Scribd Logo
Carica

Benvenuto in Scribd!

  • Use of Inhibitors For Scale Control

    Caricato da

    Régis Ongollo
    7 visualizzazioni6 pagine
    Monitoring of scale inhibitors

    Titolo originale

    Use of Inhibitors for Scale Control

    Copyright

    © © All Rights Reserved

    Formati disponibili

    PDF o leggi online da Scribd

    Hai trovato utile questo documento?

    Questo contenuto è inappropriato?

    Segnala questo documento
    Monitoring of scale inhibitors

    Copyright:

    © All Rights Reserved
    Scarica in formato PDF o leggi online su Scribd
    Segnala contenuti inappropriati
    7 visualizzazioni6 pagine

    Use of Inhibitors For Scale Control

    Caricato da

    Régis Ongollo
    Monitoring of scale inhibitors

    Copyright:

    © All Rights Reserved
    Scarica in formato PDF o leggi online su Scribd
    Segnala contenuti inappropriati
    di 6
    Use of Inhibitors for Scale Control in Brine-Producing Gas and Oil Wells L.A. Rogers, SPE, Gas Research Inst; K. Varughese, Alquatani Pipe Coating Terminal; S.M. Prestwich, U.S. DOE; @.G, Waggett,* South Texas College of Law; and M.H. Sallml,** JAE. Oddo, SPE, E.H. Street Jr., and M.B. Tomson, Rice U. ‘Summary. Field and laboratory work sponsored by the Gas Research Inst. (GRD and the U.S. DOE showed that calcium carbonate (CaCOs) setle formation in waters produced with natural gas and oil can be prevented by injection of phosphonate inhibitor ito the ormation, even ifthe formation is sandstone without calcite binding material. Inhibitor squeeze jobs were carried out on the DOB’s _geopressured/ geothermal Gladys McCall brine/gas well and GRI’s coproduction wells in the Hitchcock field. After the inhibitor squeeze ‘on Gladys McCall, the well produced more than S million bbl [800% 10° m?] water ata rate of about 30,000 B/D [4770 m*/d] without ‘CaCO5 scaling. Before the inhibitor squeeze, the well could not be produced above 15,000 B/D [2385 m°/d] without significant scale formation. In the GRI brine/gas coproduction field test, inhibitor squeezes have been successfully used to prevent scaling. Laboratory ‘work has been conducted to determine what types of oilfield waters are subject to scaling. This research has led to the development ‘of a saturation index and accompanying nomographs that allow prediction of when scale will evelop into a problem in brine production. ‘Core samples from both fields were used in laboratory studies. Analytical methods to analyze inhibitors in brine at low levels were extended. A complete history of field development and the laboratory backup experiments is included in this paper. Introduction Progress has been made toward controlling scale formation from brines often associated with geopressured energy production, coproduction wells, and oil wells that make large amounts of as sociated water, As brine flows oot ofthe formation and up the wel, the pressure drops. This pressure drop causes dissolved CO> to 0 out of solution, increasing the solution pH. The pH rise causes aqueous bicarbonate, HCO, to be converted to carbonate, CO}, ‘which tends t initiate CaCO, precipitation in the formation pore ‘throats near the wellbore, onthe production tubing walls, or in sur- face handling equipment. The scale-conrol options include (1 limit ing production so tht the drop in pressure is not suicient to induce precipitation (a discussed later), (2) injecting trace concentration ‘of inhibitors in the surface equipment, (3) injecting trace concen trations of inhibitors downbole trough a small-diameter teat tring, sand (4) squeezing inhibitor into the formation so thatthe inhibitor Will be released slowly when production begins. ‘The First option generally entails an unacceptable loss in revenve. Option 2 does not protect downhole production tubing, and Option 3s often prohibitively expensive. Option 