COMPOSITIONS, SYSTEMS, AND METHODS FOR IRON SULFIDE SCALE IDENTIFICATION, PREVENTION, AND REDUCTION

Abstract

Compositions and methods for prevention and reduction of iron sulfide scale formation, one method including detecting at least one component indicative of an iron sulfide scale precursor, the at least one component selected from the group consisting of: H.sub.2S; HS.sup.−; S.sup.2−; S.sub.n.sup.2−; FeS.sub.(aq); Fe.sup.2+; Fe.sup.3+, and combinations of the same; preparing a composition to react with the iron sulfide scale precursor, the composition comprising at least one compound selected from the group consisting of: a methylating agent; a metal operable to react with sulfide species; a compound to increase the oxidation state of Fe.sup.2+; and combinations of the same; and applying the composition to the iron sulfide scale precursor to consume the iron sulfide scale precursor.

Claims

1. A method for prevention and reduction of iron sulfide scale formation, the method comprising the steps of: detecting at least one component indicative of an iron sulfide scale precursor, the at least one component selected from the group consisting of: H.sub.2S; HS.sup.−; S.sup.2−; S.sub.n.sup.2−; FeS.sub.(aq); Fe.sup.2+; Fe.sup.3+; and combinations of the same; preparing a composition to react with the iron sulfide scale precursor, the composition comprising at least one compound selected from the group consisting of: a methylating agent; a metal operable to react with sulfide species; a compound to increase the oxidation state of Fe.sup.2+; and combinations of the same; and applying the composition to the iron sulfide scale precursor to consume the iron sulfide scale precursor.

2. The method according to claim 1, wherein the step of detecting comprises the use of a solid state glass Au-amalgam electrode comprising activated carbon particles.

3. The method according to claim 2, wherein the Au-amalgam electrode comprises a gold wire about 100 μm in diameter.

4. The method according to claim 3, further comprising the use of a Pt counter electrode, and a Ag/AgCl reference electrode with the Au-amalgam electrode.

5. The method according to claim 1, wherein the composition comprises the methylating agent, the metal operable to react with sulfide species; and the compound to increase the oxidation state of Fe.sup.2+.

6. The method according to claim 5, wherein the methylating agent comprises methyl trifluoromethanesulfonate, the metal comprises zinc, and the compound to increase the oxidation state of Fe.sup.2+ comprises chlorine.

7. The method according to claim 1, wherein the step of preparing comprises mixing methyl trifluoromethanesulfonate with copper chloride and zinc acetate.

8. The method according to claim 7, wherein the molar ratio of methyl trifluoromethanesulfonate to zinc acetate is about 1:1 and the molar ratio of methyl trifluoromethanesulfonate to copper chloride is about 10:1.

9. The method according to claim 7, wherein the step of mixing includes the use of an organic solvent.

10. The method according to claim 9, wherein the organic solvent comprises ethanol.

11. The method according to claim 1, wherein before the step of applying the composition is cooled to below room temperature.

12. The method according to claim 1, further comprising the step of applying voltammetry to verify a decrease of concentration in at least one component selected from the group consisting of: H.sub.2S; HS.sup.−; S.sup.2−; S.sub.n.sup.2−; FeS.sub.(aq); Fe.sup.2+; and combinations of the same, or to verify an increase in concentration of Fe.sup.3+.

13. The method according to claim 1, further comprising the step of applying the composition to reduce the formation of a compound selected from the group consisting of: PbS, ZnS, HgS, and combinations of the same.

14. The method according to claim 1, where the step of applying the composition to the iron sulfide scale precursor to consume the iron sulfide scale precursor comprises applying the composition in a batch of about 3 barrels to about 5 barrels to a wellbore proximate a hydrocarbon-bearing formation every about 30 to about 45 days.

