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WO1990004159A1 - Procede de controle de la teneur en antitartre polyacrylique - Google Patents

Procede de controle de la teneur en antitartre polyacrylique Download PDF

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Publication number
WO1990004159A1
WO1990004159A1 PCT/US1989/004563 US8904563W WO9004159A1 WO 1990004159 A1 WO1990004159 A1 WO 1990004159A1 US 8904563 W US8904563 W US 8904563W WO 9004159 A1 WO9004159 A1 WO 9004159A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyacrylic acid
acid
solution
polyacrylic
concentration
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.)
Ceased
Application number
PCT/US1989/004563
Other languages
English (en)
Inventor
John Hen
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.)
Mobil Oil AS
Original Assignee
Mobil Oil AS
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 Mobil Oil AS filed Critical Mobil Oil AS
Publication of WO1990004159A1 publication Critical patent/WO1990004159A1/fr
Priority to GB9105089A priority Critical patent/GB2245360B/en
Priority to NO911363A priority patent/NO302675B1/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1826—Organic contamination in water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment

Definitions

  • This invention relates to a method for monitoring polyacrylic scale inhibitor content in the presence of an interfering polyvalent cation.
  • Scale deposits frequently occur in the production of water, oil and gas from subterranean formations and can result in plugging of well bores, well casing perforations and tubing strings, as well as sticking of downhole safety valves, downhole pumps and other downhole and surface equipment and lines. Scale deposits can occur as a result of mixing of incompatible waters in the well which produce precipitates, or as a result of temperature and pressure changes in the produced waters during production. Generally, incompatible waters occur in waterflooding, such as when injected sea water mixes with formation water in the borehole during water breakthrough.
  • scale deposited due to changes in supersaturation or solubility of minerals in the formation or produced waters caused by pressure and temperature changes, or changes in other physical and chemical parameters, such as gas composition and ratio of gas/oil/water.
  • Scale may also be formed from corrosion of metal equipment used in the subterranean oil and gas production. Scale formation is also a problem in aqueous systems used in cooling towers, boilers and the like. Precipitation frequently encountered as scale includes calcium carbonate, calcium sulfate, barium sul ate, magnesium carbonate, magnesium sulfate, and strontium sulfate.
  • Scale formation can be reduced by the introduction of inhibitors into the formation.
  • Various inhibitors are known, including a widely used class of materials which are carboxylated polymers. Typically, these are polymers and copolymers of acrylic or methacrylic acids, commonly referred to as polyacrylic acids.
  • polyacrylic acids As disclosed by Rothman in U.S. Patent 4,514,504, it is desirable to have a method for monitoring the polyacrylic acid content of aqueous systems to know whether additional quantities of polyacrylic acid need to be added to maintain the optimum levels necessary to reduce scale formation.
  • the method disclosed in Rothman involves initially lowering the pH of the system to 2-3, but this leads to a problem where the aqueous system contains ions having a valence equal to or greater than 3, such as Fe (III), Cr (III) and Al (III), since the latter form complexes with polyacrylic acid at such pH values.
  • An object of the present invention is therefore to obviate or alleviate this problem.
  • this invention resides in a method for determining the concentration of polyacrylic acid in a solution containing a polyvalent cation which has a valence of at least 3, and is capable of reacting with the polyacrylic acid, comprising:
  • Figure 1 is a plot of the degree of ionization as a function of pH for polyacrylic acid of molecular weight of 1000 in a 1 molar (1M) aqueous solution of NaCl.
  • Figure 3 contains plots of absorbance vs. content of phosphino-polyacrylic acid inhibitor in the absence of Fe (III), and in the presence of 25 ppm Fe (III) at a pH of 2.5.
  • Figure 4 is a plot of absorbance as a function of content of polyacrylic acid inhibitor in the presence of Fe (III) obtained at pH of 1.0.
  • Figure 5 is a plot of absorbance as a function of content of phosphino-polyacrylic acid inhibitor in the presence of Cr (III) and Al (III) obtained at pH of 1.0.
  • Polyacrylic acid inhibitors which can be quantitatively analyzed in accordance with this invention include all homopolymers of alpha, beta-ethylenically unsaturated acid monomers, such as 5 acrylic acid or methacrylic acid; diacids, such as maleic acid (or maleic anhydride), itaconic acid, fumaric acid, mesoconic acid, citraconic acid; and monoesters of diacids with alkanols having 1-8 carbon atoms.
  • the polyacrylic acid inhibitors may also be copolymers of unsaturated acid monomers, with any monomer 10 copolymerizable therewith, such as olefinic monomers with: (a) non-polar groups, e.g., styrene; (b) polar funtional groups, e.g., vinylacetate, vinyl chloride, vinyl alcohol, acrylate ester, vinylpyridine, vinyl pyrrolidone, acrylamide or acrylamide derivatives; and (c) ionic functional groups, e.g., styrenesulfonic 15 acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), vinylsulfonic acid or vinylphosphonic acid.
