WO2002066704A1 - Laser coating of a part used in an oil refinery - Google Patents

Laser coating of a part used in an oil refinery Download PDF

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Publication number
WO2002066704A1
WO2002066704A1 PCT/FI2002/000145 FI0200145W WO02066704A1 WO 2002066704 A1 WO2002066704 A1 WO 2002066704A1 FI 0200145 W FI0200145 W FI 0200145W WO 02066704 A1 WO02066704 A1 WO 02066704A1
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WO
WIPO (PCT)
Prior art keywords
coating
nickel
coating layer
laser
layer
Prior art date
Application number
PCT/FI2002/000145
Other languages
French (fr)
Other versions
WO2002066704A8 (en
Inventor
Esko Ainasoja
Mark Cederberg
Jari Lyytinen
Matti Nissinen
Arto Kiiski
Olli Kortelainen
Original Assignee
Fortum Oyj
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
Priority claimed from FI20010338A external-priority patent/FI114401B/en
Application filed by Fortum Oyj filed Critical Fortum Oyj
Publication of WO2002066704A1 publication Critical patent/WO2002066704A1/en
Publication of WO2002066704A8 publication Critical patent/WO2002066704A8/en

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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/18—Apparatus
    • C10G9/20—Tube furnaces
    • C10G9/203—Tube furnaces chemical composition of the tubes
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate

Definitions

  • the invention relates to a method according to the preamble of claim 1 for coating a part used in an oil refinery unit with a layer of a nickel alloy material.
  • the invention also relates to a coated part according to the preamble of claim 9 for use in an oil refinery unit.
  • Hydrofluoric acid is an important basic chemical commonly used in the indus- try. For instance, in alkylation units of oil refineries this acid is used as a catalyst. Hydrofluoric acid attacks most metals and metal alloys in a corrosive manner. The rate of corrosion is affected, among other factors, by the concentration, temperature and moisture content of the acid. The corrosion rate may additionally be accelerated by air and oxidizing metal ions that often occur in hydrofluoric acid as impurities.
  • Construction materials commonly used in the handling of hydrofluoric acid are carbon steels and, in particularly demanding cases, nickel alloys of which particularly well known is a nickel-copper alloy marketed under tradename Monel 400.
  • carbon steel parts have generally been replaced in applications most severely subjected to corrosion by similar components made from a nickel-based alloy.
  • nickel alloys have a limited use in plural sites due to their high, even hundred-fold price and weaker structural properties in regard to carbon steels.
  • carbon steel parts may also be protected by a coating of a nickel alloy material.
  • the coating is applied to the surface of the base material generally by spraying, welding or dip-coating, the latter taking place by dipping the part to be coated into a bath of molten coating material.
  • a disadvantage of these methods is that the coating layer contains pores via which the corrosive medium can penetrate to the surface of the base material, whereby local corrosion at the points subjected to the corrosive material may proceed extremely rapidly.
  • it must be made thick with the inevitable consequence, that the coated part often requires machining after the application of the coating layer.
  • conventional coating methods are often awkward in the application of a sufficiently solid and thin coating layer.
  • the goal of the invention is achieved by means of forming the coating layer with the help of a laser coating method wherein the nickel alloy coating material is melted on the base material surface with the help of a laser beam.
  • a separate intermediary layer can be applied between the base material and the coating material layers if these two materials are not inherently metallurgically compatible with each other.
  • part according to the invention is characterized by what is stated in the characterizing part of claim 9.
  • the invention offers significant benefits.
  • the coating layer applied by means of laser coating is solid and free from pores because the operating parameters of laser coating equipment can be effectively controlled during the entire coating process. This makes it possible to produce a coating layer free from pores, whereby the corrosion resistance of the coated part is improved substantially over coatings applied by conventional thermal coating methods.
  • the part 1 to be coated is a part intended for use in an oil refinery unit, such as the alkylation unit thereof, wherein the part will become in contact with a corrosive medium such as hydrofluoric acid (HF).
  • a corrosive medium such as hydrofluoric acid (HF).
  • HF hydrofluoric acid
  • Such parts are, e.g., flanges used in piping.
  • the base material 2 of part 1 is carbon steel which in itself is not sufficiently resistant to very moist hydrofluoric acid.
  • the base material 2 of part 1 may also be any other material typically used in the oil refinery industry such as structural, alloy or stainless steel.
  • the part 1 is coated in laser coating equipment 5 with a coating layer 4 of a nickel alloy material such as a commercially available nickel-copper alloy known as Monel 400.
  • a nickel alloy material such as a commercially available nickel-copper alloy known as Monel 400.
  • the basic component is nickel having copper and trace amounts of other elements alloyed therewith.
  • the composition is about 64 % nickel (Ni), about 31 % copper (Cu) with trace amounts of iron (Fe), chromium (Cr), silicon (Si), carbon (C), sulfur (S) and manganese (Mn).
  • Nickel-copper alloys have a high corrosion resistance against hydrofluoric acid and silicon hydrofluoric acid as well as salt water, high-concentration chloride solutions. Furthermore, they are resistant to alkaline solutions having a concentration less than 50 %.
  • the coating layer may also be nickel or some other nickel alloy material such as a nickel-chromium(Cr), nickel-molybdenum(Mo), nickel-chromium-molybdenum or nickel-chromium-molybdenum-copper alloy.
  • nickel-chromium(Cr) nickel-chromium(Cr)
  • Mo nickel-molybdenum
  • Ni-chromium-molybdenum nickel-chromium-molybdenum-copper alloy.
  • Typical compositions of the most commonly used nickel-based alloys are listed in the following table.
  • the laser coating equipment 5 comprises a laser gun 6, wherefrom coating material in pulverized form is applied with the help of a carrier gas to an area of the part 1 premelted by the laser beam 7. Prior to coating, the surface of part 1 can be machined to a desired roughness and cleaned in order to improve the adhesion of the coating material 4 thereto.
  • the feed of the coating material in the laser gun takes place coaxially about the laser beam 7, whereby the flow of the coating material with the shielding gas surrounds the laser beam 7.
  • the coating material may also be introduced to the working area of the laser beam 7 as a sheet or wire.
  • the shielding gas is carbon dioxide or argon.
  • the surface of the part 1 being coated is moved relative to the laser beam 7 and/or the laser beam 7 is moved over the part 1 relative to the surface being coated.
  • the part 1 to be coated may have a rotation-symmetrical or planar shape, for instance. Rotation- symmetrical parts 1 can be coated when mounted, e.g., on a lathe.
  • the scanning speed of the laser beam 7 over the surface of the part 1 being coated is advantageously 100 to 1000 mm/min, most advantageously 230 to 270 mm/min.
  • the heat imported by the laser beam 7 is primarily absorbed by the part 1 , the melted coating material 4 solidifies rapidly with the progress of the coating process. Due to the low total amount of thermal energy and fast cooling rate used in the process, the coating layer 4 becomes pore-free. Since the laser beam 7 melts only a small area on the surface of part 1, the cooling thereof does not cause a major shrinkage of the coating layer 4. Moreover, the shielding gas protects the molten coating material 4.
  • the width of a coating layer strip 4 applied in a single sweep of the beam is deter- mined by the distance of the focus point of the laser beam 7 relative to the surface 2 being coated.
  • the width of a single strip of the coating layer 4 formed by moving the laser gun 6 and/or the surface to be coated is 2 to 3 mm.
  • the thickness of the coating layer 4 formed by the laser coating method is typically 0.1 to 4 mm, most advantageously about 1 mm. When necessary, a greater number of coating layers 4 can be superposed on each other.
  • the center axis of the laser beam 7 is aligned substantially perpendicular to the envelope surface of the part 1 to be coated.
  • envelope surface is used in making reference to the surface delineating an ideal shape of the part being handled wherefrom the actual shape may differ due to, e.g., manufacturing tolerances, wear and other deformations.
  • the coating material must be metallurgically compatible with the base material 2.
  • the mutual compatibility may be improved by a proper choice of additives in the coating material or through altering its composition.
  • the qualities achievable by means of the coating are determined by the application, base material, coating material and process parameters used.
  • the material of the coating layer 4 and the base material 2 are not metallurgically compatible, cracking of the coating layer 4 may occur.
  • the intermediary layer 3 can be deposited using, e.g., the laser coating method or by spraying. Next, the intermediary layer 3 is machined to a desired roughness and cleaned to improve the adhesion of the coating material 4 thereto.
  • the intermediary layer 3 may in certain cases be necessary between the surface of the base material 2 and the coating layer 4.
  • the intermediary layer 3 from some other type of a nickel-based alloy, such as a nickel chromium or nickel-chromium-molybdenum alloy.

