STIMULATION Corrosion Inhibitors for Acid Jobs ‘Wayne W. Frenier Donald G. Hill Raymond J. Jasinski Tulsa, Oklahoma, USA 10] 5 6 | 0.05| o_O of ea 14020284 Temperature crease of coutsion wih temperature over a Sour period. The acid 20 % yeochlore {301 IHCI and the meter swan. An aecoprable level of protection 0.05 It rete ine Coreion soll round us—fom rsy nis pied pos ond pans. The cli is ‘exception. Casing and tubing strings corrode continuously and require protec- fen hraughut hele ofa well pareve hyragen suid or cen diode is produced. Special care is required when concentrated hydrochloric [HCl] or hy- drofluoric [HF] acid is pumped down a wel to clean up wellbore damage, create fissures deep into the formation or simply remove seale from casing and tubing.’ Without s well tubular ial chemicals that inhibit corrosion, these acids would lars. This article reports advances by chemists at Dowell Nombege Tulsa, Oklahoma, USA concerning how inhibition works. It also describes recently developed inhibitors that improve protection in hot wells Corrosion inhibitors are an indispensable part of the fluid mix pumped downhole when a well is acidized. To prevent acid damaging well tubulars, inhibitors must function for at least two hours during a frac- turing job and up to 24 hours when acid is being used to clean wellbore damage or scale, They must not fal at high temperature when corrosion intensifies tlef). And they must inhibit corrosion effectively for the variety of steels used to complete wells, These range from the commonly used! APL sade J55 (which has a 55,000-pounds-pox square-inch [ps] minimum yield strength) to the increasingly popular stainless steels con= taining chrome. Finding improved inhibitors that satisfy these constraints provides a ‘ough challenge tothe research chemist Comox ona set surface. At anodic sts, positively charged iron ions, Fe" Jeave the ‘neta surface and score tons in solution Elec: trans meanihile low tous the see 0 cathot sies where they reduce hydrogen ions Inthe acid forming yarogen gas Downhole Corrosion: Mechanism and Inhibition The process of corrosion has been well understood for years.* When acid meets steel, the two materials act like a battery The steel surface provides both the battery's cathode and anode, while the acid consti- tutes the electrolyte (below, lei. Parts of the steel surface, acting as anodes, lose positive iron ions to the acid and generate free elec- ‘ons inthe ste! Fe Fett + 20" Other parts of the steel surface, acting as cathodes, use these electrons to reduce pos itive hydrogen ions in the acid to form hydrogen gas: 2Ht 26 > H, “Together these reactions create small cur- rents that loop between the steel and the acid, AS long as curtent flows, anodic sites steadily lose iron and corrode, But if either the anodic or cathodic reactions are imped ed, current stops flowing and corrasion Thanks 10 Bock and his keri Texas ABM Une Calle Station, oa USA kr ther work ‘relpsonerc easements The wo wae funded Dy Dowel Schlamberer |For an veri of aiding techni: ‘Wins 8, Gly ane Schecter RS: Aciing Finda Dal, fess USA: Sect rou Ene cd AIME, 1979 2. Foran inet study covosion chery an "ype of coon an eionos {ss Basie A fed NACE Base Caoron Cause, Howson Tos, USA:Navonl Asacatono Como ‘Se Engine, 1970. 15slows. This is precisely what inhibition seeks to achieve (right). Until the 1960s, the most common Inhibitors were arsenic salts, which interfere with corrosion by impeding the cathodic reaction, Since then, these salts have been replaced by organic materials that adhere to steel surfaces and form protective films that prevent both anodic and cathodic reactions. ‘Today, wo or more organic inhibiting compounds are typically mixed with an “aid or “intensifier” to enhance inhibition ‘at high temperature, a solvent, and various additives to facilitate pumping the mixture downhole. Additives include demulsifiers, ‘wetting agents and iron and silicate stabiliz~ rs that reduce shale swelling, The most important group af organic inhibitors, acetylenic alcohols, was the focus of research at Dowell Schlumberger. To simplify the number of reactions that ‘occur in a typical inhibition system, researchers investigated a system with just three components: steel, hydrochloric acid and an acetylenic alcohol inhibitor, octynol ICH, -(CH,],-CH(OH}-C=CH1, Using a Variety of surface analytical