WO2025065547A1 - Inhibiteurs de tartre polymères marqués au phosphonate et leurs procédés de production et d'utilisation - Google Patents

Inhibiteurs de tartre polymères marqués au phosphonate et leurs procédés de production et d'utilisation Download PDF

Info

Publication number
WO2025065547A1
WO2025065547A1 PCT/CN2023/122692 CN2023122692W WO2025065547A1 WO 2025065547 A1 WO2025065547 A1 WO 2025065547A1 CN 2023122692 W CN2023122692 W CN 2023122692W WO 2025065547 A1 WO2025065547 A1 WO 2025065547A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylenically unsaturated
phosphonate
composition
copolymer
scale
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2023/122692
Other languages
English (en)
Inventor
Shaohua Chen
Norah A. Aljeaban
Tianping Huang
Tao Chen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aramco Far East Beijing Business Services Co Ltd
Saudi Arabian Oil Co
Original Assignee
Aramco Far East Beijing Business Services Co Ltd
Saudi Arabian Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aramco Far East Beijing Business Services Co Ltd, Saudi Arabian Oil Co filed Critical Aramco Far East Beijing Business Services Co Ltd
Priority to PCT/CN2023/122692 priority Critical patent/WO2025065547A1/fr
Publication of WO2025065547A1 publication Critical patent/WO2025065547A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates

Definitions

  • the present disclosure generally relates to scale inhibition and, more specifically, polymeric scale inhibitors and methods for use thereof.
  • Scaling may commonly occur when operating a wellbore through natural processes and/or as a consequence of treatment operations utilized to promote production of a hydrocarbon resource from the wellbore.
  • scale refers to a mineral or salt residue formed through deposition from a fluid.
  • scaling refers to a deposition process that results in formation of a scale.
  • scaling and scaling formation may be used interchangeably herein.
  • scaling in a wellbore may result from one or more geothermal processes, oversaturation of produced formation water, re-precipitation of dissolved substances following a stimulation operation, contact between incompatible fluids, changing physical conditions (e.g., pressure, temperature, concentration, composition, and the like) , the like, and any combination thereof. Beyond the oilfield space, scaling may also occur in numerous other applications as well, such as in industrial processes employing cooling water, for instance.
  • Scale formation may result in significant negative consequences when operating a wellbore or during other industrial processes.
  • difficulties that may result from scaling in a wellbore include, but are not limited to, decreased formation permeability, occlusion of fluid flow pathways, damage to tools or production equipment and/or rendering such tools and production equipment inoperative, corrosion, and the like. Any of the foregoing may decrease productivity of a wellbore, shorten the lifetime of tools and production equipment, and sometimes necessitate costly and time-consuming operations to remove the scale. Consequently, there can be significant economic ramifications and process delays associated with scale formation.
  • Commonly encountered types of scale may include carbonate scale, sulfate scale, and siliceous scale. While all types of scale can be problematic, carbonate scale may be somewhat less difficult to address, since carbonate scale may sometimes be remediated through dissolution with a dilute organic acid and/or a mineral acid (e.g., hydrochloric acid or hydrobromic acid) . Chelating agents may also be used to re-dissolve carbonate and sulfate scales in some instances. Siliceous scales can be considerably more difficult to remediate and require a fluoride reagent, such as hydrofluoric acid, to affect their re-dissolution.
  • a fluoride reagent such as hydrofluoric acid
  • scale inhibitors are commonly used in the oilfield and other industries in which scaling may be problematic. Without being bound by theory or mechanism, scale inhibitors may prevent or slow crystallization and/or nucleation processes resulting in formation of a scale. In some instances, scale inhibitors may not entirely prevent the formation of scale, but they may limit the amount of scale that is formed and/or prevent formation of dense, crust-like scales that may be more difficult to remove.
  • scale inhibitors are commonly deployed in a subterranean formation using a squeeze treatment, in which a fluid containing the scale inhibitor is injected into a wellbore and slowly adsorbs into the surrounding subterranean formation. Pressure may be applied to promote this process. Once adsorbed into the subterranean formation, the scale inhibitor may be slowly released during production of a hydrocarbon resource and other fluids from the wellbore, thereby providing an ongoing supply of the scale inhibitor to limit or prevent scaling.
  • a commonly used small-molecule phosphonate scale inhibitor is aminotris (methylenephosphonic acid) (ATMP) , which is industrially synthesized via a Mannich reaction of phosphorus trichloride, formaldehyde, and ammonium chloride.
  • ATMP aminotris (methylenephosphonic acid)
  • a Mannich reaction of phosphorus trichloride, formaldehyde, and ammonium chloride is problematic for this scale inhibitor, in particular. For this reason, polymeric scale inhibitors are often more frequently used.
  • Polymeric scale inhibitors are commonly polyanionic polymers containing monomers such as, for example, acrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) , styrenesulfonic acid, and combinations thereof. Like small-molecule phosphonates, some polymeric scale inhibitors may also be synthetically challenging to produce. Even more problematically, it may be difficult to determine whether a polymeric scale inhibitor has been placed in a wellbore in a desired location and in an effective amount to prevent or limit scale formation, such as during a squeeze treatment. Similarly, it may be difficult to determine whether sufficient polymeric scale inhibitor remains during production to continue suppression of scaling. Extended retention of polymeric scale inhibitors in a subterranean formation may also be problematic in some instances.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • compositions comprising: a polymeric scale inhibitor comprising a copolymer of at least one anionic ethylenically unsaturated monomer and at least one ethylenically unsaturated phosphonate monomer.
  • the copolymer comprises a plurality of anionic groups and a plurality of phosphonate groups pendant to a backbone of the copolymer.
  • the present disclosure provides methods for inhibiting scale, comprising: providing a composition comprising a polymeric scale inhibitor comprising a copolymer of at least one anionic ethylenically unsaturated monomer and at least one ethylenically unsaturated phosphonate monomer, the copolymer comprising a plurality of anionic groups and a plurality of phosphonate groups pendant to a backbone of the copolymer; introducing the composition into a subterranean formation; and interacting the composition with a fluid susceptible to scale formation in the subterranean formation.
  • FIGS. 1A-1C are diagrams of a wellbore at various stages of a squeeze treatment according to one or more embodiments of the present disclosure.
  • FIG. 2 is a 1 H NMR spectrum in D 2 O of a copolymer scale inhibitor of the present disclosure.
  • Embodiments in accordance with the present disclosure generally relate to scale inhibition and, more specifically, polymeric scale inhibitors and methods for production and use thereof.
  • Scale inhibitors may be utilized to prevent or limit formation of various types of scale.
  • Polymeric scale inhibitors may be effective for this purpose, but it can be difficult to determine if a polymeric scale inhibitor has been placed in a desired location in a subterranean formation and in an effective amount to prevent or limit scale formation, such as during a squeeze treatment. Similarly, it may be difficult to determine whether sufficient polymeric scale inhibitor remains during production to continue suppression of scaling.