4 can protect the forma- ‘ion near the wellbore, dhe production tubing, and the surface equip- ‘ment, Successful inhibitor squeeze jobs have been carried cut on the geopressured/ geothermal Gladys McCall rine/gas well n Grand ‘Chanier, LA, and the coproducton wells inthe Hitchcock field near Galveston, TX. The producing formation of the Gladys McCall was sandstone cemented by secondary quartz and contained no calcite, Which made designing successful inhibitor squeeze considerably ‘more complicated. Previous laboratory work led to the develop- ‘ment of a method to predict when scale would begin to form and the proper amount of inhibitor needed to prevent scale formation In this paper, we first discuss the field applications and results of phosphonate inhibitor squeezes to prevent CxCOs scale formation And then describe laboratory experiments and theoretical consider- lations that led tothe development of the inhibitor squeeze tech- niques used. Flold Exporiments—Gladys McCall ‘The first attempts at phosphonate inhibitor squeezes at Gladys McCall were unsuccessful because the inhibitor could not be pumped ito the formation, Two causes seemed possible: poor surface-water ‘quality with high iron and calcium content and interaction of the ‘phosphonate with formation brine that contained 40,000 mg/L Ca ton (Table 1). The fist ofthese problems could be handled by the use of good-quality water that had passed through an ion exchange and a good filtering unit to remove aay iron hydroxide. The sec- are Pinteitee Taner, Feces Oe cond problem could be solved by use of a brine spacer ahead of the inhibitor to fore the calcium-contining formation water away from the wellbore. On the bass ofthese conclusions, an inhibitor pill was designed tobe injected follows. Inhibitor Squeeze I. 1, Purp 300 bl [47.7,m?} of 15% NaCl spacer. 2: Use 100 bbl [15.9 m'] of 6% inhibitor in 15% NaC! [the in- Iribitor was nitiloti-(methylene phosphonic) acid from Champion Chemical Co... Houston]. 3, Inject 100 BbI [15.9 m°] of 18% NaCl spacer. 44 Add 100 bbl [15.9 m!] of 10% CaCl overflish. 5. Pump $00 bb [79.5 m:] of 15% NaCl into the formation as pusher. 6. Shut in the well for 24 hours to allow reaction. In fact, 6% inhibitor was used (Sep 2). At first, everything went wel withthe treatment. Pmping rate was hed at 3 bbI/min (0.0053 m/s] with only a slight pressure increase over original shut-in ‘wellhead pressure. When the 100 bbl {15.9 m:] of inhibitor ht the formation, the pressure built up rapidly and the pump rate was re- dduced to 1 bbV/min (0.0026 m’Vs} to keep from exceeding the frac- ture presure. The 100 bbl [15.9 m'] of inhibitor and 100 bb [15.9 sm] of NaCl spacer were squeezed away at 1 bblimin [0.0026 mvs}. When the CaCl; overfush hit the formation, the pressure built up rapidly tothe preset iit, Pump rate was reduced to 0.2 bbvnin [0.53%10~2 m2/s} and the 100 bb (15.9 m'] of CaCl solution ‘was slowly pumped away. This was followed by about 25 bb (3.97 zm] of 15% NaCl solution to clear the tubing. The well was shut in because all the inhibitor was in the formation and had been ex- posed t caleium from the formation brine and tothe CaCl; over- flush, as evidenced by the pressure increase. ‘fcr 24 hours, the well was allowed to flow back at 100 bbU/br (0.0044 ons). Brine samples were taken every 10 bb [1.6 m*] during the flowack ofthe pill an pesiodically thereafter. These samples were analyzed for numerous elements, in addition to the inhibitor isl (ig. 1) Ttwas found that magnesium was the most ee | Gverluh would be necessary. The pil was pumped a consiera- 138 | Si distance from te wellbore. Ts procedure would avoid the 1.06 at 7796 | presure increase observed when the calcium inthe CaCl; over ND, <5 flush hit the formation and would greatly simplify the overall pill ND.