techniques, they Unraveled the chemical and physical pro- ‘cesses by which acetylenic alcohols inhibit corrosion. The techniques also guided them in synthesizing new organic compounds Fim Interlerence pattern sampe that give Improved protection, Thetr first, ‘goal was understanding the chemistry of a polymer thought to form when octynol, acid ‘and stee! meet, possibly aiding inhibition. Probing Polymer Chemistry “Their main tool for understanding chemistry ‘was infrared spectroscopy. With this tech nique, researchers note the frequencies of incident inirared radiation that the sample absorbs and thereby identity molecular groupings in a sample, such as CH, OF, and the carbon-carbon triple bond, C=C. ‘Michelson Interferometer Fed mittor = Moving micor ‘Beam soltter fi tein —— I \ Detector a Source 1 Fourier transou ifared (FTIR) spectrometer for identi the chemical ructre of iohibitor fins. Each functional group i.e. CH, OH and C=C) absorbs ceiainfequencies of ifared racation. Poti transmissivity versus equency identifies the chemical groups. Ta create infrared spec, 9 bean spite divides a source beam no two components. One compo- ‘en is unchanged elect of he fed miro: the other undergoes phase changes eects othe ‘moving ror The bvo ate recombined, passe though the sample and detected 2s an interferogram. ‘Ast Fourier tansonm converts the measured intererence pattem nos reuency components [Coupes (samples (Of 10S carbon see) production ting (hich has a 103,000- ‘sini vied Strengih) ners ia 8 718% HCl solution Tor 6 hours. One coupon ight) was protected with an fective inhibitor the father was not, Prote: tiom is dtine as less than ul (000 inch; 0.03 men) aver: ‘age metal theres Toss forthe time ofthe treaimont or 005 Ii meaiment ove Each absorbed! frequency coincides with a particular grouping’s natural frequency of vibration, which is well-documented red spectroscopy used to be a time: ‘consurning business. Previously, radiation ‘was split int its diferent frequencies using 2 rating or prism and laboriously guided through the sample. Today, a technique called Fourier transform infrared (FTIR) ‘spectroscopy uses the more eifcient tech. nique of moving-mirtor interferometry to convert broad-band infrared radiation into its individual frequency components (le The single beam is split, led through the sample, detected, reconstituted into a con- ventional spectrum, which is converted into its frequency components using a fast Four tr transform algorithm. One spectrum takes less than a second to generate, so hundeeds of scans can be easily made to Increase spectrum quality. The FTIR spectrum of pure octynol reveals numerous inverted absorption peaks that correspond to the compound’s molecular groupings (next page, mille. Five peaks are caused by the C-H grouping, to by CO, and one each by OH and C=C. This spectsum is octyno!’ fingerprint. Oilfield ReviewThe Dowell Schlumberger researcher fist checked that without steel, hydrochlo acid did not affect the actynol structure Using a 15-percent HCI solution, they mixed the two compounds for 24 hours, then stipped of the acid by dissolving the ‘tynol in chloroform. After the chleroou evaporated, they measured the octynol spectrum again and found it unchanged ‘Mixed with steel beads, however, the ctynolacid mixture ceated a greasy pro- tectve film over the beads. Removing this film with chloroform anel analyzing it with FTIR specvomeny, they found asigniticamly dlferent spectrogram. The C-H peaks were still present, as expected. But new peaks indicated C=C bonds, the presence of a small number of unsaturated carbons (meaning they possess free electrons) and the probability of terminal double bonds, {Terminal means one end of the boned sits on the outside ofthe structure.) Oetynol’s triple bond was not present, To verily that extraction using chloroform had not affected the film’ structure, an FTIR spectrum was made by bouncing the Infrared beam off a steel mirror that had been exposed to the octynol-acid mixture (hotom). This spectrum, of poorer quality duc tothe thinness of the film, produced the same peaks as the previous experiment as ‘well as evidence of unreacted octynol. Armed with clues about the film’ chem cal structure, the researchers next used size ia [Dinard spectrum of a ectynol Dips inthe ee ‘Spectrum indicate wave a umber veiproca of wavelength) that were 2a €-4 absorbed by certain a oH funetinalgrounsin g 6 on ‘cro Pie at he 2 Move number scale = x Be: c-o changes by a factor of al rare ic wo at 2,000) : o-H o a Weave Number emt 10035 [nared spectrum of «ste! mitmor exposed roo. Tocetynal na 13% HI solution at 63°C 99.89] [49°F for 24 ours. a This spectrum was 3 averaged for 1,500 4 Scans The inverted 2 os absorption peaks were E wad Interpreted to inicate that both ocynol and Dolymer were present a ‘om the ste soraee ey ‘The wave number seo0 20002000 1600 Wave Number em! Volume 1 Number 2 THD BOD AO0 ea charges bya {actor of 0 2t2000. 