15. A composition for prevention and reduction of iron sulfide scale formation, the composition comprising: a methylating agent; a metal operable to react with sulfide species; and a compound to increase the oxidation state of Fe.sup.2+, where at least one of the methylating agent, the metal, and the compound to increase the oxidation state of Fe.sup.2+ react with at least one component selected from the group consisting of: H.sub.2S; HS.sup.−; S.sup.2−; Sr; FeS.sub.(aq); Fe.sup.2+; and combinations of the same.

16. The composition according to claim 15, wherein the methylating agent comprises methyl trifluoromethanesulfonate, the metal comprises zinc, and the compound to increase the oxidation state of Fe.sup.2+ comprises chlorine.

17. The composition according to claim 15, wherein the composition comprises methyl trifluoromethanesulfonate, copper chloride, and zinc acetate.

18. The composition according to claim 17, wherein the molar ratio of methyl trifluoromethanesulfonate to zinc acetate is about 1:1 and the molar ratio of methyl trifluoromethanesulfonate to copper chloride is about 10:1.

19. The composition according to claim 17, wherein the composition further comprises an organic solvent.

20. The composition according to claim 19, wherein the organic solvent comprises ethanol.

21. The composition according to claim 15, wherein the composition consists essentially of methyl trifluoromethanesulfonate, copper chloride, and zinc acetate.

22. The composition according to claim 15, wherein the composition consists of methyl trifluoromethanesulfonate, copper chloride, and zinc acetate.

23. A method for producing a solid state glass gold-amalgam electrode, the method comprising the steps of: disposing a wire comprising gold in and through a high-temperature glass electrode body to expose a portion of the wire external to the high-temperature glass electrode body for detecting electrical current, the exposed portion of the wire located proximate mercury; and encasing a portion of the wire proximate the exposed portion with an epoxy resin containing gold and carbon particles.

24. The method according to claim 23, wherein the high-temperature glass electrode body comprises borosilicate glass.

25. The method according to claim 23, further comprising the step of detecting at least one component indicative of an iron sulfide scale precursor, the at least one component selected from the group consisting of: H.sub.2S; HS.sup.−; S.sup.−; S.sub.n.sup.2−; FeS.sub.(aq); Fe.sup.2+; Fe.sup.3+; and combinations of the same.

26. The method according to claim 25, further comprising the steps of preparing a composition to react with the iron sulfide scale precursor, the composition comprising at least one compound selected from the group consisting of: a methylating agent; a metal operable to react with sulfide species; a compound to increase the oxidation state of Fe.sup.2+; and combinations of the same; and applying the composition to the iron sulfide scale precursor to consume the iron sulfide scale precursor.

27. The method according to claim 23, further comprising the steps of: pulverizing activated carbon; combining the pulverized activated carbon with gold; and combining the pulverized activated carbon and gold with ultra-high temperature epoxy resin stable up to about 600° F. to form the epoxy resin containing gold and carbon particles.

28. The method according to claim 27, further comprising the steps of: acidifying the pulverized activated carbon; combining the pulverized activated carbon with a stabilizing functionalized amine; and sonicating the pulverized activated carbon and gold with ultra-high temperature epoxy resin stable up to about 600° F., wherein the step of combining the pulverized activated carbon with gold comprises the use of chloroauric acid.

29. The method according to claim 27, wherein the pulverized activated carbon comprises particles with a median particle size between about 5 μm to about 10 μm and the gold comprises particles with a median particle size between about 2 nm to about 8 nm.

30. A solid state glass gold-amalgam electrode, the electrode comprising: a high-temperature glass electrode body comprising borosilicate glass; a wire comprising gold disposed in and through the high-temperature glass electrode body exposing a portion of the wire external to the high-temperature glass electrode body for detecting electrical current, the exposed portion of the wire located proximate mercury; and an epoxy resin containing gold and carbon particles encasing a portion of the wire proximate the exposed portion.

31. The electrode according to claim 30, wherein the wire comprising gold is about 100 μm in diameter.

32. The electrode according to claim 30, wherein the epoxy resin once dried is stable up to about 500° F.

33. The electrode according to claim 30, wherein a portion of the wire not encased by the epoxy resin containing gold and carbon particles is encased by epoxy resin without gold and carbon particulates.

