RU2636210C2 - Composition of corrosion-resistant coating for protection of technological petrochemical equipment - Google Patents

Composition of corrosion-resistant coating for protection of technological petrochemical equipment Download PDF

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RU2636210C2
RU2636210C2 RU2016104928A RU2016104928A RU2636210C2 RU 2636210 C2 RU2636210 C2 RU 2636210C2 RU 2016104928 A RU2016104928 A RU 2016104928A RU 2016104928 A RU2016104928 A RU 2016104928A RU 2636210 C2 RU2636210 C2 RU 2636210C2
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corrosion
mo
ni
cr
fe
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RU2016104928A
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RU2016104928A (en
Inventor
Лев Христофорович Балдаев
Раиса Дмитриевна Бакаева
Динар Зуфарович Ишмухаметов
Максим Викторович Ершов
Вадим Сергеевич Шарыгин
Александр Николаевич Ригин
Александр Геннадиевич Александров
Владимир Вячеславович Каминский
Игнат Михайлович Старшов
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Общество С Ограниченной Ответственностью "Технологические Системы Защитных Покрытий" (Ооо "Тсзп")
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Priority to RU2016104928A priority Critical patent/RU2636210C2/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • C23C4/08Metallic material containing only metal elements

Abstract

FIELD: chemistry.SUBSTANCE: corrosion-resistant coating to protect the internal surface of process equipment exposed to wear under the influence of a medium with a hydrogen sulfide content of up to 20% contains, wt %: Cr 13-22, C 0.01-0.1, Mo 1.0-3.0, Ni 10.0-14.0, Fe is the rest, or Cr 20-28.5, C 0.1-1.5, Si 1.0-2.0, Mn 0.5-1.1, Mo 3.0-5.0, Ni 14.5-17.0, Fe - the rest. Corrosion-resistant coating for the protection of the internal surface of process equipment subjected to wear under the influence of a medium with a hydrogen sulphide content of more than 20% contains, wt %: Cr 16.0-18.0, C 0.01-0.1, Mo 1.0-3.0, Ti 0.5-1.2, Ni 12.0-14.0, Fe - the rest, at the carbon equivalent of Cequ in the range of 4.50 to 5.3 and the coefficient of pitting resistance PREN in the range of 22.6 to 30.2, or Cr 20-24.0, C 0.01-0.02, Fe 3.0-5.0, Mo 13.0-15.0, W 2.0-4.0, Ni - the rest, with the carbon equivalent of Cequ in the range of 9.5 to 11.2, and the coefficient of pitting resistance PREN in the range of 60.25 to 76.4.EFFECT: invention makes it possible to increase the adhesion to the base material, corrosion-mechanical properties: wear resistance, abrasion resistance, corrosion resistance.4 cl, 4 ex

Description

FIELD OF THE INVENTION

The invention relates to chemical, petrochemical, oil refining engineering, and in particular to compositions for protecting the main and auxiliary equipment of these industries from the effects of aggressive corrosive environments, as well as environments in which abrasive particles, rust, solid by-products of production may be additionally present, or additional hydrodynamic phenomena in the form of cavitation, water hammer.

State of the art

The operation of technological equipment of petrochemical and oil refineries is accompanied by processes of corrosion, corrosion and mechanical wear. To protect the equipment, the following materials are used as traditional materials: low alloy steels (or low carbon), high alloy steels and alloys, or two-layer steels.

As a rule, the use of low alloy steels (or low carbon steels) is associated with minimal equipment manufacturing costs, but is limited by their resistance to a wide range of aggressive corrosive environments of oil refineries and petrochemical enterprises. For example, 20YuCH steel has satisfactory resistance to general corrosion processes (for example, when exposed to H 2 S), but low resistance to local types of corrosion (pitting, ulcers), which inhibits its use.

The use of high alloy steels and alloys is relevant in cases where it is not possible to use less expensive low alloy steels, due to the aggressiveness of the environment. Moreover, the use of high alloy steels and alloys is mainly limited by their high cost and reduced bearing capacity (limited weight and size parameters).