1. cer HDlnton ae des of ion ot ecochemial ectode Rescion ” Proceeng of the 3d rope Symposium on Caron Fano, Fea tly Sepembe 117, 1970, sche Schaal Ean Thorsen Gum Mach iss einai gaara [en iy System Cues” Zetec fr no. home, 3119595 427-40, 41 Bal ntockton fowe ans Sects ‘New Yu, Rew Sr, USA: ae rs 1972 Polymer. Absoration ety! Tre size-exclusion chromatogram of inhibitor lil coating tet beads large molecule, thought to be a polymer, emerges beter the ‘etynol, indicating ts larger size, likely veto polymerization ‘exclusion chromatography to investigate the size of the molecules in the film. In this Aechnique, a sample is injected in a column Containing porous material Large molecules in the sample move rapidly through the porous medium whereas small molecules follow longer, more tortuous paths. As the sample's molecular components emerge from the columa, they are detected by an ultraviolet (UV) spectrophotometer. This device shines UV light through molecules ‘and measures the amount of light absorbed. “The researchers used a wavelength of 254 nanometers because it is absorbed by the triple carbon bonds found in octynol. It is also the wavelength absorbed by another bond they suspected was inthe film, conju gated double bonds (alternating chains of single and double carbon bonds). The size-exclusion chromatogram of the film extracted from the beads shows two ‘compounds (above). The sharp absorption peak recorded later was interpreted as unre acted octynol. The broad peak occurring earlier was interpreted as a polymer of vari- able length, but larger than octynol, and hhaving conjugated double bonds. Combining the structural information pro- vided by the FTIR spectra with clues about the molecular size of the film given by the ”Odtynol Polymer on GHiyClyo-c=CH rl + on : OhiyCHeCH- CH=CH, “| (CHy(CHe)aCH= CH=CH = CH | Oty Ch Crs Has ‘CHa(CHs) ~ CH - CHy CH CHp ~ GH ~ GH = C= CHp i i cH cH ‘ i Ho HC (Chas (oy Ch CH “chemical chao ene tion tht forms the polymer fi. The pro posed chemical sm ture ofthe polyer is ‘asd on infrared specta and sizeexcls Sion chromatography. [Model or aternating current inpcdance spectroscopy (ACIS), ted 0 explore como. Sion acy on met Saudaces. Tis tec igue mode the cor resistor representing the electoite, Ryn series with a paalel Combination of resis: top the estance to charge transfer, across thesee-fec- trlyt intriace, anda capacity, Cyt ‘apactance ofthe Interface double ayer, which together repre Sent the inhibitor ik, chromatogram, the researchers deduced a likely structure for the polymer and the chain of reactions leading to it et. Inhibition Mechanism With the film’s stucture and development understood, the researchers next investigat ‘ed how the octynol and polymer worked together to inhibit cozrosion. Their main tool was an alternating current impedance spectroscope (ACIS), a device for measuring the AC impedance becween the steel surface and the acid-octynol mixture at many difer- ent frequencies. They interpreted the results in terms of an equivalent circuit comprising a resistance representing the electrolyte, Re in series with a parallel combination of 3 resistor, R, the resistance to charge transfer across the stee-electroyte interface, and a ‘capacitor, Gy, the capacitance of the intr {ace double-layer (below; le) Because costosion is caused by ion flow cross the inerace, the tanser resistance, Ry directly yields the degree of protection—the Breater Ry the more corrosion is inhibited.» The capacitance, Cy, is interpreted to yield the amount of surface area covered by the Inhibitor and polymer film. In a first experiment, the researchers mixed several concentrations of octynal with a 15-percent HCI solution for 20 min- ‘utes and allowed the mixtures to react with N80 oilfield carbon stee! (80,000-psi