EP4179129A1 - Verfahren zur entfernung von ablagerungen von einer oberfläche unter verwendung eines salzfeldes der erfindung - Google Patents

Verfahren zur entfernung von ablagerungen von einer oberfläche unter verwendung eines salzfeldes der erfindung

Info

Publication number
EP4179129A1
EP4179129A1 EP20944976.8A EP20944976A EP4179129A1 EP 4179129 A1 EP4179129 A1 EP 4179129A1 EP 20944976 A EP20944976 A EP 20944976A EP 4179129 A1 EP4179129 A1 EP 4179129A1
Authority
EP
European Patent Office
Prior art keywords
torr
sulfate
chloride
salt
sodium
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
EP20944976.8A
Other languages
English (en)
French (fr)
Other versions
EP4179129A4 (de
Inventor
Ilya Yurievich RODIN
Gennady Sergeevich STAROSTIN
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.)
Angara Global Ltd
Original Assignee
Angara Global Ltd
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 Angara Global Ltd filed Critical Angara Global Ltd
Publication of EP4179129A1 publication Critical patent/EP4179129A1/de
Publication of EP4179129A4 publication Critical patent/EP4179129A4/de
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents

Definitions

  • the invention relates to the field of removing deposits from a surface, preferably the surface of industrial equipment.
  • volume expansion refers to the increase of volume when an anhydrous salt becomes a hydrate salt and is defined as the ratio of the volume of the hydrate salt over that of the anhydrous salt.
  • the stable forms of sodium sulfate are the decahydrate (mirabilite) and the anhydrite (thenardite).
  • the transition from thenardite to mirabilite and the incorporation of 10 water molecules in the crystal lattice causes a volume expansion of about 320%.
  • the disclosure relates to a method of removing various types of deposits from a surface.
  • the deposits can be salt deposits, deposits of a petroleum nature including fouling of heat exchangers, asphaltene-resin-paraffin, and resin and biological (bacterial) deposits.
  • the deposit is the fouling in a heat exchanger. In an embodiment, the deposit is the fouling in a heat exchanger used in oil refinery. In some embodiments, the surface is the surface of a metal or a glass, or a ceramic material, or a polymer material.
  • the method for removing deposits from a surface comprises the steps of wetting the surface in a first salt solution so that the first salt solution penetrates into the cracks or pores of the deposits; removing the first salt solution outside the cracks or pores of the deposits; drying the surface so that the first salt solution inside the cracks or pores of the deposits becomes an anhydrous salt; wetting the surface in a second salt solution; wherein the anhydrous salt forms a salt hydrate inside the cracks or pores of the deposits and causes volume expansion, resulting in breaking the deposits from the surface.
  • the method described herein takes advantage of volume expansion when an anhydrous salt becomes a hydrate thereof.
  • the hydrate is in a crystalline form.
  • any of the steps may be repeated 2, 3, 4, or more times till surface cleaning is achieved.
  • the surface is a metal surface.
  • the deposits comprise barite deposit or a heavy oil deposit, or petcoke deposit, or a iron oxide/sulfide deposit, or a hardness salt deposit.
  • the deposit is a thin layer on the surface with an average thickness of about 1 mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, about 10 mm, about 11 mm, about 12 mm, about 13 mm, about 14 mm, about 15 mm, about 16 mm, about 17 mm, about 18 mm, about 19 mm, or about 20 mm.
  • the first salt solution is the same as the second salt solution. In some embodiments, the first salt solution is different from the second salt solution.
  • the first salt solution is a saturated solution of the salt.
  • the first salt solution is an unsaturated solution of the salt.
  • the second salt solution is a saturated solution of the salt. In some embodiments, the second salt solution is a unsaturated solution of the salt.
  • the first salt solution and the second salt solution independently comprise a salt selected from the group consisting of copper(II) sulfate, zinc sulfate, calcium chloride, magnesium sulfate, iron(II) sulfate, magnesium chloride, sodium carbonate, sodium thiosulfate, barium hydroxide, iron(II) acetate, zinc nitrate, magnesium ammonium phosphate, iridium(III) bromide, gold chloride, sodium acetate, calcium sulfate, sodium dihydrogen phosphate, sodium sulfate, nickel(II) nitrate, iron(III) chloride, nickel(II) sulfate, manganese(II) sulfate, sodium monohydrogen phosphate, manganese(II) chloride, copper(II) nitrate, calcium nitrate, cobalt(II) chloride, nickel(II) chloride, nickel(II)
  • the concentration of the first salt solution is about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, 55%, about 60%, about 65%, about 70%, or about 75% by the weight of the salt.
  • the concentration of the second salt solution is about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, 55%, about 60%, about 65%, about 70%, or about 75% by the weight of the salt.
  • wetting the surface includes immersing the surface in the first salt solution or the second salt solution. In some embodiments, wetting the surface includes applying certain amount of the first salt solution or the second salt solution to the surface.
  • the amount of solution is decided by area size of the surface, the solution concentration, temperature, and the volume of the deposits.
  • the first salt solution is a solution of sodium sulfate. In some embodiments, the concentration of the first salt solution is about 14% by weight
  • the second salt solution is a solution of sodium sulfate.
  • the concentration of the second salt solution is about 14%.
  • the first salt solution or the second salt solution independently contains an additive.
  • the additive may be comprised by wetting agent, detergent, and/or chelating agent.
  • the surface is wetted with the first salt solution.
  • the wetting may last an amount of time sufficient to allow the first salt solution to penetrate to the cracks or pores of the deposits on the surface.
  • the amount of time for the first salt solution to penetrate to the cracks or pores of the deposits on the surface is selected from the group consisting of about 30 minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, and about 12 hours.
  • the amount of time for the first salt solution to penetrate to the cracks or pores of the deposits on the surface is about 3-24 hours. Thereafter, the first salt solution outside the cracks or pores of the deposits is removed.
  • the surface is dried so that the first salt solution inside the cracks or pores of the deposits evaporates, resulting an anhydrous salt or a partially anhydrous salt.
  • the surface is dried at a temperature for a certain amount of time.