  • scaling may become unexpectedly problematic if the amount of the polymeric scale inhibitor drops to an insufficient level for preventing or limiting scaling and/or if the polymeric scale inhibitor was not correctly placed during a squeeze treatment. Although subsequent squeeze treatments may be conducted to replenish the polymeric scale inhibitor in the subterranean formation, doing so without knowledge of the current scale inhibitor loading may lead to unnecessary treatments and increased production costs.
  • the present disclosure addresses the foregoing issues by providing polymeric scale inhibitors that may be readily detected within a subterranean formation or in fluids produced therefrom.
  • the polymeric scale inhibitors resemble conventional polymeric scale inhibitors in terms of being polyanionic polymers but further incorporate a small amount of a monomer containing a phosphonate group, which may facilitate ready detection of the polymeric scale inhibitors, as well as provide other advantages.
  • the detection may be based upon detection of phosphorus or the phosphonate group.
  • any phosphonic acid groups i.e., in phosphonate half esters and phosphonic acids
  • the phosphonate group may further interact chemically with a subterranean formation to promote extended retention of the polymeric scale inhibitor therein.
  • the polymeric scale inhibitors of the present disclosure incorporate the phosphonate functional group found in small-molecule phosphonate scale inhibitors, scale inhibition by two different mechanisms, including potential synergy therebetween, may also occur when using the polymeric scale inhibitors described herein.
  • compositions comprising a polymeric scale inhibitor, in which the polymeric scale inhibitor comprises a copolymer of at least one anionic ethylenically unsaturated monomer and at least one ethylenically unsaturated phosphonate monomer.
  • the at least one ethylenically unsaturated phosphonate monomer may comprise a phosphonate ester, a phosphonate half ester, a phosphonic acid, or any combination thereof, any of which may be located pendant to a backbone of the copolymer.
  • the phosphonate group is a phosphonate ester.
  • the backbone of the copolymer is formed from a plurality of polymerized groups having ethylenic unsaturation, such that the backbone consists of a plurality of secondary carbon atoms (i.e., methylene carbons) and a plurality of tertiary carbon atoms (i.e., methine carbon atoms) linked by single bonds, wherein the anionic groups and the phosphonate groups are attached directly or indirectly to the backbone.
  • Suitable examples of anionic ethylenically unsaturated monomers and ethylenically unsaturated phosphonate monomers are provided hereinbelow.
  • the resulting copolymer may be a random copolymer comprising a plurality of anionic groups and a plurality of phosphonate groups pendant to the backbone of the copolymer. That is, the anionic groups and the phosphonate groups may be present within a side chain (or define the entirety of a side chain) extending from the polymer backbone via the tertiary carbon atoms.
  • compositions of the present disclosure may be formulated with an aqueous fluid in which the polymeric scale inhibitor is at least partially dissolved and preferably fully dissolved.
  • Suitable aqueous fluids may include, but are not limited to, water, salt water, mixtures of water and a water-miscible organic solvent, brine, seawater, produced water, or any combination thereof.
  • the term “brine” refers to any aqueous salt solution having a greater amount of total dissolved salt than does seawater, including saturated aqueous salt solutions.
  • the polymeric scale inhibitor When at least partially dissolved in an aqueous fluid, the polymeric scale inhibitor may be present in the aqueous fluid in an amount sufficient to limit or prevent scaling once the polymeric scale inhibitor is suitably placed.
  • the polymeric scale inhibitor may be present in the aqueous fluid in an amount ranging from about 0.5 wt%to about 50 wt%, or about 1 wt%to about 40 wt%, or about 5 wt%to about 50 wt%, or about 5 wt%to about 30 wt%, or about 10 wt%to about 25 wt%, or about 10 wt%to about 40 wt%, each based on total mass of the composition.
  • the at least one anionic ethylenically unsaturated monomer may comprise at least one anionic ethylenically unsaturated monomer that is not an ethylenically unsaturated phosphonate monomer.
  • suitable anionic ethylenically unsaturated monomers may include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, vinylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and any combination thereof.
  • anionic ethylenically unsaturated monomers may also be suitable for forming a polymeric scale inhibitor of the present disclosure, and the foregoing listing of anionic ethylenically unsaturated monomers should be considered illustrative and non-limiting.
  • the at least one anionic ethylenically unsaturated monomer may comprise two or more anionic ethylenically unsaturated monomers, such that the copolymer comprises at least a terpolymer (e.g., a random terpolymer) of the two or more anionic ethylenically unsaturated monomers and the at least one ethylenically unsaturated phosphonate monomer.
  • the at least one anionic ethylenically unsaturated monomer may comprise at least styrenesulfonic acid, an acrylic acid (including acrylic acid, methacrylic acid, or any combination thereof) , or any combination thereof.
  • the molar ratio may range from 1: 99 to 99: 1, or 1: 9 to 9:1, or 1: 5 to 5: 1, based on a combined molar amount of the two anionic ethylenically unsaturated monomers.
  • Suitable ethylenically unsaturated phosphonate monomers may include, but are not limited, to, vinylphosphonic acid, mono-or dialkyl vinylphosphonates, vinylidenediphosphonic acid; mono-, di-, tri-, or tetraalkyl vinylidenediphosphonates; allylphosphonic acid; mono-or dialkyl allylphosphonates; N-acrylamidomethylphosphonic acid; mono-or dialkyl N-acrylamidomethylphosphonates; N-methacrylamidomethylphosphonic acid; mono-or dialkyl N-methacrylamidomethylphosphonates; 2- (acryloyloxy) ethylphosphonic acid; mono-or dialkyl 2- (acryloyloxy) ethylphosphonates; 2- (methacryloyloxy) ethylphosphonic acid; mono-or dialkyl 2- (methacryloyloxy) ethylphosphonic acid; mono-or dialkyl 2- (methacryl
  • ethylenically unsaturated phosphonate monomers may also be suitable for forming a polymeric scale inhibitor of the present disclosure, and the foregoing listing of ethylenically unsaturated phosphonate monomers should be considered illustrative and non-limiting.