mini- mum yield strength), frequently used in wells of moderate temperature, 95°C to 150°C [203°F to 302°F] (below), Measuring the steel surlace’s impedance spectra, they deduced the degree of protection and sur- face area covered by the film and plotted both parameters versus actynol concentra tion. As expected, protection and coverage increased with concentration. But surpris: ingly, protection always exceeded coverage: Protection ° = © Cetynol Concentration, 10-2 malelter Degree of CoveragelProtection 5 Corson protection and surface coverage ver ‘sus octynol concentration, for octyno in 1 HC solation at 25°C 177. Te degre of po lection is aheays greater than surtoce coveae, suprising nding thai explained by the ‘nhibor preferentially adsorbing onto the mest chemically active ses on the seo nace Oilfield Review8 v.00] | rater Zoos 3 Ce Bal Coveane a 3085 gaa T w 700 Exposure Time, rin ACIS measurements made using a 27-milinok? ther ociyno! concentation ina stong 28% HCL Solution 9 65°C (140 F. The lat chap in cover age and protection occurs because he polymer ike consumes actyno leaving noe er ohibiton. This diforence was also seen in a second ‘experiment in which impedance spectra ‘were measured after a fixed concentration ‘of ectynal mixed with 15-percent HCI was allowed to react with a stool suriace for dif- ferent times (below). Protection reached a high value after 1 minute and improved ‘only slightly over the next 100 minutes ‘whereas the surface coverage was less than 50 percent after 1 minute and increased slowly thereafter To explain why proteetion is always high- ec than surface coverage, the Dowell ‘Schlumberger team proposed that octynol adsorbs nonuniformly, acting preferentially ‘on steel components that drive corrosion. Cementite, FesC, a brite iron carbide, isan example, It enhances corrosion by acceler- ating H, evolution (page 15, bottom) Cementite, however, occupies much less of, the stee’s surface than less reactive phases such as ferite, a for of pure ivon.? ‘A similar impedance spectra experiment ‘with stronger acid, 28 percent, began simi larly but ended differently. At around 40 minutes, surface coverage, having steadily 19] oa] Protection Za Coverase o4 02 T 6 700 Exoosure Tima, ein Dagieso! CoveragelProtection [lMore ACIS resus: Degree of protection and coverage plated 3 3 fiction a tine fora 35 ‘milmaefier ociyno concentaton ina 15% I solution a 25° C LF. The prada in crease in both parameters comesponds 0 oh~ ‘reformation, increased, dropped precipitously (left) Degree of protection also began dropping, This seemed to indicate that polymer growth somehow interfered with inhibition, ‘More insight into inhibition was obtained with Fourier transform ellipsometry, a tech nique that determines the average thickness ‘of very thin films# The time dependence of filmy growth on stee! was determined using vatious concentrations of octynol mixed with a 0.02 molefiter concentration of HCI (below). At the lowest octynol concentra- tion of 0.025 millimole/liter, the film appears to develop in two stages (see the two plateaus on the plod). This could indi- cate a change in orientation of the actyno! molecule with time, The molecule is Concentration in millmolesiter 10 oa Time, min aa LiEtipsomewic measurements ofl ticknes for various concentration of ectynol in a 0.02 molefiterconcentation of HCV. oma steel surface. AU the lowes octynol concentration, 8025 milmoleriter vo platens ae seen, ‘nating 3 posible change inthe orientation ofthe octynol molecule 2s 3 Fiction of tne, At higher concent ations the thickness ofthe adotbed layer Inreazes inary with tne, incating the development ofthe polymer film, assumed to be initially adsorbed parallel to the surface, the major attachment point ‘being the triple bond and the OH group. At later times, the molecule may assume a ‘more perpendicular attitude ‘At higher concentrations, film thickness Increases linearly with tne. This was inter= preted as the development of polymer, con firmed by observing absorption at the fre- quency of the visible specicum where conjugated double bonds absorb light. time as the film thickened, the absorption maxima shifted toward the red pant of the spectrum, indicating an increase in the ‘number of conjugated carbon bonds and therefore polymer growth. ‘The Fourier taansform ellipsometry also confirmed the ACIS data. Assuming a uni