34. The electrode according to claim 30, wherein the carbon particles exhibit a median particle size between about 5 μm to about 10 μm and the gold particles exhibit a median particle size between about 2 nm to about 8 nm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0034] These and other features, aspects, and advantages of the present disclosure will become better understood with regard to the following descriptions, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the disclosure and are therefore not to be considered limiting of the disclosure's scope as it can admit to other equally effective embodiments.

[0035] FIG. 1 shows a voltammogram of electroactive species detected by modified HPHT solid state glass Au-amalgam electrodes of the present disclosure under simulated petroleum reservoir conditions.

[0036] FIG. 2 shows real-time voltammetric scans in a glass reactor for experiments monitoring the formation and subsequent inhibition of molecular FeS.sub.(aq) clusters, iron(II), and sulfides after injecting a newly-formulated organic-ionic solvent inhibition mixture under simulated HPHT reservoir conditions.

[0037] FIG. 3 shows real-time in situ voltammetric scans monitoring the formation and subsequent inhibition of molecular FeS.sub.(aq) clusters and iron(II) in coreflood experiments, described further herein, after injecting organic-ionic solvent inhibition mixtures.

[0038] FIG. 4 is a graph showing the inhibition performance (approximately 90%) of formulations against molecular FeS.sub.(aq) cluster formation under coreflood experimental conditions.

[0039] FIG. 5 is a graph showing a concentration drop (approximately 81%) in iron (II) species and showing the R2-values that were affected by a scale inhibition solvent formulation under core flood experimental conditions.

[0040] FIG. 6 is a graphic representation of a reaction profile for the inhibition and potential nucleation of nano-particulate iron sulfide molecular clusters, FeS.sub.(aq), where after nucleation, aggregation of bulk stable and metastable FeS minerals and scaling in HPHT petroleum reservoir conditions can occur.

[0041] FIG. 7 is a schematic representation of the experimental procedure for the preparation of gold-coated, pulverized carbon particles mixed with ultra-high temperature epoxy resin for the manufacturing of the disclosed modified HPHT solid state glass Au-amalgam electrodes of the present disclosure.

[0042] FIG. 8 shows a schematic design for the modified HPHT solid state glass Au-amalgam electrodes of the present disclosure.

DETAILED DESCRIPTION

[0043] So that the manner in which the features and advantages of the embodiments of systems, processes, and compositions for the accurate detection of and environmentally-friendly prevention and removal of FeS.sub.(aq) molecular clusters and solid FeS scale in hydrocarbon production and processing operations, as well as others, which will become apparent, may be understood in more detail, a more particular description of the embodiments of the present disclosure briefly summarized previously may be had by reference to the embodiments thereof, which form a part of this specification. It is to be noted, however, that the experiments and drawings illustrate only various embodiments of the disclosure and are therefore not to be considered limiting of the present disclosure's scope, as it may include other effective embodiments as well.

[0044] Experimental & Analytical Methods

[0045] Glassware and plasticware materials used in the experiments were acid washed with 10% (V/V) HNO.sub.3 and triple rinsed with sterilized 18 MΩ water before use. Solutions for iron sulfide molecular cluster preparation, FeS.sub.(aq) preparation, for FeS scale mineralization tests were prepared from 18 MΩ, UV-sterilized water purged for at least 30 minutes with ultra-high-purity (UHP), O.sub.2-free N.sub.2, in order to remove traces of oxygen. Stock solutions of FeCl.sub.2, Na.sub.2S.9H.sub.2O, and Fe(NH.sub.4).sub.2.6H.sub.2O (Mohr's salt) were made from their analytical, reagent-grade salts. 0.01 M PIPES (Piperazine-1,4-bis(2-ethanesulfonic acid)) from Sigma Aldrich (St. Louis, Mo.) was buffered with 0.01 M sodium chloride solution and used as a formation and condensed water medium. Research grade ethanol, methyl triflate (methyl trifluoromethanesulfonate (CF.sub.3SO.sub.3CH.sub.3)), zinc acetate (Zn (CH.sub.3CO.sub.2).sub.2), and copper chloride (CuCl.sub.2) were obtained from Acros chemicals (Geel, Belgium). Molecular FeS.sub.(aq) clusters were prepared under anoxic conditions by direct addition of 50-100 μM Fe.sup.2+ prepared from standard Mohr's salt to 10-50 μM solutions of H.sub.2S/HS.sup.− prepared from standard Na.sub.2S.9H.sub.2O.