  • other ethylenically unsaturated phosphonate monomers that may also be suitable include those described in U.S. Patent 9,187,503, which is incorporated herein by reference.
  • the at least one ethylenically unsaturated phosphonate monomer may comprise at least one ethylenically unsaturated phosphonate ester, which may be a full ester, a half ester, or any combination thereof, preferably a full ester ethylenically unsaturated phosphonate monomer.
  • the at least one ethylenically unsaturated phosphonate monomer may comprise at least a dialkyl allylphosphonate, such as diethyl allylphosphonate. Vinylidenediphosphonic acid and its full-and half esters are additional illustrative examples.
  • the polymeric scale inhibitors of the present disclosure may contain the at least one ethylenically unsaturated phosphonate monomer in any amount that is at least effective to facilitate detection of the polymeric scale inhibitor in a given location.
  • the amount effective for detection may vary depending upon the chosen detection technique and the location or fluid in which the polymeric scale inhibitor needs to be detected.
  • a molar percentage of the at least one ethylenically unsaturated phosphonate monomer may be about 5 mol%or below, or about 4 mol%or below, or about 3 mol%or below, or about 2 mol%or below, or about 1 mol%or below, as measured relative to a total molar amount of monomers in the copolymer.
  • the balance of the copolymer may comprise the at least one anionic ethylenically unsaturated monomer, such as about 95 mol%or above, or about 96 mol%or above, or about 97 mol%or above, or about 98 mol%or above, or about 99 mol%or above, provided that a non-zero amount of the at least one ethylenically unsaturated phosphonate is present in an amount effective to promote detection.
  • the amount of the at least one ethylenically unsaturated phosphonate monomer may also be effective to increase retention of the polymeric scale inhibitor in a subterranean formation, such as during and following a squeeze treatment, as measured relative to a copolymer comprising the at least one anionic ethylenically unsaturated monomer alone.
  • the above amounts of the at least one ethylenically unsaturated phosphonate monomer may be sufficient for this purpose.
  • Higher loadings of the at least one ethylenically unsaturated phosphonate monomer may also be included, if needed, to increase retention of the polymeric scale inhibitor in a subterranean formation during or following a squeeze treatment.
  • the molar percentage of the at least one ethylenically unsaturated phosphonate monomer may be up to about 25 mol%, or up to about 20 mol%, or up to about 15 mol%, or up to about 10 mol%, as measured relative to a total molar amount of monomers in the copolymer.
  • the polymeric scale inhibitors of the present disclosure may be produced by free radical polymerization using a suitable radical initiator, preferably in an aqueous fluid.
  • suitable radical initiators may include, but are not limited to, organic peroxides, organic peroxyacids, organic hydroperoxides, inorganic peroxides, inorganic peracetates, inorganic persulfates, inorganic hydroperoxides, hydrogen peroxide, chlorine dioxide, sodium chlorate, sodium hypochlorite, organotin hydrides, azo compounds such as 4, 4'-azobiscyanovaleric acid or 4, 4’-azobisisobutyronitrile, and the like.
  • Electromagnetic radiation e.g., ultraviolet or ionizing radiation, such as gamma radiation
  • electrolysis, ultrasound, or the like may also be utilized to initiate radical polymerization as well.
  • compositions of the present disclosure may further comprise a second scale inhibitor comprising at least one non-polymeric scale inhibitor, such as a non-polymeric phosphonate scale inhibitor.
  • non-polymeric phosphonate scale inhibitors that may be present in the compositions of the present disclosure include, but are not limited to, 1-hydroxyethane 1, 1-diphosphonic acid (HEDP) , aminotris (methylenephosphonic acid) (ATMP) , ethylenediamine tetrakis (methylenephosphonic acid) (EDTMP) , tetramethylenediamine tetrakis (methylenephosphonic acid) (TDTMP) , hexamethylenediamine tetrakis (methylenephosphonic acid) (HDTMP) , diethylenetriamine pentakis (methylenephosphonic acid) (DTPMP) , triethylenetetramine hexakis (methylenephosphonic acid) , bis (hexamethylenetriamine) pentakis (methylenephosphonic acid)
  • compositions of the present disclosure may include, but are not limited to, surfactants, foaming compounds, anti-foaming compounds, particulates, metal oxides (e.g., silica, alumina, titania, zirconia, and the like) , salts, organic solvents, wetting agents, dispersants, emulsifying agents, de-emulsifying agents, penetrants, preservatives, colorants, acids, bases, buffers, chelating agents, viscosifiers, thixotropic agents, stabilizers, film-forming agents, plasticizers, antioxidants, fluid loss additives, diverting agents, tackifying agents, corrosion inhibitors, scavengers, breakers, the like, and any combination thereof.
  • Suitable examples of these optional components will be familiar to persons having ordinary skill in the art. Furthermore, persons having ordinary skill in the art will be
  • compositions of the present disclosure may be introduced into a subterranean formation, such as by performing a squeeze treatment, and then interacted with a fluid susceptible to scale formation in the subterranean formation. Through such an interaction, the compositions may prevent, limit, decrease, or delay formation of scale from the fluid in at least a portion of the subterranean formation or in a fluid produced from the subterranean formation, as measured relative to an amount of uninhibited scaling from the fluid (i.e., without a scale inhibitor being present) .
  • the fluid may be susceptible to formation of carbonate scale, sulfate scale, sulfide scale, siliceous scale, or any combination thereof.
  • compositions of the present disclosure may prevent or limit formation of at least carbonate scale and/or sulfate scale.
  • Metal ions that may promote formation of carbonate scale, sulfate scale, or any combination thereof may include, but are not limited to, magnesium, calcium, strontium, and barium.
  • compositions containing the polymeric scale inhibitors of the present disclosure may be introduced to a subterranean formation by performing a squeeze treatment.
  • a polymeric scale inhibitor of the present disclosure may be at least partially dissolved in an aqueous fluid and introduced into a wellbore penetrating the subterranean formation.