<1 application. CO, ges, wots aie’ | "Bascom observations fromthe behavior af the rat sees fect coos oot ful phosphonate inhibitor squeeze, a simplified pill procedure was Sa ea toy wea tee vay apr | Ht OOD te tsi ci teen Saatee | dese Senecirewmameemescuenee | “ihblor Spee 2 Sect cnnaraion anaes simbeon tone | 1 Pym 160 bl (1.9 m') of prefs of 10% NaCl solution to push most of the calcium ions in the reservoir brine away from tion of about 70% of the inhibitor remaining in the formation, or 21% of that originally injected. ‘To measure such low inhibitor concentrations in field brine, it was necessary to modify standard colorimetric phosphonate proce- ures. Before the ihibitor squeeze, production was limited to about 15,000 B/D [2385 m°/d] to avoid scale formation. This severely curtailed gas production, After the squeeze, it was possible to in frease the production rate to about 30,000 B/D [4770 m°/d] ‘without scale formation inthe production tubing. During this pert- fd, about 25 sef [0.71 std m3] of natural gas was separated and sold per 1 bbl [0.16 m'] of produced brine. the wellbore. 2. Use 100 bbl [15.9 m°] of pH-nevtral 3% ammonium phos- ‘honate inhibitor satin 10% NaC! solution to react withthe cal ‘um from the formation water. "3. Overflush with 900 bbl [143 m] of 10% NaCl solution fol- owed by 300 bb [47.7 m] of oilfield brine to clean the tubing. "f. Shut in for 36 hours and bring back slowly at 100 bo\ir 10.0044 m*/s}. 's. After 2 days, resume flow of 30,000 BID [4770 m°/d] ‘Because these fluids had roughly the same density asthe forma- tion brine and viscosities were low, the injection rate aftr preflush was chosen as 6 bplimin (0.016 m°/s} 7) Volume of Brine Produced (Barrels) Fig. 1—Concentration of NH,, P (as phosphonate), produced after the first successful inhibitor squee 1. Na, K, and Ca vs. barra of brine Gladys MeCall design well. SSPE Production Engineering, February 1990 4a0 4600 4400 4200 4000 3000 SURFACE TUBING PRESSURE (peta) 3600 a4ne L - L 4 HOURS AFTER 11:02 ON 4 FEB 1966 Fig, 2—Surface tubing pressure vs. time during the second successful Inhibitor squeeze at the Gladys McCall design well. ‘An oxygen scavenger, (NH,)HSOs, and an iron chelating agent, EDTA, were added to all the brine to prevent formation of iron hydroxide, and a2'4-yan filter was used just upstream of the pump suction. In addition, 100 mCi (3.7 GBaj of iodine-131 was mixed withthe phosphonate pill asa tracer. Fig. 2 shows the pressure ‘curve forthe injection. No problems were encountered that would force us to slow the pumping rate. Maximum pressure ise was ap- proximately 400 to 500 psi [2.76 to 3.45 MPa] as the pill was ‘pumped into the formation, ‘The well was brought back on stream. after 36 hours and pro- duced at the rate of 100 bbl [0.0044 m*/s] for 2 days, Flow rate ‘was then increased to about 30,000 B/D [4770 m3/d] and has re- ‘mained there for more than year, except for a slow rate decrease that was a function of the reservoir flow properties. Fig, 3 shows the iodine-131 scintillation count data vs. barrels ‘of brine produced. A well-defined curve with a maximum at around 1,450 to 1,500 bbl (231 to 238 m) of brine flow results. ‘Samples ofthe brine were also used to determine the phospho- nate concentrations in solution (Table 2). Contrary to the first squeeze job, the large backflow of calcium phosphonate was not ‘observed in this squeeze treatment, probably because the phospho- rate pill was pushed back into the reservoir far enough to disperse ~ 5 & “a ans? noc, ibncI0 Fig, 3—Plot of microcurle of "1 per 1-mL sample vs. brine production after second successful inhibitor squeeze at Gla- ‘Sys MoCall design well. The "1 was added to the 100 bbi ‘of inhibitor as KI, The scintillation counting was done after ‘about 4 halt-lives a ‘TABLE 2—PHOSPHONATE CONCENTRATION IN GLADYS MCCALL BRINE FLOWBACK AFTER INHIBITOR SQUEEZE 2 Brine