  • the temperature is selected from the group consisting of about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 100°C, about 120°C, about 125°C, about 130°C, about 135°C, about 140°C, about 150°C, about 155°C, about 160°C, about 165°C, about 170°C, about 175°C, about 180°C, about 185°C, about 190°C, about 195°C, and about 200°C.
  • the temperature is within a range of 50°C-200°C.
  • the surface is dried at a temperature for about 30 minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, or more.
  • the surface is dried for about one day, two days, three days, four days, five days, six days, or a week. In some embodiments, the surface is dried within a range of time periods 0.5 - 24 hours.
  • the surface is dried by vacuum at room temperature or a high temperature selected from the group consisting of about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 100°C, about 120°C, about 125°C, about 130°C, about 135°C, about 140°C, about 150°C, about 155°C, about 160°C, about 165°C, about 170°C, about 175°C, about 180°C, about 185°C, about 190°C, about 195°C, and about 200.
  • the surface is dried by vacuum at a temperature within a range of 50-90°C.
  • a vacuum selected from the group consisting of about 1 Torr, about 10 Torr, about 25 Torr, about 50 Torr, about 75 Torr, about 100 Torr, about 125 Torr, about 150 Torr, about 175 Torr, about 200 Torr, about 225 Torr, about 250 Torr, about 275 Torr, about 300 Torr, about 325 Torr, about 350 Torr, about 350 Torr, about 375 Torr, about 400 Torr, about 425 Torr, about 450 Torr, about 475 Torr, about 500 Torr, about 525 Torr, about 550 Torr, about 575 Torr, about 600 Torr, about 625 Torr, about 650 Torr, about 675 Torr, and about 700 Torr.
  • the surface is cooled to room temperature. Then a second salt solution is applied to the surface. In some embodiments, the surface is immersed in the second salt solution. The second salt solution is allowed to stay in contact with the surface for certain amount of time sufficient to penetrate the cracks or pores of the deposits. In some embodiments, the amount of time for the second salt solution to penetrate to the cracks or pores of the deposits on the surface is selected from the group consisting of about 30 minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, and about 12 hours.
  • the amount of time for the second salt solution to penetrate to the cracks or pores of the deposits on the surface is in the range of 3-24 hours.
  • the second salt solution is in contact with the anhydrous salt or the partially anhydrous salt formed in the drying step. Then, the anhydrous salt or the partially anhydrous salt forms a salt hydrate.
  • the salt hydrate is in a crystalline form.
  • the salt hydrate tends to have larger volume than the corresponding anhydrous salt or partially anhydrous salt.
  • Such volume expansion inside the cracks or pores of the deposits leads to the break-away of the deposits from the surface.
  • the volume expansion is at least about 2 times. In some embodiments, the volume expansion is at least about 3 times, at least about 4 times, at least about 5 times, at least about 6 times, at least about 7 times, at least about 8 times, at least about 9 times, or at least about 10 times.
  • the method described herein further comprises the step of removing the second salt solution outside the cracks or pores of the deposits.
  • the first salt solution and the second salt solution independently comprise a salt selected from the group consisting of copper(II) sulfate, zinc sulfate, calcium chloride, magnesium sulfate, iron(II) sulfate, magnesium chloride, sodium carbonate, sodium thiosulfate, barium hydroxide, iron(II) acetate, zinc nitrate, magnesium ammonium phosphate, iridium(III) bromide, gold chloride, sodium acetate, calcium sulfate, sodium dihydrogen phosphate, sodium sulfate, nickel(II) nitrate, iron(III) chloride, nickel(II) sulfate, manganese(II) sulfate, sodium monohydrogen phosphate, manganese(II) chloride, copper(II) nitrate, calcium nitrate, cobalt(II) chloride, nickel(II) chloride, nickel(Il) sulfate, sodium
  • the salt hydrate is selected from the group consisting of copper(II) sulfate pentahydrate, zinc sulfate heptahydrate, calcium chloride dihydrate, magnesium sulfate heptahydrate, iron(II) sulfate heptahydrate, magnesium chloride hexahydrate, sodium carbonate decahydrate, sodium thiosulfate pentahydrate, barium hydroxide octahydrate, iron(II) acetate tetrahydrate, zinc nitrate hexahydrate, magnesium ammonium phosphate hexahydrate, iridium(III) bromide tetrahydrate, sodium acetate trihydrate, calcium sulfate dihydrate, sodium dihydrogen phosphate heptahydrate, sodium sulfate decahydrate, nickel(ll) nitrate hexahydrate, iron(III) chloride hexahydrate, nickel(II) sulfate hex
  • the method disclosed herein may further comprise the step of the cleaning the surface using a composition comprising hydrogen peroxide, catalyst for decomposing peroxide compounds, SAA, chelating agent, water-soluble calixarene, antifoaming agent and water.
  • a composition comprising hydrogen peroxide, catalyst for decomposing peroxide compounds, SAA, chelating agent, water-soluble calixarene, antifoaming agent and water.
  • Example 1 Removing deposits from a metal surface using sodium sulfate
  • the sample is a steel cylindrical part (height 10 cm, diameter 5 cm) of oil production equipment covered with a layer of barite deposit (thickness 5 mm). 1.
  • the sample is immersed in 14 % Na 2 SC> 4 solution at 25 °C for an hour.
  • Example 2 Removing deposits from a CDU preheat train heat-exchanger
  • the following prophetic example illustrates the applying of method for clean-up of a shell side of a small-size shell-and-tube heat-exchanger fouled with porous petcoke deposits.
  • the fouling consists mostly of elemental carbon, the average thickness of fouling layer is 5 mm.
  • the median pore diameter is 0.02 mm. 14% solution of sodium sulfate is used for the first and the second immersions.
  • the shell side of the heat-exchanger (hereinafter referred to as contour) is filled with sodium sulfate solution and left undisturbed for 6 hours for the solution to soak the deposits. After 3 hours the solution is drained from the contour to the recycle storage tank. The contour is than dried for 1 hour with a 150°C steam supplied to the tube side. After drying the contour is filled with the same sodium sulfate solution and left undisturbed for 3 hours. The contour is then connected to the circulation loop comprising pump and filter units. Circulation of the solution resulted in accumulation of the fouling debris in the filter units. The commissioning of the dismantled tube bundle showed complete removal of all fouling material.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP20944976.8A 2020-07-13 2020-07-13 Verfahren zur entfernung von ablagerungen von einer oberfläche unter verwendung eines salzfeldes der erfindung Pending EP4179129A4 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/RU2020/000345 WO2022015186A1 (en) 2020-07-13 2020-07-13 Methods of removing deposits from a surface using a salt field of the invention