  • the manner in which the squeeze treatment is performed may depend on various factors, such as, for example, the downhole temperature, the downhole pH, the geology of the subterranean formation, and the like. Additional details in this regard are provided hereinafter.
  • a squeeze treatment may be conducted in conjunction with any subterranean operation in which inhibition of scaling is desired, either during the subterranean operation itself or during subsequent production of a hydrocarbon resource.
  • the polymeric scale inhibitor may be introduced into the subterranean formation using a fluid separate from that performing a main subterranean operation, or the polymeric scale inhibitor may be introduced within the fluid performing the main subterranean operation.
  • Illustrative subterranean operations which the polymeric scale inhibitors of the present disclosure may be utilized in conjunction with include, but are not limited to, drilling operations, stimulation operations, remediation operations, and sand control operations. The foregoing may include specific examples, such as, but not limited to, fracturing operations, gravel packing operations, acidizing operations, descaling operations, consolidation operations, workover operations, cleanup operations, diversion operations, and the like.
  • the fluid containing the polymeric scale inhibitor may be preceded by a pre-flush fluid lacking the polymeric scale inhibitor.
  • the pre-flush fluid may contain additional components that may encourage the polymeric scale inhibitor to enter the subterranean formation more readily.
  • the pre-flush fluid may contain one or more surfactants that may encourage uptake of the polymeric scale inhibitor by the subterranean formation.
  • a shut-in period of suitable length may follow to allow the polymeric scale inhibitor sufficient time to adsorb into the subterranean formation.
  • the shut-in period may range from about 1 hour to about 72 hours, or about 6 hours to about 30 hours, or about 12 hours to about 24 hours, or about 18 hours to about 36 hours.
  • fluids may be produced from the subterranean formation, including a hydrocarbon resource, produced formation water, and/or other aqueous fluids introduced to the subterranean formation.
  • the polymeric scale inhibitor may prevent or limit scale formation in the subterranean formation and/or in fluids leaving the subterranean formation and subsequently collected and/or further processed.
  • the polymeric scale inhibitor may undergo leeching from the subterranean formation during production, and the amount of polymeric scale inhibitor leeched from the formation may be effective to prevent, limit, decrease, or delay scaling associated with the fluid production.
  • the amount effective to prevent, limit, decrease, or delay scaling may be referred to as the minimum inhibitor concentration (MIC) .
  • the MIC of the polymeric scale inhibitor may range from about 1 ppm to about 10,000 ppm, or about 1 ppm to about 1,000 ppm, or about 1 ppm to about 250 ppm, or about 1 ppm to about 100 ppm, or about 1 ppm to about 50 ppm.
  • the amount of the polymeric scale inhibitor in a fluid produced from the subterranean formation may be determined by a suitable monitoring technique.
  • the fluid may be analyzed for the polymeric scale inhibitor downhole, or the subterranean formation itself may be analyzed to determine the location of the polymeric scale inhibitor and amount thereof.
  • a fluid sample may be obtained from the wellbore and analyzed in a testing facility by a suitable assay technique.
  • Suitable monitoring techniques for determining the amount of polymeric scale inhibitor will be familiar to one having ordinary skill in the art.
  • Illustrative techniques include 1 H NMR, 31 P NMR, inductively coupled plasma (ICP) spectroscopy, spectrophotometry, gas chromatography, particle-induced X-ray emission (PIXE) , and the like.
  • monitoring may be take place by analyzing for phosphorus within the polymeric scale inhibitor.
  • the sample may be analyzed as-obtained or undergo various treatment steps to render the sample into a form suitable for analysis.
  • the polymeric scale inhibitor itself may be directly detected or undergo conversion into a form more suitable to detect the phosphorus that is present therein.
  • the sample when conducting 1 H NMR or 31 P NMR, protons or phosphorus within the polymeric scale inhibitor itself may be detected.
  • the sample When conducting ICP spectroscopy or spectrophotometry, for example, the sample may be processed to degrade the polymeric scale inhibitor into inorganic phosphorous, which may then be analyzed.
  • a chromogenic reagent may be utilized in conjunction with spectrophotometric determination of the polymeric scale inhibitor to facilitate detection thereof.
  • the squeeze treatment may be repeated as needed to replenish the polymeric scale inhibitor within the subterranean formation.
  • a determination of the amount of polymeric scale inhibitor present in the subterranean formation may be conducted in accordance with the description above.
  • FIGS. 1A-1C are diagrams of a wellbore at various stages of a squeeze treatment according to one or more embodiments of the present disclosure.
  • FIG. 1A shows the stage during which a polymeric scale inhibitor within fluid 104 is initially introduced to wellbore 102 within subterranean formation 100.
  • pre-flush fluid 106 may precede fluid 104 containing the polymeric scale inhibitor.
  • Pre-flush fluid 106 and fluid 104 approach treatment zone 110, which may contain a plurality of fractures 112 or sufficient porosity to receive the polymeric scale inhibitor.
  • FIG. 1B shows the shut-in stage of the squeeze treatment, during which time the polymeric scale inhibitor interacts with subterranean formation 100 and becomes adsorbed therein.
  • FIG. 1C shows the production stage following a squeeze treatment and removal of fluid 104 and pre-flush fluid 106 from wellbore 102.
  • polymeric scale inhibitor 116 may remain adsorbed within treatment zone 110 of subterranean formation 100.
  • formation fluids 120 including formation water and/or hydrocarbons, may enter wellbore 102 and progress toward the exit thereof at the earth’s surface.
  • Polymeric scale inhibitor 116 may gradually leach from subterranean formation 100 into formation fluids 120 and be conveyed therewith during production.
  • polymeric scale inhibitor 116 may prevent, limit, decrease, or delay scaling within wellbore 102 or after exiting wellbore 102.