  • olefinic monomers with: (a) non-polar groups, e.g., styrene; (b) polar funtional groups, e.g., vinylacetate, vinyl chloride, vinyl alcohol, acrylate ester, vinylpyridine, vinyl pyr
  • the copolymers are preferably copolymers of at least 50% by weight of acrylic acid, methacrylic acid or maleic anhydride and 50% or less by weight of the aforementioned different copolymerizable monomer.
  • the 20 polyacrylic acid inhibitor includes modifications of the polymers described above, such as phosphino-polyacrylic acid sold under the tradenames "Belsperse 161" or "Belasol S-29" by Ciba Geigy.
  • the preferred polyacrylic acid inhibitor is phosphino-polyacrylic acid.
  • the polyacrylic acid inhibitor which is quantitatively 25 analyzed in accordance with this invention is in the form of an aqueous solution containing polyvalent cations of a valence of at least 3.
  • Such cations are typically produced in situ in subteranean formations by, for example, corrosion of metal equipment or from minerals, such as siderite. «. 30
  • the step of adjusting the pH of the solution which is essential to this invention is conducted in any conventional * manner.
  • the pH of the sample to be analyzed is treated with an acid because the field-generated samples, e.g., from offshore oil exploration, usually have pH higher than 2.0, e.g., generally, a pH of between 5.0 and 9.0.
  • the acid is any conventionally-known acid, e.g., hydrochloric, sulfuric or nitric acid, most preferably hydrochloric acid.
  • the sample is contacted with a sufficient amount of the acid to lower pH thereof to a value of 0.5 to less than 2.0, preferably 0.5 to 1.9, more preferably 0.6 to 1.5 and most preferably about 0.9 to 1.2.
  • a suitable conventionally-known alkaline agent to adjust the pH thereof to within the range specified above. If particulates and oil are present after the pH of the sample has been adjusted to the desired range specified above, the sample can be filtered or the particulates and the oil separated by any conventional means.
  • the polyacrylic acid content analysis subsequent to the pH-adjustment step is conducted using a method similar to that described by Rothman in U.S. Patent 4,514,504.
  • the analysis steps comprise adsorbing the sample at a pH of 0.5 to less than 2.0 on a non-polar adsorbent, such as a non-polar, bonded phase silica gel or a rigid, macroreticular styrene-divinylbenzene polymer; desorbing the polyacrylic acid from the adsorbent with a displacement fluid, such as methanol or an aqueous sodium hydroxide; and determining the carboxyl content of the polyacrylic acid by the iron-thiocyanate method or by complexing with a cationic surfactant.
  • a non-polar adsorbent such as a non-polar, bonded phase silica gel or a rigid, macroreticular styrene-divinylbenzene polymer
  • a displacement fluid such as methanol or an
  • the iron-thiocyanate method is based on the formation of a colorless complex between iron (III) and polyacrylic acids while the complex formed between iron (III) and thiocyanate ions is red. Therefore, a decrease in the color of iron-thiocyanate complex, upon complexing of iron with polyacrylic acids, is directly proportional to the polyacrylic acid concentration.
  • potassium thiocyanate is added as an aqueous solution to the complex. The thiocyanate (SCN-) ions will react with non-complexed iron (III) ions to form the red iron-thiocyanate complex.
  • the color of the resulting solution can be correlated with the quantity of iron (III) and thiocyanate ion added to arrive at the concentration of the polyacrylic acids.
  • the color of the resulting solution in terms of the percentage of light transmitted therethrough, is an accurate measure of the polyacrylic acid concentration.
  • the method of this invention can be successfully used to measure the polyacrylic acid concentration in a solution because at the pH range of 0.5 to less than 2.0, polyacrylic acid is substantially not ionized in an aqueous solution and therefore it does not react with polyvalent cations having a valence equal to or
  • the polyacrylic acid is not ionized and therefore it is not likely to react with the polyvalent cations or complexes thereof.
  • the polyvalent ions such as ferric ions
  • the polyacrylic acids remain free in the solution and can be selectively adsorbed on the non-polar adsorbent for quantitative analysis in accordance with this invention.
  • Ciba Geigy was used as the model polyelectrolyte inhibitor.
  • a master brine solution containing the following salts was prepared.
  • valve One end of the valve was connected to a 30 cc Luer-Lock syringe while the other end was attached to a flexible tubing used to aspirate or to discard liquids. After pre-rinsing the syringe with 5 cc of a sample solution, 20 cc of a sample solution was aspirated and pumped through the LC cartridge over at least 15 seconds to adsorb the
  • the sample When no polymer is present, the sample exhibits the most red color due to the ferri-thiocyanate complex. The presence of the polymer reduces the intensity of the red color. The extent of reduction of the red color is a measure of the polymer concentration.
  • EXAMPLE 1 This example illustrates the quantitative analysis of polyacrylic acid present in a solution which also contains trivalent ion, conducted according to this invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