[0046] HPHT Detection of Iron Sulfide Precursors. Analytical protocols for detecting iron sulfide molecular clusters, FeS.sub.(aq), under HPHT hydrocarbon reservoir conditions are needed. Prior art detection limits are greater than the concentrations at which the aqueous FeS.sub.(aq) molecular clusters generally exist; that is at greater prior-art-detectable concentrations, FeS.sub.(aq) visibly coalesces into nano-crystalline FeS.sub.(mackinawite).

[0047] As a result, new and modified HPHT solid state glass Au-amalgam electrodes (for example, 100 μm in diameter) plated with sensitive carbon were developed as an electrochemical detection system for in situ analysis of FeS.sub.(aq), Fe.sup.2+, Fe.sup.3+, S.sup.2−/S.sub.n.sup.2−, O.sub.2 and other dissolved species. The HPHT solid state glass Au-amalgam electrodes were used with a Pt counter electrode, and a Ag/AgCl reference electrode, operated with Analytical Instrument Systems, Inc. (AIS) software.

[0048] FIG. 7 is a schematic representation of the experimental procedure for the preparation of gold-coated carbon particles mixed with ultra-high temperature epoxy resin for the manufacturing of the disclosed modified HPHT solid state glass Au-amalgam electrodes. FIG. 8 shows a schematic design for the modified HPHT solid state glass Au-amalgam electrodes of the present disclosure.

[0049] A modified HPHT solid state glass Au-amalgam electrode was prepared using pulverized activated carbon stabilized with gold nanoparticles. A stabilizing functionalized amine, dimethylamine, was used as shown in FIG. 7, along with nitric acid to treat the pulverized activated carbon. The pulverized activated carbon, represented as a lattice at left in FIG. 7, was acidified with hot nitric acid solution at 75° C. for 30 mins. The oxidized carbon particles were then rinsed three times with deionized water and dried in oven at 45° C. overnight. After drying, the activated carbon was allowed to undergo a reductive amination reaction with anhydrous dimethylamine at room temperature for 1 hour. Excess amine solution was washed twice with ethyl alcohol leaving the functionalized activated carbon, which was allowed to dry again at 45° C. overnight.

[0050] Median particle size for activated carbon was between about 5 μm to about 10 μm, and that of gold nanoparticles ranged from about 2 nm to about 8 nm, with an average of about 6 nm. Without being bound by any theory or practice, it is believed that the gold and carbon particles are at least partially covalently bonded or linked together to yield nanocomposite products during synthesis and manufacturing as a final product.

[0051] To deposit gold nanoparticles onto the functionalized activated carbon, 100 mL of 0.25 mM HAuCl4 (chloroauric acid) aqueous solution was mixed with a heated solution of 1.25 mM sodium citrate, and this mixture was allowed to reflux for 20 minutes with stirring to yield a wine-red colored solution. After heating for 30 min, the functionalized activated carbon was slowly added to the wine-red solution to produce an electroactive gold supported carbon nanocomposite colloidal solution, which was cooled to room temperature and stored in the dark. The obtained gold nanoparticles, electrostatically attracted by the carbon surfaces, and carbon were later mixed with ultra-high temperature epoxy resin (Duralco™ 4460 by Cotronics Corp. of Brooklyn, N.Y., stable up to about 600° F.), which exhibits excellent adhesion to glass, high bond strength, and high electrical resistance (volume resistivity of 10.sup.14 ohm.Math.cm). Other similar epoxy resins can be used with high temperature resistance and high electrical resistance.