  • the amount of polymeric scale inhibitor 116 within formation fluids 120 may be determined using a suitable monitoring technique to evaluate the effectiveness of the squeeze treatment and/or to determine when a squeeze treatment needs to be repeated to replenish polymeric scale inhibitor 116 within treatment zone 110.
  • Embodiments disclosed herein include:
  • compositions for inhibiting scale comprise: a polymeric scale inhibitor comprising a copolymer of at least one anionic ethylenically unsaturated monomer and at least one ethylenically unsaturated phosphonate monomer; wherein the copolymer comprises a plurality of anionic groups and a plurality of phosphonate groups pendant to a backbone of the copolymer.
  • Methods for inhibiting scale comprise: providing the composition of any one of A; introducing the composition into a subterranean formation; and interacting the composition with a fluid susceptible to scale formation in the subterranean formation.
  • Embodiments A and B may comprise one or more of the following additional embodiments in any combination.
  • Element 1 wherein the at least one anionic ethylenically unsaturated monomer comprises two or more anionic ethylenically unsaturated monomers.
  • Element 2 wherein the at least one anionic ethylenically unsaturated monomer comprises styrenesulfonic acid, an acrylic acid, or any combination thereof.
  • Element 3 wherein the at least one ethylenically unsaturated phosphonate monomer comprises at least two phosphonate ester groups or at least two phosphonic acid groups.
  • Element 4 wherein the at least one ethylenically unsaturated phosphonate monomer comprises at least one ethylenically unsaturated phosphonate ester.
  • Element 5 wherein the at least one ethylenically unsaturated phosphonate ester comprises a dialkyl allylphosphonate.
  • Element 6 wherein a molar percentage of the at least one ethylenically unsaturated phosphonate monomer is about 5 mol%or below, as measured relative to a total molar amount of monomers in the copolymer.
  • composition further comprises at least one non-polymeric phosphonate scale inhibitor.
  • composition further comprises an aqueous fluid in which the copolymer is at least partially dissolved.
  • Element 9 wherein the fluid is susceptible to formation of carbonate scale, sulfate scale, siliceous scale, or any combination thereof.
  • Element 9A wherein the fluid is susceptible to formation of carbonate scale, sulfate scale, or any combination thereof.
  • Element 10 wherein the composition decreases formation of scale from the fluid in at least a portion of the subterranean formation, as measured relative to an amount of uninhibited scaling from the fluid.
  • Element 11 wherein the composition is introduced into the subterranean formation by performing a squeeze treatment.
  • Element 12 wherein the method further comprises determining a location of the copolymer in the subterranean formation by analyzing for phosphorus.
  • Element 13 wherein the method further comprises determining an amount of the copolymer in a fluid produced from the subterranean formation by analyzing for phosphorus.
  • exemplary combinations applicable to A include, but are not limited to: 1 or 2, and 3; 1 or 2, and 4; 1 or 2, and 5; 1 or 2, and 6; 1 or 2, and 7; 1 or 2, and 8; 3 and 5; 3 and 6; 3 and 7; 3 and 8; 4 and 5; 4 and 6; 4 and 7; 4 and 8; 6 and 7; 6 and 8; 7 and 8; 6-8; 1 or 2, 6, and 7; 1 or 2, 6 and 8; 1 or 2, and 6-8; 1 or 2, 7, and 8; 5-7; 5, and 6-8; 5, 6, and 8; and 5, 7, and 8.
  • Additional exemplary combinations applicable to B include any of the foregoing, optionally in further combination with one or more of 9, 9A, 10, 11, or 12.
  • Additional exemplary combinations applicable to B include, but are not limited to, 9 or 9A, and 1 or 2; 9 or 9A, and 3; 9 or 9A, and 4; 9 or 9A, and 5; 9 or 9A, and 6; 9 or 9A, and 7; 9 or 9A, and 8; 9 or 9A, and 10; 9 or 9A, and 11; 9 or 9A, and 12; 9 or 9A, and 13; 9 or 9A, 12, and 13; 10, and 1 or 2; 10 and 3; 10 and 4; 10 and 5; 10 and 6; 10 and 7; 10 and 8; 10 and 11; 10 and 12; 10 and 13; 10, 12, and 13; 11, and 1 or 2; 11 and 3; 11 and 4; 11 and 5; 11 and 6; 11 and 7; 11 and 8; 11 and 12; 11 and 13; 11-13; 11, 8, and 1 or 2; 11, 8, and 3; 11, 8, and 4; 11, 8, and 5; 11, 8, and 6; 11, 8, and 7; 11, 8, and 12; 11, 8, and 13; 8 and 11-13; 11, and 1 or 2
  • a composition comprising:
  • a polymeric scale inhibitor comprising a copolymer of at least one anionic ethylenically unsaturated monomer and at least one ethylenically unsaturated phosphonate monomer;
  • the copolymer comprises a plurality of anionic groups and a plurality of phosphonate groups pendant to a backbone of the copolymer.
  • Clause 2 The composition of clause 1, wherein the at least one anionic ethylenically unsaturated monomer comprises two or more anionic ethylenically unsaturated monomers.
  • Clause 3 The composition of clause 1 or clause 2, wherein the at least one anionic ethylenically unsaturated monomer comprises styrenesulfonic acid, an acrylic acid, or any combination thereof.
  • Clause 4 The composition of any one of clauses 1-3, wherein the at least one ethylenically unsaturated phosphonate monomer comprises at least two phosphonate ester groups or at least two phosphonic acid groups.
  • Clause 5 The composition of any one of clauses 1-4, wherein the at least one ethylenically unsaturated phosphonate monomer comprises at least one ethylenically unsaturated phosphonate ester.
  • Clause 6 The composition of clause 5, wherein the at least one ethylenically unsaturated phosphonate ester comprises a dialkyl allylphosphonate.
  • Clause 7 The composition of any one of clauses 1-6, wherein a molar percentage of the at least one ethylenically unsaturated phosphonate monomer is about 5 mol%or below, as measured relative to a total molar amount of monomers in the copolymer.
  • Clause 8 The composition of any one of clauses 1-7, further comprising: at least one non-polymeric phosphonate scale inhibitor.
  • Clause 9 The composition of any one of clauses 1-8, further comprising: an aqueous fluid in which the copolymer is at least partially dissolved.
  • composition interacting the composition with a fluid susceptible to scale formation in the subterranean formation.
  • Clause 11 The method of clause 10, wherein the fluid is susceptible to formation of carbonate scale, sulfate scale, siliceous scale, or any combination thereof.
  • Clause 12 The method of clause 10 or clause 11, wherein the composition decreases formation of scale from the fluid in at least a portion of the subterranean formation, as measured relative to an amount of uninhibited scaling from the fluid.
  • Clause 13 The method of any one of clauses 10-12, wherein the at least one anionic ethylenically unsaturated monomer comprises two or more anionic ethylenically unsaturated monomers.