The use of double-layer steels is an alternative between expensive high alloy steels and alloys and low alloy steels, since the structural bearing capacity is provided by a layer of low alloy steel, and the corrosion properties are due to the clad layer. However, currently used two-layer steels have a limited range of cladding layers: 08X13, 10X17H13MZT, 08Kh22N6T, 12Kh18N10T and others. In this case, the manufacturing process of the final structure (column, apparatus, capacity, etc.) significantly affects the operational stability of the material of the cladding layer. The most common damage to the cladding layer is pitting, ulcerative damage, accompanied by general corrosion processes, as well as stress cracking.

The prior art known powder deposited by thermal spraying to create a corrosion layer containing tungsten, chromium, carbon, cobalt (see [1] US 6503290, IPC C23C 4/08, publ. 07.01.2003). The disadvantage of this analogue is the limited applicability under conditions of exposure to corrosive environments, due to the high hardness of the coating material (low ductility), which during operation (temperature drops, pressure drops of the medium) will contribute to cracking of the material with subsequent delamination from the base.

Also known is a corrosion-resistant coating for steel pipes made in the form of an MCrX coating, where M is nickel, cobalt, iron, and X is molybdenum, silicon, and tungsten. The coating is applied by plasma spraying with preliminary heating of the pipe (see [2] US 6749894, IPC С23С 4/02, publ. 15.06.2004).

The disadvantage of this analogue is its excessive porosity due to the plasma coating method, which under the influence of corrosive environments will contribute to the occurrence of electrochemical corrosion between the coating and the base material. The elimination of porosity can be achieved by melting the coating material, however, this requires precise control of the process parameters (a narrow range of melting of this type of coating), and it can also contribute to the deterioration of the mechanical properties of the base material under high temperatures (more than 900 degrees Celsius) required for reflow coverings.

A known method of thermal spraying of a composite powder (see [3] US 6513728, IPC С23С 4/12, published 04.02.2003), which includes Ni, Cr, Fe, Mn, Al, Mo, Ta + Cb.

The disadvantage of this analogue is the high resistance of the material due to alloying with refractory elements (Ta + Cb), as well as the condition of the material in the form of a wire, which is due to the fact that the corrosion resistance of coatings obtained from wire materials (gas-flame wire spraying) is inferior to the resistance of coatings obtained from powder materials (high-speed flame spraying)

Disclosure of invention

The objective of the invention is to increase the resource of internal surfaces (volumes) of technological equipment subjected to corrosion-abrasive wear under the influence of an aggressive environment during operation (corrosive components: chlorides, hydrogen sulfide, mercaptans, products of adverse reactions, etc .; and also solid abrasive impurities: rust, particles of the catalyst complex, particles of deposits on the inner walls).

The technical result of the invention is to increase the protection of metal-intensive equipment (reactors, columns); in increasing adhesion to the base material; in increasing the corrosion and mechanical properties: wear resistance, abrasion resistance, corrosion resistance, reliability - compared with the base material.

The specified technical result is ensured by a corrosion-resistant coating to protect the inner surface of technological equipment subjected to wear under the influence of a medium with a hydrogen sulfide content of up to 20%, while it contains chromium, carbon, molybdenum, nickel and iron in the following ratio of ingredients, wt. %: Cr - 13-22; C - 0.01-0.1; Mo - 1.0-3.0; Ni - 10.0-14.0; Fe is the rest.

Also, the technical result is achieved due to the corrosion-resistant coating to protect the inner surface of technological equipment subjected to wear under the influence of a medium with a hydrogen sulfide content of up to 20%, while it contains chromium, carbon, molybdenum, nickel, manganese, silicon and iron in the following ratio of ingredients wt. %: Cr - 20-28.5; C 0.1-1.5; Si - 1.0-2.0; Mn - 0.5-1.1; Mo - 3.0-5.0; Ni - 14.5-17.0; Fe is the rest.

Also, the technical result is achieved due to the corrosion-resistant coating to protect the inner surface of technological equipment subjected to wear under the influence of a medium with a hydrogen sulfide content of more than 20%, while it contains chromium, carbon, molybdenum, nickel, titanium and iron in the following ratio of ingredients, wt . %: Cr - 16.0-18.0; C - 0.01-0.1; Mo - 1.0-3.0; Ti - 0.5-1.2; Ni - 12.0-14.0; Fe - the rest, at the carbon equivalent of Seq. in the range from 4.50 to 5.3 and the pitting resistance coefficient PREN in the range from 22.6 to 30.2.