Phosphonate eo) (git) 306 None 406 None 605 200 206 175 1,028 110 1,088 124 4148, 128 1208 168 1268 148, 1328 138 11368 1 11406 134 1506 we 4750 64 48473 os 225.832 on? 28,401 013 4.826428 oa ” ‘TABLE 3—XRD AND MICROPROBE ANALYSES ‘OF GLADYS MCCALL CORE SAMPLES Mineral _XAD*_—Microprobe Quartz 819% Present as sand grain and a cement Caleta 0% None found Feldspar 6% As pure albite (NaAISi,Os) and ure orthoclase (KAISI,O4) Kaolinite 210.9% Pure ite Pure Chlerte Trace Aluminumich ro ong an Tang Pon, I aoa Gspresred extra {ESaseo Say Meat ha, T Wale 8 DOE Heads Oprons On, SechwarFre& Season in 106). the reaction over a larger volume of the sand gr ‘of production at 30,000 B/D [4770 m°/d}, the inhibitor concen- tration dropped to about 0.15 mg/L and has remained therefor more than a year (Table 2). “The successful application of the phosphonate allowed the Gla- dys MeCall to be produced at the maximum fate available from the reservoir. About 12 million Bbl [1.9% 10® m] of brine has been produced with this second pill with no apparent reduction in protection from CaCO scale, The well was subsequently shat in for reservoir buildup tess Laboratory Studies and Theoretical Considerations [Numerous laboratory experiments were conducted to prepare for the field work. Core material from the producing formation atthe Gladys McCall was analyzed by X-ray in gas phase, with p in psia'and T in °F. ‘Oddo and Tomson! derived a similar equation for pH. All the variables of Eq, 2 are readily measurable. A simple kt to measure Ca, A, and V, on-site is available from LaMotte Chemical Co. (Chestertown, MD) and the gas-phase percent CO2 can be easily, measured by Drager tubes or gas chromatography. The T and p are generally available atthe Sample point. To facilitate the use ‘of Eq, 2, a nomograph was constructed? and a slide rule is avail fable from Shell Canada (Calgary, Alta., Canada). At intial shut- in conditions, the downhole Zs in Eq. 2 is theoretically zero for any formation tat is calcite cemented. Therefore, a change in satu- ration index, Als, was defined as the sum ofthe changes resulting from p, T, Ca, A, Po,» and V,, independently? als @ Isa—Isi Ga) ) During prociction, in the absence of scale formation, the only variables that change fom bottombole to wellhead are T and p. Nomographs to calculate Als were also developed.? A semi- {quantitative correlation of seale formation process vs. I was de- ‘eloped from field and laboratory studies. For Ag values between Zero and 1.1 to 1.4, scale will probably not start form in equip- tment fee of scale, For Als values between 1.4 and 2.3, scale can generally be controlled by trace concentrations of inhibitors. Above Als of about 2.3, it may not be possible to prevent scale with in- hibitors (soe below). Below AJs=0, scale will not form, but cor- rosion wil likely be the prime concern, especialy if Als < ~1.0. =Alsy+Alsr+AlscatAlsa+Alsco, +Alsy, Inhibitors. In 1935, Rosenstein found that extremely low concen- trations of metaphosphates could be used to prevent seale forma: SPE Production Engineering, February 1990 tion.? Today several classes of compounds are used for this substoichiometric threshold. scale inhibition: inorganic poly ‘Phosphates, polyphosphate esters, phosphonates, and low-molecular- ‘weight polyacrylates and polymaleates.* Most of these threshold inhibitors are surfuce-active. They probably prevent nucleation of, ‘a new scale phase by interacting withthe forming nucle and prevent- ing formation of a stable slid phase.* They prevent further growth ‘ofan already existing phase by adsorbing onto active growth sites ‘on the surface and preventing ieorporauon of more late ions.