  • Clause 14 The method of any one of clauses 10-13, wherein the at least one anionic ethylenically unsaturated monomer comprises styrenesulfonic acid, an acrylic acid, or any combination thereof.
  • Clause 15 The method of any one of clauses 10-14, wherein the at least one ethylenically unsaturated phosphonate monomer comprises at least two phosphonate ester groups or at least two phosphonic acid groups.
  • Clause 16 The method of any one of clauses 10-15, wherein the at least one ethylenically unsaturated phosphonate monomer comprises at least one ethylenically unsaturated phosphonate ester.
  • Clause 17 The method of clause 16, wherein the at least one ethylenically unsaturated phosphonate ester comprises a dialkyl allylphosphonate.
  • Clause 18 The method of any one of clauses 10-17, wherein a molar percentage of the at least one ethylenically unsaturated phosphonate monomer is about 5 mol%or below, as measured relative to a total molar amount of monomers in the copolymer.
  • Clause 19 The method of any one of clauses 10-18, wherein the composition further comprises an aqueous fluid in which the copolymer is at least partially dissolved.
  • Clause 20 The method of clause 19, wherein the composition is introduced into the subterranean formation by performing a squeeze treatment.
  • Diethyl allylphosphonate (DEAP) , acrylic acid (AA) , and styrenesulfonic acid (SSA) were combined in deionized water.
  • concentration of diethyl allylphosphonate was fixed at 1 mol%relative to total monomers, and the relative ratio of the other two monomers was varied, as specified in Table 1 below.
  • the pH was adjusted to a range of 6-7 with NaOH before heating to 50°C and then adding ammonium persulfate initiator (0.15 wt%relative to total monomers) to initiate polymerization. After heating overnight at 50°C, the reaction mixture was dialyzed against deionized water to remove monomer residues.
  • the dialysis was conducted by transferring the reaction mixture into a dialysis bag having a molecular weight cutoff of 3500 g/mol, and allowing the dialysis to take place over three days to remove unreacted monomers and initiator.
  • the resulting aqueous polymer solutions had a polymer content ranging from 30-50%by mass.
  • Polymer molecular weights (Mw values) and molecular weight distributions were determined by gel permeation chromatography using a single-pump Agilent Technologies system employing a light-scattering detector, refractive index detector, and a viscosity detector.
  • FIG. 2 is a 1 H NMR spectrum in D 2 O of a copolymer formed as above. As shown, the phosphonate protons were observed as sharp signals and were well-resolved from the signals of the other monomers. No signals from residual DEAP monomer were observed. 31 P NMR spectroscopy (not shown) indicated essentially a single chemical shift environment for phosphorus. Analysis of the 1 H or 31 P signals may be utilized to promote detection of the copolymers during use.
  • CaCO 3 scale inhibition testing was conducted by combining 10 mL of Brine B with various amounts of the copolymer solutions prepared as above, and 10 mL of Brine A was then added. The combined samples were sealed in a bottle and heated at 105°C for 24 hours. Control samples omitting the copolymer solutions were prepared and handled similarly. After heating, the samples were cooled to room temperature and then filtered through a 0.45 ⁇ m syringe filter. The filtrate was then diluted with a known volume of water to afford an anticipated calcium concentration ranging from 10 ppm to 200 ppm.
  • the initially prepared samples were further diluted with a known volume of water to afford a Ca 2+ concentration within the calibration range. From the measured Ca 2+ concentrations, the scale inhibition rate percentage (SIR%) was determined according to Equation 1,
  • [Ca 2+ ] a is the Ca 2+ concentration of the copolymer-containing sample after heat aging
  • [Ca 2+ ] b is the Ca 2+ concentration of a blank sample lacking scale inhibitor
  • [Ca 2+ ] o is the original Ca 2+ concentration of the copolymer-containing sample obtained from the mixed brine before heat aging.
  • Table 3 summarizes SIR%values for Sample 2 [99% (50%AA/50%SSA) /1%DEAP] at various loading of the copolymer in the brine mixture when used for suppressing CaCO 3 scaling and CaSO 4 scaling. Without the polymeric scale inhibitor being present, about 70%of the calcium precipitated, both for the carbonate and the sulfate brines.
  • the copolymer was effective for inhibiting precipitation of both CaCO 3 and CaSO 4 , and the effectiveness for suppressing precipitation increased with increasing concentration of the copolymer.
  • references in the appended claims to an apparatus or system or a component of an apparatus or system being adapted to, arranged to, capable of, configured to, enabled to, operable to, or operative to perform a particular function encompasses that apparatus, system, or component, whether or not it or that particular function is activated, turned on, or unlocked, as long as that apparatus, system, or component is so adapted, arranged, capable, configured, enabled, operable, or operative.
  • compositions described herein may be free of any component or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein.
  • the term “comprising” is considered synonymous with the term “including.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des compositions comprenant un inhibiteur de tartre polymère pouvant être utilisées pour prévenir la formation de tartre dans une formation souterraine ou d'autres emplacements soumis à l'entartrage. L'inhibiteur de tartre polymère comprend un copolymère d'au moins un monomère anionique éthylénique insaturé et d'au moins un monomère phosphonate éthylénique insaturé, le copolymère comprenant une pluralité de groupes anioniques et une pluralité de groupes phosphonate pendant à un squelette du copolymère. Les groupes phosphonate peuvent faciliter la détection du copolymère dans la formation souterraine ou après l'extraction dans la formation souterraine.
PCT/CN2023/122692 2023-09-28 2023-09-28 Inhibiteurs de tartre polymères marqués au phosphonate et leurs procédés de production et d'utilisation Pending WO2025065547A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/122692 WO2025065547A1 (fr) 2023-09-28 2023-09-28 Inhibiteurs de tartre polymères marqués au phosphonate et leurs procédés de production et d'utilisation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/122692 WO2025065547A1 (fr) 2023-09-28 2023-09-28 Inhibiteurs de tartre polymères marqués au phosphonate et leurs procédés de production et d'utilisation