[0052] The final mixture was sonicated for 3 hours with heating at 65° C. to obtain a homogenous gelatinous solution, which was employed in manufacturing of highly sensitive solid state glass gold-amalgam electrodes. In FIG. 7, carbon and chloroauric acid are shown at left followed by the mixture of activated, functionalized carbon and gold nanoparticles, then the mixture added to ultra-high temperature (UHT) epoxy, and a final product at right for use with a glass electrode after sonication.

[0053] The glass gold-amalgam electrodes with plated carbon, represented in FIG. 8, were made by placing a 100 μm-diameter Au wire in and through a 0.5 mm diameter tipped borosilicate glass tubing. One end of the wire was exposed external to the glass tubing, while the other end of the gold wire was soldered onto a 0.75 mm high-temperature, epoxy-coated flexible coaxial cable. The Au wire was fixed within the borosilicate glass tubing by injecting a freshly prepared ultra-high temperature epoxy resin mixed with electroactive gold plated on carbon particle surfaces (from FIG. 7). After final solidification and drying of the epoxy overnight, the 0.5 mm diameter tip borosilicate glass tubing was polished with fine sand paper, followed by subsequent amalgamation with a mercury solution before use in in situ style electrochemical analyses. The proposed glass gold-amalgam electrodes plated with nanocomposite carbon exhibit ideal electrochemical behavior for in situ detection of iron, sulfide, and iron sulfide precursor clusters with a wide linear dynamic range, low detection limit, and excellent selectivity and reproducibility under HPHT reservoir conditions.

[0054] In general, deposition of mercury on carbon-coated gold surfaces (as a solid amalgam electrode) described here and according to Equation 3, is convenient for electrodic surfaces because they are nontoxic, easily prepared, and mechanically stable and thus compatible with measurement in combination with flowing systems at HPHT conditions. They also show long durability and allow for rapid surface pretreatment and simple electrochemical regeneration. In addition, the proposed glass gold-amalgam electrodes plated with nanocomposite carbon and mercury exhibit a homogeneous surface, large surface-to-volume ratios, and an advantageously wide linear range with Hg.sup.2+. They also exhibit a high overpotential to the hydrogen evolution reaction. Additionally, the electrodes minimize any environmental contamination compared to traditional hanging mercury drop electrodes (HMDE's), because the surface layer of the amalgam is very thin.

Hg.sup.2++Au+2e.sup.−.fwdarw.Hg(Au)  Eq. 3

[0055] In FIG. 8, modified HPHT solid state glass Au-amalgam electrode 100 includes high temperature borosilicate glass body 102, shielded high temperature epoxy resin filling 104 disposed above the region containing gold nanoparticles plated on activated carbon mixed with epoxy resin 106. The detecting end of gold sensing wire 108 is disposed proximate mercury amalgam 110, and modified HPHT solid state glass Au-amalgam electrode 100 further includes electrode head 112, coaxial cable 114, and Bayonet Neill-Concelman (BNC) connector for an electrochemical analyzer 116. The durable electrodes can be used in organic, aqueous, and/or solid phases at HPHT conditions without risking damage, for example in cyclic voltammetry.

[0056] To test performance of the HPHT solid state glass Au-amalgam electrodes in petroleum applications and to investigate FeS.sub.(aq) molecular cluster formation, batch experiments were conducted in a HPHT glass reactor equipped with a magnetic stir bar, a thermocouple probe, a glass stopper, and a nitrogen bubbler. The batch experiments were initiated by direct addition of standard Fe.sup.2+ and Na.sub.2S to solutions at micromolar (μM) concentrations to form FeS.sub.(aq) clusters, specifically in 0.01 M PIPES/0.01 M NaCl buffer solutions. The tests were carried out in an anaerobic chamber that was constantly flashed with UHP nitrogen gas. HPHT glass reactor temperature and pressure ranges for experiments described herein ranged from about 32° F. to about 212° F. and about 0 to about 10 psi, respectively.