Publications (2)

Publication Number Publication Date
EP4179129A1 true EP4179129A1 (de) 2023-05-17
EP4179129A4 EP4179129A4 (de) 2024-07-24

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP20944976.8A Pending EP4179129A4 (de) 2020-07-13 2020-07-13 Verfahren zur entfernung von ablagerungen von einer oberfläche unter verwendung eines salzfeldes der erfindung

Country Status (2)

Country Link
EP (1) EP4179129A4 (de)
WO (1) WO2022015186A1 (de)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2154109C1 (ru) * 1999-11-02 2000-08-10 Открытое акционерное общество совместное предприятие акционерная компания "Тулачермет" Способ очистки внутренних поверхностей холодильников доменных печей от накипно-коррозионных отложений
EP1411149A1 (de) * 2002-10-18 2004-04-21 Siemens Aktiengesellschaft Verfahren zum Entfernen eines Schichtbereichs eines Bauteils
US7125457B2 (en) * 2003-12-31 2006-10-24 General Electric Company Method for removing oxide from cracks in turbine components
WO2006039983A1 (de) * 2004-09-25 2006-04-20 Chemetall Gmbh Verfahren zur entfernung von laserzunder
RU2581347C1 (ru) * 2014-12-05 2016-04-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный машиностроительный университет (МАМИ)" Способ удаления с металлических поверхностей из углеродистых нелегированных сталей накипно-коррозионных отложений
FR3035403B1 (fr) * 2015-04-21 2017-05-19 Arkema France Utilisation d'acide alcane sulfonique pour le nettoyage dans les industries sucrieres
RU2016123122A (ru) * 2016-06-10 2017-12-12 Олег Савельевич Кочетов Средство для очистки поверхностей, загрязненных нефтью и нефтепродуктами
RU2696990C2 (ru) * 2017-12-26 2019-08-08 Общество с ограниченной ответственностью "АНГАРА ДЕВЕЛОПМЕНТ" (ООО "АНГАРА ДЕВЕЛОПМЕНТ") Раствор для очистки поверхности от отложений различной природы
CN109201567B (zh) * 2018-08-29 2019-12-24 海南省博物馆(海南省文物考古研究所） 一种海洋出水石质文物复合高效清洗方法

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Publication number Publication date
EP4179129A4 (de) 2024-07-24
WO2022015186A1 (en) 2022-01-20

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