On détermine la concentration d'un acide polyacrylique dans une solution contenant des cations polyvalents possédant une valence supérieure ou égale à 3, par exemple du Fe (III), qui interfèrent dans l'analyse quantitative d'agents antitartre à base d'acide polyacrylique, en ajustant initialement le pH de la solution à une valeur comprise entre 0,5 et moins de 2, et en effectuant ensuite de la façon usuelle la mesure quantitative de la teneur en acide polyacrylique.
PCT/US1989/004563 1988-10-14 1989-10-11 Procede de controle de la teneur en antitartre polyacrylique Ceased WO1990004159A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
GB9105089A GB2245360B (en) 1988-10-14 1991-03-11 Method for monitoring polyacrylic scale inhibitor content
NO911363A NO302675B1 (no) 1988-10-14 1991-04-08 Fremgangsmåte for bestemmelse av konsentrasjonen av polyakrylsyre i en opplösning inneholdende et flerverdig kation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25756788A 1988-10-14 1988-10-14
US257,567 1988-10-14

Publications (1)

Publication Number Publication Date
WO1990004159A1 true WO1990004159A1 (fr) 1990-04-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1989/004563 Ceased WO1990004159A1 (fr) 1988-10-14 1989-10-11 Procede de controle de la teneur en antitartre polyacrylique

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GB (1) GB2245360B (fr)
NO (1) NO302675B1 (fr)
WO (1) WO1990004159A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997035192A1 (fr) * 1996-03-21 1997-09-25 Nalco Chemical Company Polymeres a marquage fluorescent servant a traiter l'interieur de chaudieres

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104237455B (zh) * 2013-06-18 2017-09-08 中国石油天然气股份有限公司 催化裂化装置烟气轮机结垢预测与阻垢评价实验设备

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4514504A (en) * 1983-07-22 1985-04-30 Rohm And Haas Company Monitoring method for polyacrylic acids in aqueous systems
US4581145A (en) * 1982-09-27 1986-04-08 Dearborn Chemical Company Composition and method for inhibiting scale

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4581145A (en) * 1982-09-27 1986-04-08 Dearborn Chemical Company Composition and method for inhibiting scale
US4514504A (en) * 1983-07-22 1985-04-30 Rohm And Haas Company Monitoring method for polyacrylic acids in aqueous systems

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997035192A1 (fr) * 1996-03-21 1997-09-25 Nalco Chemical Company Polymeres a marquage fluorescent servant a traiter l'interieur de chaudieres
AU718338B2 (en) * 1996-03-21 2000-04-13 Nalco Chemical Company Fluorescent-tagged polymers for boiler internal treatment

Also Published As

Publication number Publication date
NO911363L (no) 1991-04-08
GB2245360A (en) 1992-01-02
NO911363D0 (no) 1991-04-08
GB2245360B (en) 1992-10-14
NO302675B1 (no) 1998-04-06
GB9105089D0 (en) 1991-09-25

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