[0057] Once nano-particulate iron sulfide molecular clusters were formed, generally within 30 seconds, the tip (see FIG. 8 units 108, 110) of the HPHT glass Au-amalgam electrode was carefully inserted into the glass reactor, which was continuously flashed with an inert gas N.sub.2-bubbler. Cyclic voltammetry scans were performed from −0.05 V to −1.8 V and back to −0.05 V using Ag/AgCl as a reference electrode and Pt wire as a counter electrode. The potentials of the electroactive species were monitored to yield the following as shown in FIG. 1: trace amounts of oxygen (O.sub.2) at −0.25 V; −0.6 V for H.sub.2S/HS.sup.−; −1.2 V for molecular clusters, FeS.sub.(aq) cluster complexes; and about −1.4 to −1.5 V for Fe.sup.2+ as illustrated in FIGS. 1 and 2. All electrochemical measurements shown in FIG. 1 were taken using a computer-controlled Analytical Instrument Systems, Inc. (AIS) DLK-100 Potentiostat and a Princeton Applied Research Model 301 hanging drop mercury electrode (HDME).

[0058] Chemical Formulation And Synthesis Of Inhibition Solvent. In sour petroleum reservoirs, reactive sulfur and its intermediate species are responsible for FeS mineralization and scale deposition, reactive species including hydrogen sulfide (H.sub.2S), bisulfide (HS), and polysulfides (S.sup.2−/S.sub.n.sup.2−) as illustrated in Equation 1. Methyl triflate (methyl trifluoromethanesulfonate (CF.sub.3SO.sub.3CH.sub.3)), zinc acetate (Zn(CH.sub.3CO.sub.2).sub.2), and copper chloride (CuCl.sub.2) can protect and preserve groups in organic and inorganic synthesis processes due, in part, to their stability and fast chemical reactivity they impart on the sulfides species to which they attach. Other methylating agents, metals, and components operable to react with iron species can additionally or alternatively be used.

[0059] A unique chemical formulation based on the aforementioned chemistries was developed by using a three-necked, 250-mL, round-bottomed flask equipped with a nitrogen bubbler inlet, a Dean-Stark trap with reflux condenser, thermocouple probe, rubber septum, and an overhead mechanical stirrer that was charged with methyl trifluoromethanesulfonate (13.40 mL, 120.1 mmol, 2.10 equiv.) and ethanol solution (60 mL). The resulting solution was cooled to 0° C. in an ice bath followed by dropwise addition of a light blue homogeneous mixture of zinc acetate (20 g, 0.109 mol, 1.0 equiv.) and copper chloride (1.2 g, 0.009 mol, 0.1 equiv.) dissolved in 15 mL of ethanol. The reaction with methyl triflate was exothermic during dropwise addition. The ice bath was removed and the viscous solution was allowed to warm to ambient temperature. After 1 hour, a clear homogeneous mixture was formed, which optionally can be stored in a refrigerator for about 24 to about 78 hours, or directly used in iron sulfide molecular cluster inhibition or sulfide inhibition methods.

[0060] Equivalent molar ranges for suitable embodiments include a ratio of methyl trifluoromethanesulfonate:zinc acetate:copper chloride from about 0.12:0.1:0.01 to 2.3:2.0:0.5.