Abstract

The invention relates to a method for coating a part (1) used in an oil refinery unit by a coating layer (4) of a nickel-based material. In the method according to the invention, the coating layer ( 4) is formed using a laser coating method. The invention alsorelates to a part (1) for use in an oil refinery unit and having a coating layer (4) of a nickel-based material applied thereon. In a part (1) according to the invention, the coating layer (4) isformed using a laser coating method.

Description

Laser coating of a part used in an oil refinery.
The invention relates to a method according to the preamble of claim 1 for coating a part used in an oil refinery unit with a layer of a nickel alloy material. The invention also relates to a coated part according to the preamble of claim 9 for use in an oil refinery unit.
Hydrofluoric acid (HF) is an important basic chemical commonly used in the indus- try. For instance, in alkylation units of oil refineries this acid is used as a catalyst. Hydrofluoric acid attacks most metals and metal alloys in a corrosive manner. The rate of corrosion is affected, among other factors, by the concentration, temperature and moisture content of the acid. The corrosion rate may additionally be accelerated by air and oxidizing metal ions that often occur in hydrofluoric acid as impurities.
Construction materials commonly used in the handling of hydrofluoric acid are carbon steels and, in particularly demanding cases, nickel alloys of which particularly well known is a nickel-copper alloy marketed under tradename Monel 400. In fact, carbon steel parts have generally been replaced in applications most severely subjected to corrosion by similar components made from a nickel-based alloy. However, nickel alloys have a limited use in plural sites due to their high, even hundred-fold price and weaker structural properties in regard to carbon steels.
To improve their corrosion resistance, carbon steel parts may also be protected by a coating of a nickel alloy material. Herein, the coating is applied to the surface of the base material generally by spraying, welding or dip-coating, the latter taking place by dipping the part to be coated into a bath of molten coating material. A disadvantage of these methods is that the coating layer contains pores via which the corrosive medium can penetrate to the surface of the base material, whereby local corrosion at the points subjected to the corrosive material may proceed extremely rapidly. To provide an unpenetrable coating layer, it must be made thick with the inevitable consequence, that the coated part often requires machining after the application of the coating layer. Hence, conventional coating methods are often awkward in the application of a sufficiently solid and thin coating layer.
It is an object of the present invention to provide an entirely novel type of coating method for applying a coating of a nickel alloy material onto the surface of a part employed in an oil refinery unit.
The goal of the invention is achieved by means of forming the coating layer with the help of a laser coating method wherein the nickel alloy coating material is melted on the base material surface with the help of a laser beam. When necessary, a separate intermediary layer can be applied between the base material and the coating material layers if these two materials are not inherently metallurgically compatible with each other.
More specifically, the method according to the invention is characterized by what is stated in the characterizing part of claim 1.
Furthermore, the part according to the invention is characterized by what is stated in the characterizing part of claim 9.
The invention offers significant benefits.
The coating layer applied by means of laser coating is solid and free from pores because the operating parameters of laser coating equipment can be effectively controlled during the entire coating process. This makes it possible to produce a coating layer free from pores, whereby the corrosion resistance of the coated part is improved substantially over coatings applied by conventional thermal coating methods.
In the following, the invention is described in more detail with reference to the appended drawing illustrating a laser coating apparatus and a part being coated. The part 1 to be coated is a part intended for use in an oil refinery unit, such as the alkylation unit thereof, wherein the part will become in contact with a corrosive medium such as hydrofluoric acid (HF). Such parts are, e.g., flanges used in piping. Typically, the base material 2 of part 1 is carbon steel which in itself is not sufficiently resistant to very moist hydrofluoric acid. Obviously, the base material 2 of part 1 may also be any other material typically used in the oil refinery industry such as structural, alloy or stainless steel.