Also, the technical result is achieved due to the corrosion-resistant coating to protect the inner surface of technological equipment subjected to wear under the influence of a medium with a hydrogen sulfide content of more than 20%, while it contains chromium, carbon, iron, molybdenum, tungsten and nickel in the following ratio of ingredients, wt . %: Cr - 20-24.0; C - 0.01-0.02; Fe - 3.0-5.0; Mo - 13.0-15.0; W - 2.0-4.0; Ni - the rest, at the carbon equivalent of Seq. in the range from 9.5 to 11.2, and the pitting resistance coefficient PREN in the range from 60.25 to 76.4.

The implementation of the invention

Functional coating is applied to the inner surface of technological equipment by thermal spraying. The composition and properties of the coating vary depending on the operating conditions of the process equipment, the aggressiveness of the ongoing corrosion-mechanical processes, their localization, the type of thermal spraying technology used.

The composition of the coating material is selected in such a way as to provide high resistance to local types of corrosion in the form of pits and ulcers, structural stability for the temperature range of operation of technological equipment, and the rate of general corrosion of not more than 0.1 mm / year. This is achieved by choosing the ratios of such alloying elements as: chromium (Cr), nickel (Ni), carbon (C), manganese (Mn), molybdenum (Mo or tungsten (W) instead of molybdenum, boron (B) or silicon (Si ), niobium (Nb) or titanium (Ti).

In this case, nickel and iron are considered as the base material, which are subsequently alloyed with such elements as Cr, Ni, C, Mn, Mo, W, B, Si, Nb, Ti.

The ratio of elements varies based on the aggressiveness of the environment in the following form:

- for media with a H 2 S content of up to 20%, mass. %:

Cr - 13-22%; C - 0.01-0.1%; Mo - 1.0-3.0%; Ni - 10.0-14.0%; Fe - the rest is composition No. 1;

or Cr, 20-28.5%; C - 0.1-1.5%; Si - 1.0-2.0%; Mn - 0.5-1.1%; Mo - 3.0-5.0%; Ni - 14.5-17.0%; Fe - the rest - composition No. 2.

For composition No. 1, an excess of carbon content of more than 0.1% contributes to a decrease in the corrosion resistance of the alloy due to an increase in carbide emissions along grain boundaries; carbon reduction contributes to higher cost of material production technology. The chromium content is due to: the upper limit - the requirements of economical alloying, and the lower limit - the requirements of corrosion resistance. The molybdenum content is due to: the upper limit - the requirements of economical alloying, and the lower - resistance to pitting. The nickel content is due to: the upper limit of the requirements of economical alloying, and the lower limit - corrosion resistance.

For composition No. 2 (with increased hardness), the carbon content: the upper limit is due to the requirements of optimal wear resistance while maintaining corrosion resistance, the lower limit due to the requirements of corrosion resistance. The content of chromium and silicon: the upper limit - the requirements of economical alloying, and the lower limit - the requirements of corrosion resistance and the formation of wear-resistant phases (carboborides, carbosilicides). The molybdenum content is due to: the upper limit - the requirements of economical alloying, and the lower - resistance to pitting. The nickel content is due to: the upper limit of the requirements of economical alloying, and the lower limit - corrosion resistance.

- for media with a H 2 S content of more than 20%, mass. %:

Cr - 16.0-18.0%; C - 0.01-0.1%; Mo - 1.0-3.0%; Ti - 0.5-1.2%; Ni - 12.0-14.0%; Fe - the rest - composition No. 3, while Seq. (carbon equivalent) should be in the range from 4.50 to 5.3, and the pitting resistance coefficient PREN (Pitting resistance equivalent number) in the range from 22.6 to 30.2;

or Cr, 20-24.0%; C - not more than 0.02%; Fe - 3.0-5.0%, Mo - 13.0-15.0%; W - 2.0-4.0%; Ni - the rest - composition No. 4, while Seq. (carbon equivalent) should be in the range of 9.5 to 11.2, and the pitting resistance coefficient PREN in the range of 60.25 to 76.4.