[0061] Iron Sulfide And Sulfides Inhibition Experiments. As previously discussed with respect to HPHT detection of iron sulfide precursors, after the formation of nano-particulate iron sulfide molecular clusters in a glass reactor, the composition comprising methyl triflate, zinc acetate, and copper chloride (having been stored in a refrigerator) was used to conduct inhibition tests by injecting the clear homogeneous mixture with an airtight syringe into the glass reactor. Within about 5 to 10 minutes, the inhibition of sulfide species was observed to adversely affect the yields of iron sulfide molecular cluster formation, as well as the iron concentration in the systems. As shown in the voltammogram of FIG. 2, the injection of the scale inhibition solvent formulation removed the sulfide species (HS.sup.−/H.sub.2S), inhibited FeS.sub.(aq) formation from 0.6 μAmps to 0.05 μAmps, and reduced the Fe.sup.2+ concentrations from 1.8 μAmps to 0.95 μAmps while slightly increasing Fe.sup.2+ concentration. The initial concentration used for iron sulfide tests ranged from 100-125 μM for Fe.sup.2+ solution and 70-100 μM for H.sub.2S/HS.sup.− solution.

[0062] In FIGS. 2 and 3, the 5 mL, 10 mL, 15 mL, and 20 mL “injections” specifically refer to the injection or addition of inhibition solvent mixtures comprising CF.sub.3SO.sub.3CH.sub.3, Zn(CH.sub.3CO.sub.2).sub.2, and ZnCl.sub.2 during the simulated glass reactor and coreflood experiments to further prevent FeS and precursor formation. The dotted arrows in FIGS. 2 and 3 show a decreasing trend in both FeS.sub.(aq) and Fe.sup.2+ upon addition of the described chemical formulations. Based on core flood inhibition pilot tests described above (see FIG. 3), a suitable volume to completely inhibit FeS and analogous precursors (Fe.sup.2+ and H.sub.2S/HS.sup.−) ranged from about 20 mL to about 30 mL of the blended inhibition solvent mixture with correlated FeS.sub.(aq), Fe.sup.2+, and H.sub.2S/HS.sup.− current intensities of 0.15 μAmps, 2.0 μAmps, and 0.0 μAmps, respectively. For large scale field application in situ in a wellbore proximate a hydrocarbon-bearing formation, periodic batch injections of about 3 barrels to about 5 barrels for every about 30 to about 45 days will maintain the FeS.sub.(aq), Fe.sup.2+, and H.sub.2S/HS.sup.− current intensities leading to efficient prevention of FeS scale formation at reservoir conditions.

[0063] Overall reactions governing the FeS scale inhibition can generally be represented via Equations 4 through 6. Equations 4 and 5 show elimination of reactive sulfide species, which inhibits FeS.sub.(aq) formation, and Equation 6 shows reduction in the amounts of reactive iron(II), via transition to Fe.sup.2+ in FeCl.sub.3.

##STR00001##

[0064] Injection of the chemical solvent formulation including CF.sub.3SO.sub.3CH.sub.3, Zn(CH.sub.3CO.sub.2).sub.2, and CuCl.sub.2 not only prevented the crystal growth of molecular FeS.sub.(aq) clusters, but also removed the sulfide species and reduced the concentration of iron (II). This shows the capability of preventing FeS scale formation, for example at HPHT reservoir conditions. In addition to FeS products, typified transition metal sulfides such as PbS, ZnS, and HgS that usually occur as scale/deposition products in many hydrocarbon producing environments can be prevented or inhibited using methyl trifluoromethanesulfonate and copper chloride with zinc acetate. Treatment compositions and methods of the present disclosure can inhibit and remove both metastable polymorphs and stable polymorphs of scale, for example as shown in FIG. 6.

[0065] Coreflood Scale Inhibition Experiments In The Laboratory. Core flood injectivity tests were carried out on low-permeability, sulfur-bearing carbonate core samples to observe the growth, aggregation, and inhibition behavior of iron sulfide precursors. The core sample used in the present example exhibited the following properties: permeability, K=0.437 mD, porosity, 1=0.123, length, L=3.75 cm, and pore volume, V=5.4 mL. For each run under downhole conditions, the coreflood system was continuously flushed with UHP-N.sub.2 during the course of the experiments. The study was carried out in a linear mode at a temperature value of 310° F., a back-pressure of 1,000 psi, and an overburden pressure of 2,000 psi.