To improve its corrosion resistance, the part 1 is coated in laser coating equipment 5 with a coating layer 4 of a nickel alloy material such as a commercially available nickel-copper alloy known as Monel 400. In nickel-copper alloys, the basic component is nickel having copper and trace amounts of other elements alloyed therewith. In Monel 400, for instance, the composition is about 64 % nickel (Ni), about 31 % copper (Cu) with trace amounts of iron (Fe), chromium (Cr), silicon (Si), carbon (C), sulfur (S) and manganese (Mn). Nickel-copper alloys have a high corrosion resistance against hydrofluoric acid and silicon hydrofluoric acid as well as salt water, high-concentration chloride solutions. Furthermore, they are resistant to alkaline solutions having a concentration less than 50 %.
The coating layer may also be nickel or some other nickel alloy material such as a nickel-chromium(Cr), nickel-molybdenum(Mo), nickel-chromium-molybdenum or nickel-chromium-molybdenum-copper alloy. Typical compositions of the most commonly used nickel-based alloys are listed in the following table.
Figure imgf000005_0001
The laser coating equipment 5 comprises a laser gun 6, wherefrom coating material in pulverized form is applied with the help of a carrier gas to an area of the part 1 premelted by the laser beam 7. Prior to coating, the surface of part 1 can be machined to a desired roughness and cleaned in order to improve the adhesion of the coating material 4 thereto. The feed of the coating material in the laser gun takes place coaxially about the laser beam 7, whereby the flow of the coating material with the shielding gas surrounds the laser beam 7. Instead of using pulverized coating material, the coating material may also be introduced to the working area of the laser beam 7 as a sheet or wire. The shielding gas is carbon dioxide or argon. The surface of the part 1 being coated is moved relative to the laser beam 7 and/or the laser beam 7 is moved over the part 1 relative to the surface being coated. The part 1 to be coated may have a rotation-symmetrical or planar shape, for instance. Rotation- symmetrical parts 1 can be coated when mounted, e.g., on a lathe.
The scanning speed of the laser beam 7 over the surface of the part 1 being coated is advantageously 100 to 1000 mm/min, most advantageously 230 to 270 mm/min. As the heat imported by the laser beam 7 is primarily absorbed by the part 1 , the melted coating material 4 solidifies rapidly with the progress of the coating process. Due to the low total amount of thermal energy and fast cooling rate used in the process, the coating layer 4 becomes pore-free. Since the laser beam 7 melts only a small area on the surface of part 1, the cooling thereof does not cause a major shrinkage of the coating layer 4. Moreover, the shielding gas protects the molten coating material 4. The width of a coating layer strip 4 applied in a single sweep of the beam is deter- mined by the distance of the focus point of the laser beam 7 relative to the surface 2 being coated. Typically, the width of a single strip of the coating layer 4 formed by moving the laser gun 6 and/or the surface to be coated is 2 to 3 mm. The thickness of the coating layer 4 formed by the laser coating method is typically 0.1 to 4 mm, most advantageously about 1 mm. When necessary, a greater number of coating layers 4 can be superposed on each other.
The center axis of the laser beam 7 is aligned substantially perpendicular to the envelope surface of the part 1 to be coated. In the context of the present invention, the term envelope surface is used in making reference to the surface delineating an ideal shape of the part being handled wherefrom the actual shape may differ due to, e.g., manufacturing tolerances, wear and other deformations.
The coating material must be metallurgically compatible with the base material 2. The mutual compatibility may be improved by a proper choice of additives in the coating material or through altering its composition. The qualities achievable by means of the coating are determined by the application, base material, coating material and process parameters used.
If the material of the coating layer 4 and the base material 2 are not metallurgically compatible, cracking of the coating layer 4 may occur. To prevent this, it may be advantageous to form onto the surface of the base material 2 an intermediary layer 3 of a material that is metallurgically compatible with both the base material 2 and the material of the coating layer 4. Since the intermediary layer 3 thus remains protected between the base material 2 and the coating material 4, it cannot be attacked by the corrosive medium. The intermediary layer 3 can be deposited using, e.g., the laser coating method or by spraying. Next, the intermediary layer 3 is machined to a desired roughness and cleaned to improve the adhesion of the coating material 4 thereto. If the base material 2 is carbon steel and the coating material 4 is a nickel- copper alloy, the intermediary layer 3 may in certain cases be necessary between the surface of the base material 2 and the coating layer 4. Herein, it is possible to make the intermediary layer 3 from some other type of a nickel-based alloy, such as a nickel chromium or nickel-chromium-molybdenum alloy.