® For brine supersaturated with respect to calcite, it has been pro- posed thatthe lowest concentration of threshold inhibitor needed frould be approximately the molar concentration of divalent car- bonat, spectially® CO} VEOO7)<1.0, a where parentheses represent molar concentrations and Q-average Charge’on the inhibitor (subscript 7) oF inhibitor unit used to ex- press concentration, The summation sign suggests strict additivity Sf mixed intbitors In laboratory tests, compounds and various ombiaton of compounds frm several chemal lasses have been Shown fo prevent nucleation at concentrations similar to those pre- dicted by Eq. 4, but no examples have been found of ealete- nucleation inition below the limit suggested by Eq. 4 ‘Aso, there i an upper limit t which an inhibitor might work ‘Tis upper limit is contolled by the solubility ofthe inhibitor. Precptation inhitors generally form insoluble salts of one ofthe tice fons ofthe phase being inhibited, Al the inhibitor classes listed above are anions and form insoluble alum sls. I'he in- hibitor concentration is too large, caleiuminhibitor salt (pseu- oscil) precipitates, For some ofthe field systems investigated, this upper limit ofiniitor concentration has been found tobe only afew maligrams per liter or less Discussion ‘The development ofa successful squeeze method to inhibit CaCOs ‘depositions from produced bres has been tested. This method has ‘been shown tobe effective in sandstone reservoirs where there is ro calcite inthe cementing material. The key ingredient in @ suc~ ‘cessfl application apparently is the formation of calcium phospho- hate in the reservoir some distance from the wellbore. This can bbe done by carefully selecting the amounts of preflush to move the brine that contains calcium ion away from the wellbore and pump- ing excess afterflush to force the phosphonate into the reservoir, ‘where it interacts with calcium from the formation water to form the insoluble calcium phosphonate "There is considerable room for improvement in the development of the inhibitor squeeze technique. For example, we are not sure thatthe 10% NaCl preflush and afteflush could not be done with regularly available oilfield brine. Precautions would need to be taken, however, fo ensure thatthe Ca and Fe levels inthe brine 8 were low, Also, the use of a small-pore-sze filter (preferably 2 tum of less) isa’ must to prevent blocking of the wellbore by aay particles inthe oilfield brine. The mixing data available from the First successful squeeze job at Gladys McCall are quite interesting. ‘The sodium concentration (Fig. 1) rises more sharply than expect- ced and then does not appear to remain atthe high concentration ‘as ong as it should In fact, the sodium concentration has returned almost to its normal formation brine level by the time 900 bbl (143 1m] of brine has been produced, whereas we would expect high values to cover atleast a 500-bbi [79.5-m°] spread. Its apparent peak atthe same point asthe phosphonate peak also is unexpected. Tm the second squeeze inhibitor test, the iodine peaks at around 1,500 bbl [238 m*] (Fig. 3), which is about 300 bbl [47.7 m:] later than expected. Iti interesting to note, however, that ifthe area tunder the iodine curve is integrated, more than 90% of the iodine has returned by the time 3,000 bbl [477 m'] of fluid has been produced. ‘At flowing wellhead conditions, the inhibitor concentration (0.15 rmgiL,) is only 15% greater chan that predicted by Eq. 4.5 This agreement may be fortuitous but is similar tothe lowest concenta- tion found in laboratory tests! As noted before, with each inhi- bitor squeeze, scale began to form in the low-pressure side ofthe surface equipment at 4 o 5 months. This occurred as the Ais in- ‘creased to about 2.3 o higher (Eq. 3)! but an additional 0.25, ‘mg/L of inhibitor was sufficient to prevent scale in the low-pressure region ofthe surface equipment. When more than 1 mg/L of inhi- bitor was injected inthe surface equipment, calcium-inhiitor pseu

    Potrebbero piacerti anche