For composition No. 3, an excess of carbon content of more than 0.1% contributes to a decrease in the corrosion resistance of the alloy due to an increase in carbide emissions along grain boundaries; carbon reduction contributes to higher cost of material production technology. The chromium content is due to: the upper limit - the requirements of economical alloying, and the lower limit - the requirements of corrosion resistance. The molybdenum content is due to: the upper limit - the requirements of economical alloying, and the lower - resistance to pitting. The titanium content is due to: the lower limit of the increase in the resistance of the material to intergranular corrosion, and the upper limit - the requirements of economical alloying. The nickel content is due to: the upper limit of the requirements of economical alloying, and the lower limit - corrosion resistance.

For composition No. 4, an excess of carbon content of more than 0.02% contributes to a decrease in the corrosion resistance of the alloy due to an increase in carbide precipitates along grain boundaries. The chromium content is due to: the upper limit - the requirements of economical alloying, and the lower limit - the requirements of corrosion resistance. The molybdenum content is due to: the upper limit - the requirements of economical alloying, and the lower - resistance to pitting. The tungsten content is due to: the lower limit by increasing the yield strength of the material, and the upper limit due to the requirements to ensure corrosion resistance, since an increase in the tungsten content contributes to the growth of carbide precipitates along grain boundaries.

The desired materials are obtained by manufacturing a cast alloy by metallurgical methods, followed by the manufacture of a metal powder by spraying in an inert gas medium in the form of argon or helium (atomization). The resulting metal powder material is then fractionated. For the method of high-speed gas-flame spraying of a material, a fraction in the range of 15-53 microns, preferably 20-45 microns, is used.

The use of compounds No. 1 and No. 2 can be carried out to protect the reboiler of a diesel hydrotreatment unit (for example, L-16-1), which is subjected to pit corrosion during operation of the lower shell shell under the action of hydrogen sulfide with steam and a solution of methyldiethanolamine (MDEA).

The use of compositions No. 1 and 2 in the form of Cr - 17.6%; C - 0.015%; Mo - 2.3%; Ni - 11.0%; Fe is the rest; or Cr, 28.3%; C - 1.3%; Si - 1.0%; Mn - 0.5%; Mo - 4.90%; Ni - 16.4%; Fe - the rest was effectively tested at the amine treatment plant at Gazprom Neftekhim Salavat.

The use of compositions No. 3 and No. 4 can be carried out to protect the tube sheets of the heater of the diesel hydrotreatment unit, the heat exchanger subjected to corrosion during operation, under the influence of water vapor, condensate, unstable hydrogenate.

Also, compositions No. 1-4 can be used to protect the absorber and stripper of the amine gas treatment unit subjected to general and local types of corrosion (pitting, ulcers) in the bottom zone of the equipment.

As is known, alloying elements such as Ni, Mn, C, Cr, can significantly increase the corrosion resistance of the material.

Modification with boron, silicon in combination with carbon, molybdenum improves the high-temperature structural stability of the material, promotes the formation of finely dispersed carbide and other hardening phases, which also gives the material wear and abrasion resistance.

The increase in carbon content is limited due to the fact that with its significant amount, stable carbides are released along grain boundaries with the main alloying elements Cr, Mo, Si, B, and thereby the elastic-plastic and corrosion properties of the solid solution are reduced due to depletion.

At the same time, the technology of high-speed flame spraying is proposed as the recommended method for applying these compositions, which is associated with the possibility of forming a dense (without through porosity) coating, as well as the possibility of using mobile complexes with a high productivity of the application process.

Thus, the proposed solution provides an increase in the resource of internal surfaces (volumes) of technological equipment subjected to corrosion-abrasive wear under the influence of an aggressive environment during operation.

