and ‘water-insoluble hydrophobic materials wherein the eoneealraton of said corrosion inbibiting con- stituents inthe third aqueous solution is more than the eon- ‘centration of said corrosion inhibiting constinients in the second aquectis solution, 18, A method of inhibiting eormosion of steel by aqueous jie solution when the stel is exposed to aqueous acidic Solution inthe course of acidic treatment of a wellbore, the method comprising ‘during a frst period of time, carrying out a preliminary ‘treatment by exposing the steel to a fist agucous sok tion containing one or more corosion inhibiting con stituents selected from the rou consisting of cartosion inhibitors able to adsorb fo a steel surface, water soluble amines, cation surfactants, non-ionic surfac= ‘ants, and water-insoluble hydrophobic liquids such that the corrosion inbbting constituents provide t last ‘acomosion inhibitorand a hydrophobic liquid and deposit ‘corrosion inhibiting film on the steel surface; and thereafter ‘during a second period of time exposing the steel to an ‘acidic second agus solution containing one or more corrosion inhibiting constituents selected from the said group: ‘wherein the second agueous solution contains a. concent tion of corrosion inhibitor or comosion inhibiting con- Jan. 14, 2016 stirvents from the said group whichis es than inthe rst ‘aqueous solution but maintains the film on the steel surface, such that the weightloss through eosrsion in the sovond period of time is lower than the weight loss ‘which would be observed withthe same acide second ‘aqueous solution but without carrying out the preimi- nary treatment 16, A method aecoring to claim 18 wherein the second agucous acidic solution contains coerosion inhibitor able to Aadsorh fo a ste! surface and the concentration of said corro- ‘ion inbibitorin the second aquedus solution Jes than inthe fist aqueous solotion 17.A method according o claim 18 wherein the corrosion inhibiting constituents in the preliminary treatment comprise atleastonecomrsion inhibitor able to adsorb taste! surface ‘and also atleast one water insoluble cationic surfactant. 18, A method acconding o claim 18 wherein the corrosion ‘nhibitors) able to adsorb toa stel surface are selected from ‘compounds with aromatic groups and compounds with tiple bonds 19. A method according 1 claim 1 wherein the concentra ‘ion of said cortosion inhibiting constitents inthe first aque ‘us solution is atleast O.1 wt Y% but aot more than 10 wt 20. A methox! aevording to claim 18 wherein the concen ‘ration of said corrosion inhibiting constituents in the second aqueous solution is not more than haf the eoneentration of said corrosion inhibiting constituents in the frst aqueous solution, 21. 4 method according to claim 18 wherein the first and second aqueous solutions are both pumped through stool coiled tubing inserted into a wellbore. 22. A method aeconding 10 claim 21 further comprising during a third peri of time subsequent to the second period ‘of time pumping through the coiled tubing a thitd aqueous acidic solution also containing ane ar mare corrosion iaib- iting constituents selected from the group consisting of cor sion inhibitors able to adsorb to a steel surface, water insoluble amines, cationic surfactants, non-ionie surfactants, and water-insoluble hydrophobic liquids wherein the concen- ‘ration of said corrosion inhibiting constituents i the third ‘aquoous solution is more than the concentration of said cor ‘rosin inhibiting constituents nthe second aqueous solution