[0066] The equivalent hydrogen sulfide (H.sub.2S) and sulfide intermediates (HS.sup.−/S.sup.2−/S.sub.n.sup.−) required to form iron sulfide molecular clusters were obtained by injecting 0.5 M solutions of hydrochloric acid to release acid-volatile sulfides from the sulfur bearing carbonate core samples. This was followed by addition of 10 μM iron (II) solution to the core flood system. Cyclic voltammetric scans immediately taken from the coreflood experiments showed the formation and build-up of the aqueous FeS.sub.(aq) molecular clusters, Fe.sup.2+, and small amount of Fe.sup.2+ at reservoir conditions (as shown in FIG. 3).

[0067] Electroactive redox species responsible for the build-up FeS.sub.(aq) molecular cluster formation were monitored in real-time to assess the range of concentrations before and after the formation of the molecular clusters in the coreflood systems. The approximate concentration ranges for electroactive species in the sulfur-bearing carbonate core samples are presented in Table 1. Reactive “free” sulfide and the intermediate species (H.sub.2S/HS.sup.−) were not detected after the formation of the FeS.sub.(aq) molecular clusters (see FIGS. 1 and 2 versus FIG. 3). The lack of free sulfides in this experiment (FIG. 3) is likely due in part to the instantaneous incorporation of the vast majority of dissolved sulfide into the FeS.sub.(aq) molecular clusters. This observation shows that molecular FeS.sub.(aq) clusters play a critical role as precursors in FeS scaling and mineralization at HPHT reservoir conditions, for example in carbonate reservoirs.

TABLE-US-00001 TABLE 1 Approximate concentration ranges for forming FeS.sub.(aq) molecular clusters under HPHT conditions for carbonate core samples. REDOX SPECIES APPROXIMATE RANGE OF DETECTION Fe.sup.2+ 5-10 μM Fe.sup.3+(inorganic/organic) molecular FeS.sub.(aq) molecular H.sub.2S/HS.sup.− 10-17 nM S.sub.x.sup.n− 1-5 nM S.sub.8 n/a

[0068] Inhibition tests performed directly in the experimental HPHT coreflood system using the previously-described inhibition solvent also showed a similar inhibition performance against the FeS.sub.(aq) molecular clusters' crystal growth and a progressive reduction in iron (II) concentrations (FIG. 3). A final yellowish-brown solution produced after inhibition can be pumped from the reservoir or flowlines and discarded as waste.

[0069] The result of the inhibition performance versus intensities of FeS.sub.(aq) molecular cluster crystal decay is illustrated in FIG. 4, for example inhibition performance up to 90%. Also shown (in FIG. 5) is an up to 81% reduction in iron (II) concentration that was effected by the inhibition chemical formulation in the coreflood experiments.

[0070] FIG. 6 is a graphic representation of a reaction profile for the inhibition and potential nucleation of nano-particulate iron sulfide molecular clusters, FeS.sub.(aq), where after nucleation, aggregation of bulk stable and metastable FeS minerals and scaling in HPHT petroleum reservoir conditions can occur. FIG. 6 shows iron sulfide phase reactions and crystal growth through FeS.sub.(aq) molecular clusters in petroleum reservoirs can be effectively prevented or controlled at the cluster phase without directly impacting the reservoir flow assurance and permeability of the rock formation.

[0071] The singular forms “a,” “an,” and “the” include plural referents, unless the context clearly dictates otherwise. The term “about” when used with respect to a value or range refers to values including plus and minus 5% of the given value or range.

[0072] In the drawing and specification, there have been disclosed example embodiments of the present disclosure, and although specific terms are employed, the terms are used in a descriptive sense only and not for purposes of limitation. The embodiments of the present disclosure have been described in considerable detail with specific reference to these illustrated embodiments. It will be apparent, however, that various modifications and changes can be made within the spirit and scope of the disclosure as described in the foregoing specification, and such modifications and changes are to be considered equivalents and part of this disclosure.