Claims

What is claimed is:
1. A method for coating a part (1) used in an oil refinery unit by a coating layer (4) of a nickel-based material, characterized in that the coating layer (4) is formed using a laser coating method.
2. The method of claim 1, characterized in that an intermediary layer (3) is formed between the base material (2) of the part (1) and the coating layer (4).
3. The method of claim 1, characterized in that the base material (2) of the part (1) is carbon steel.
4. The method of claim 1, characterized in that the material of the coating layer (4) is a nickel-copper alloy.
5. The method of claim 2, characterized in that the material of the intermediary layer (3) is a nickel-chromium or a nickel-chromium-molybdenum alloy.
6. The method of claim 2, characterized in that the surface of the intermediary layer (3) is machined prior to the application of the coating layer thereon.
7. The method of claim 1, characterized in that the base material (2) is machined prior to the start of the coating process.
8. The method of claim 1, characterized in that the thickness of the coating layer (4) is 0.1 to 4 mm, most advantageously about 1 mm.
9. Apart (1) for use in an oil refinery unit and having a coating layer (4) of a nickel- based material applied thereon, characterized in that the coating layer (4) is formed using a laser coating method. 1/1
Figure imgf000009_0001
Fig.l
PCT/FI2002/000145 2001-02-21 2002-02-21 Laser coating of a part used in an oil refinery WO2002066704A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FI20010338A FI114401B (en) 2001-02-21 2001-02-21 Method for Coating Copper and Copper Alloys
FI20010338 2001-02-21
FI20011116 2001-05-28
FI20011116A FI20011116A (en) 2001-02-21 2001-05-28 coating process

Publications (2)

Publication Number Publication Date
WO2002066704A1 true WO2002066704A1 (en) 2002-08-29
WO2002066704A8 WO2002066704A8 (en) 2003-12-04

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WO (1) WO2002066704A1 (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3310423A (en) * 1963-08-27 1967-03-21 Metco Inc Flame spraying employing laser heating
JPS5789470A (en) * 1980-11-22 1982-06-03 Kawasaki Steel Corp Formation of plasma spray-coated film on welded part
US4400408A (en) * 1980-05-14 1983-08-23 Permelec Electrode Ltd. Method for forming an anticorrosive coating on a metal substrate
JPH04297566A (en) * 1991-03-25 1992-10-21 Ishikawajima Harima Heavy Ind Co Ltd Method for treating surface of metallic material
JPH0734263A (en) * 1993-07-23 1995-02-03 Ishikawajima Harima Heavy Ind Co Ltd Method for coating sealing part
JPH09279388A (en) * 1996-04-12 1997-10-28 Japan Energy Corp Method for preventing corrosion of austenitic stainless steel
JP2000130405A (en) * 1998-10-29 2000-05-12 Mitsubishi Heavy Ind Ltd Hydraulic cylinder

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3310423A (en) * 1963-08-27 1967-03-21 Metco Inc Flame spraying employing laser heating
US4400408A (en) * 1980-05-14 1983-08-23 Permelec Electrode Ltd. Method for forming an anticorrosive coating on a metal substrate
JPS5789470A (en) * 1980-11-22 1982-06-03 Kawasaki Steel Corp Formation of plasma spray-coated film on welded part
JPH04297566A (en) * 1991-03-25 1992-10-21 Ishikawajima Harima Heavy Ind Co Ltd Method for treating surface of metallic material
JPH0734263A (en) * 1993-07-23 1995-02-03 Ishikawajima Harima Heavy Ind Co Ltd Method for coating sealing part
JPH09279388A (en) * 1996-04-12 1997-10-28 Japan Energy Corp Method for preventing corrosion of austenitic stainless steel
JP2000130405A (en) * 1998-10-29 2000-05-12 Mitsubishi Heavy Ind Ltd Hydraulic cylinder

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 198228, Derwent World Patents Index; AN 1982-58038E *
DATABASE WPI Week 199802, Derwent World Patents Index; AN 1998-015252 *
DATABASE WPI Week 200034, Derwent World Patents Index; AN 2000-390346 *
PATENT ABSTRACTS OF JAPAN *

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Publication number Publication date
WO2002066704A8 (en) 2003-12-04
FI20011116A0 (en) 2001-05-28
FI20011116A (en) 2002-08-22

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