Publications (1)

Publication Number Publication Date
WO2025065547A1 true WO2025065547A1 (fr) 2025-04-03

Family

ID=95204225

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/122692 Pending WO2025065547A1 (fr) 2023-09-28 2023-09-28 Inhibiteurs de tartre polymères marqués au phosphonate et leurs procédés de production et d'utilisation

Country Status (1)

Country Link
WO (1) WO2025065547A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1496338A (zh) * 2001-03-15 2004-05-12 Ge ���Ĺ�˾ 用于控制含水体系中水垢形成和沉积的方法
CN102066389A (zh) * 2008-10-22 2011-05-18 科莱恩金融(Bvi)有限公司 烯属不饱和膦酸盐化合物、由其制备的聚合物及其用途
CN103803729A (zh) * 2012-11-15 2014-05-21 中国石油化工股份有限公司 一种共聚物阻垢分散剂及其制备方法
CN104650273A (zh) * 2013-11-22 2015-05-27 罗门哈斯公司 (甲基)丙烯酸类-丙烯共聚物及其制备方法
TW201706393A (zh) * 2015-04-02 2017-02-16 克萊瑞特國際股份有限公司 抑制硫化物垢之組成物與方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1496338A (zh) * 2001-03-15 2004-05-12 Ge ���Ĺ�˾ 用于控制含水体系中水垢形成和沉积的方法
CN102066389A (zh) * 2008-10-22 2011-05-18 科莱恩金融(Bvi)有限公司 烯属不饱和膦酸盐化合物、由其制备的聚合物及其用途
CN103803729A (zh) * 2012-11-15 2014-05-21 中国石油化工股份有限公司 一种共聚物阻垢分散剂及其制备方法
CN104650273A (zh) * 2013-11-22 2015-05-27 罗门哈斯公司 (甲基)丙烯酸类-丙烯共聚物及其制备方法
TW201706393A (zh) * 2015-04-02 2017-02-16 克萊瑞特國際股份有限公司 抑制硫化物垢之組成物與方法

Similar Documents

Publication Publication Date Title
US5018577A (en) Phosphinate inhibitor for scale squeeze applications
US4401789A (en) Enhanced oil recovery methods and systems
AU706503B2 (en) Method for metal sulfate scale control in harsh oilfield conditions
CN109641768B (zh) 对增强的油和/或气体回收方法中的生产用水进行处理的方法
AU2016200974B2 (en) Thermally stable scale inhibitor compositions
AU2007204243B2 (en) Scale inhibiting well treatment
US5167828A (en) Phosphinate-containing polymers for controlling scale in underground petroleum-containing formations and equipment associated therewith
US20100307753A1 (en) Methods of Treating Flowback Water
EP1639228A2 (fr) Procede pour stimuler un champ petrolifere consistant a utiliser differents antitartres
EP2052050B1 (fr) Traitement de puits
CA2462417C (fr) Composition inhibitrice de depots pour les milieux riches en sels mineraux incrustants
WO2007017815A2 (fr) Inhibiteurs de calamine compatibles avec l'acidification des gres
GB2193738A (en) Barium sulfate scale control
WO2014055340A1 (fr) Inhibiteurs d'entartrage polymères traçables et procédé d'utilisation de tels inhibiteurs d'entartrage
JPH07173226A (ja) ビニルスルホン酸ポリマー
US5213691A (en) Phosphonate-containing polymers for controlling scale in underground petroleum-containing formations and equipment associated therewith
WO2025065547A1 (fr) Inhibiteurs de tartre polymères marqués au phosphonate et leurs procédés de production et d'utilisation
Khormali et al. Trends in using organic compounds as scale inhibitors: Past, present, and future scenarios
DK1910495T3 (en) BRAND TREATMENT FOR CASTLE INHIBITION
US20070062879A1 (en) Scale inhibition in water systems
EP3124510B1 (fr) Procédé d'obtention de terpolymères aléatoires dérivés d'acide itaconique et d'acide aconitique, et/ou leurs isomères, et alcénylsulfonates de sodium et utilisation du produit obtenu
CA3224442A1 (fr) Procedes et compositions d'inhibiteur d'entartrage dans des conditions de fonctionnement difficiles
NZ620018A (en) Well servicing fluid and method of servicing a well with the fluid

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23953694

Country of ref document: EP

Kind code of ref document: A1