Claims (10)

1. Corrosion-resistant coating to protect the inner surface of technological equipment subjected to wear under the influence of a medium with a hydrogen sulfide content of up to 20%, characterized in that it contains chromium, carbon, molybdenum, nickel and iron in the following ratio of ingredients, wt.%:
C  13-22 FROM  0.01-0.1 Mo  1.0-3.0 Ni  10.0-14.0 Fe  rest
2. Corrosion-resistant coating to protect the inner surface of technological equipment subjected to wear under the influence of a medium with a hydrogen sulfide content of up to 20%, characterized in that it contains chromium, carbon, molybdenum, nickel, manganese, silicon and iron in the following ratio of ingredients, wt .%:
Cr  20-28.5 FROM  0.1-1.5 Si  1.0-2.0 Mn  0.5-1.1 Mo  3.0-5.0 Ni  14.5-17.0 Fe  rest
3. Corrosion-resistant coating to protect the inner surface of technological equipment subjected to wear under the influence of a medium with a hydrogen sulfide content of more than 20%, characterized in that it contains chromium, carbon, molybdenum, nickel, titanium and iron in the following ratio of ingredients, wt.% :
Cr  16.0-18.0 FROM  0.01-0.1 Mo  1.0-3.0 Ti  0.5-1.2 Ni 12.0-14.0
Fe - the rest at the carbon equivalent of Seq. in the range from 4.50 to 5.3 and the pitting resistance coefficient PREN in the range from 22.6 to 30.2.
4. Corrosion-resistant coating to protect the inner surface of technological equipment subjected to wear under the influence of a medium with a hydrogen sulfide content of more than 20%, characterized in that it contains chromium, carbon, iron, molybdenum, tungsten and nickel in the following ratio of ingredients, wt.% :
Cr  20-24.0 FROM  0.01-0.02 Fe  3.0-5.0 Mo  13.0-15.0 W  2.0-4.0
Ni - the rest at the carbon equivalent of Seq. in the range from 9.5 to 11.2, and the pitting resistance coefficient PREN in the range from 60.25 to 76.4.
RU2016104928A 2016-02-15 2016-02-15 Composition of corrosion-resistant coating for protection of technological petrochemical equipment RU2636210C2 (en)

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RU2016104928A RU2636210C2 (en) 2016-02-15 2016-02-15 Composition of corrosion-resistant coating for protection of technological petrochemical equipment
PCT/RU2016/000078 WO2017142430A1 (en) 2016-02-15 2016-02-16 Composition of a corrosion resistant coating for protecting petrochemical equipment

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6503290B1 (en) * 2002-03-01 2003-01-07 Praxair S.T. Technology, Inc. Corrosion resistant powder and coating
US6513728B1 (en) * 2000-11-13 2003-02-04 Concept Alloys, L.L.C. Thermal spray apparatus and method having a wire electrode with core of multiplex composite powder its method of manufacture and use
US6749894B2 (en) * 2002-06-28 2004-06-15 Surface Engineered Products Corporation Corrosion-resistant coatings for steel tubes
RU65942U1 (en) * 2007-03-28 2007-08-27 Лев Христофорович Балдаев The housing assembly submersible centrifugal pumps for oil
RU69139U1 (en) * 2007-08-09 2007-12-10 Лев Христофорович Балдаев The housing assembly submersible centrifugal pumps for oil

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE0101602L (en) * 2001-05-07 2002-11-08 Alfa Laval Corp Ab Materials for surface coating and coated product material
ES2418135T3 (en) * 2009-02-17 2013-08-12 Mec Holding Gmbh Wear-resistant alloy
EP2650398B8 (en) * 2012-04-11 2015-05-13 Oerlikon Metco AG, Wohlen Spray powder with a superferritic iron base compound and a substrate, in particular brake disc with a thermal spray coating

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6513728B1 (en) * 2000-11-13 2003-02-04 Concept Alloys, L.L.C. Thermal spray apparatus and method having a wire electrode with core of multiplex composite powder its method of manufacture and use
US6503290B1 (en) * 2002-03-01 2003-01-07 Praxair S.T. Technology, Inc. Corrosion resistant powder and coating
US6749894B2 (en) * 2002-06-28 2004-06-15 Surface Engineered Products Corporation Corrosion-resistant coatings for steel tubes
RU65942U1 (en) * 2007-03-28 2007-08-27 Лев Христофорович Балдаев The housing assembly submersible centrifugal pumps for oil
RU69139U1 (en) * 2007-08-09 2007-12-10 Лев Христофорович Балдаев The housing assembly submersible centrifugal pumps for oil

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