form distibution of material on the covered S Aton “inpaance Soscwoscopy and Use naa the Sted ste AC Response Sad hd gid fecvohtes” afer eceoana ia! Chen 223109871 25-50, {Schuhmann The luce ofa Est Fon “Adsrton of Organic Sones lcs Cenezton oft Frm’ Theory om he Mot ed Modelo wo Pall Condensers” Brechin fea ace 200 91198711937 1 7. Gioncok 8: “Inhibion of Se Cora in ‘Hyder Achy Accel: NACE {Coneion'88, Heusen, ivan USA. 388 pape 38 [s.secrachin FL, Pataghs Seon RR and Set ‘orgs Mesure ncn an Ree {elon Very Thin Fl an te Optel Props i of Srey Clgsomesy Jue of Re-erch ‘ofthe Nata oa of Svea, Psst Chememy ara, no 40963) 6877 19portions of the surface, film thickness can bbe converted to factional coverage. Cover age can then be compared to degree of inhi bition estimated from the electrochemical corrosion rate (see “Ellipsometric Results in Coverage/Protection,” right). As the ACIS measurements indicae, factional coverage i always less than degree of inhibition, but par ticularly so at low octynol concentrations, Conclusion from Experiments From the considerable number of chemical and surface analytical measurements, the researchers pieced together how octynol inhibits HCI corrosion on steel, Duting the frst minute, octynol molecules adsorb on the mote active suface sites of the steel, such as cementite, and begin inhibiting cor rosion. The polymer then begins to orm. ‘This shuts off moce cowrosion by physically blocking access of acid to the metal Beneath the film, however, comosion con: tinues because the polymer lacks a surf Cleat electon density 10 remain chemically axkorbed to the steel surface. This corrosion Uncovers active sites to which remaining ‘ctynol adsorbs, followed by more polymer generation. Eventually, polymer growth con Sumes so much octyael that none remains to protect the steel. Polymer coverage then falls, as seen on the last ACIS experiment, and conosion picks up. 20 Fraction Fraction Concentration Covered Protected 00 00 00 0.05 057 0.82 30 0.84 093 Search for Better Inhibitors peratures (see “Octynol vs, Phenones,” To the researchers, the weak link in actynol technology seems to be the polymer's inability 10 adhere to the steel. They there fore began searching for organic com- pounds that would produce polymers with better sticking power, or in chemical terms, polymers with more free electrons to bond to the steel surface. They chose the «= alkenylpherone family because of multiple lunsaturation within the molecule (a ben= zene ring, a carbon-carbon double bond and a ketone double bond)” Five phenones ‘were synthesized and tested as inhibitors under a variety of conditions (next page, top), Mixed vith conventional additives such as surfactant and intensifier, they per formed similarly to octynol at low tempera tres and dramatically better at higher tem. Corrosion Rate or [ O01) | ape entation teerieg corte esas fener “aalionphenones& Ne Css Caren Iter” in Oden PH eh Thi itermetiona 'Smostan on Chemicals dhe ay ond: The yal Scety of hema 1988, ages 17°20 1 DG, Growcock 8 and opp Ve below, left), FTIR studies showed that these livers chemicals appear (0 form a polymer called polyphenylvinylketone (PPVK). This polymer is rch enough in free electrons 10 remain adsorbed to the steel surface and inhibit corrosion as it is consumed (next ‘page, botiom) Two new Dowell Schlumberger acid Inhibitors, A-260 for wells at 95°C to 150°C [203°F to 302°F), and A-270 for wells above 150°C [302°F] are based on the alkenylphenone technology and will signii- Cantly improve inhibition during acid jobs. A- 260 is a mixture of phenylvinylketones (PVKs), formulated with appropriate organic solvents and surfactants to achieve solubility and dispersibility. A-270 is a mixture of a VK and a quaternary ammonium salt (in Which nitrogen bonds to four carbons). It Inhibits more effectively than either compo- rent alone (see “A-270 Synergism,” below) and easily outperforms most other inhibitors. The interaction of A-270 and ste! is less known than that of octynol and steel, but research into its surface chemistry may lead to inhibitors that provide even better protec- tion to well tubulars. , semeiisavam — (6-01-5904 00 ‘CH, - 0 ° Prenytnyetono €S-6-c-0% Pv 4 [Five pheones este inthe serch fr polymers with sticking power hain of chemical Bonzoylal alcohol (BAA) reactors forming the bate plyphen 6 nyetone HPV. 1 -SHOH Ol Cp a