# US 8,465,599 B2 · Chromiun-enriched oxide containing material and preoxidation method of making the same to mitigate corrosion and fouling associated with heat transfer components

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- Number: US 8,465,599 B2
- Document ID: US8465599B2
- Status: Granted
- Kind: B2
- Application number: 13/193,223
- Filed: 2011-07-28
- Published: 2011-11-17
- Granted: 2013-06-18
- Earliest claimed: 2005-12-21
- Assignees: ExxonMobil Research and Engineering Company
- Applicants: ChangMin Chun; Mark A. Greaney; Thomas Bruno; Ian A. Cody; Trikur A. Ramanarayanan
- Inventors: ChangMin Chun; Mark A. Greaney; Thomas Bruno; Ian A. Cody; Trikur A. Ramanarayanan
- Web page: https://patentgrep.com/patent/US8465599B2

## CPC

- F28D 7/16: the conduits being arranged in parallel spaced relation ({F28D7/0008 - F28D7/0058 take precedence}; F28D7/02 - F28D7/10 take precedence)
- B32B 15/011: {all layers being formed of iron alloys or steels}
- B32B 15/012: {one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy}
- C10G 9/203: {chemical composition of the tubes}
- C22C 38/00: Ferrous alloys, e.g. steel alloys (cast-iron alloys C22C37/00)
- C22C 38/02: containing silicon
- C22C 38/04: containing manganese
- C22C 38/18: containing chromium
- C22C 38/22: with molybdenum or tungsten
- C22C 38/38: with more than 1.5% by weight of manganese
- C22C 38/44: with molybdenum or tungsten
- C22C 38/48: with niobium or tantalum
- C22C 38/50: with titanium or zirconium
- C22C 38/60: containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
- C23F 15/00: Other methods of preventing corrosion or incrustation
- F28F 19/00: Preventing the formation of deposits or corrosion, e.g. by using filters {or scrapers}
- F28F 19/002: {by using inserts or attachments}
- F28F 19/02: by using coatings, e.g. vitreous or enamel coatings
- F28F 19/06: of metal
- F28F 21/082: {from steel or ferrous alloys}
- F28F 21/083: {from stainless steel}
- F28F 25/08: Splashing boards or grids, e.g. for converting liquid sprays into liquid films; Elements or beds for increasing the area of the contact surface (packing elements per se B01J19/30, B01J19/32)
- F28G 7/00: Cleaning by vibration {or pressure waves}
- C10G 2300/4075: Limiting deterioration of equipment
- F28D 2021/0059: {for petrochemical plants}
- Y10T 428/12549: Adjacent to each other
- Y10T 428/1259: Oxide
- F28D: HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT (fluid heaters having heat generating means and heat transferring means F24H; furnaces F27; details of heat-exchange apparatus of general)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C22C: ALLOYS (treatment of alloys C21D, C22F)
- C23F: NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE (working metal by laser beams B23K26/00; desurfacing by applying flames B23K7/00; working of metal by electro-erosion B23H; producing decorative effects by removing surface material, e.g. by engraving, by etching, B44C1/22; electrolytic etching or polishing C25F); INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- F28F: DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION (water and air traps, air venting F16)
- F28G: CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS (cleaning pipes or tubes in general B08B9/02; devices or arrangements for removing water, minerals, or sludge from boilers while the boiler is in operation, or which remain in position while the boiler is in operation, or are specifically adapted to boilers without any other utility F22B37/48; removal or treatment of combustion products or combustion residues F23J; removing ice from heat-exchange apparatus F28F17/00)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A method of providing sulfidation corrosion resistance and corrosion induced fouling resistance for a heat transfer component is disclosed. The heat transfer component includes a heat exchange surface formed from a chromium-enriched oxide containing material formed from the composition δ, ε, and ζ, wherein ζ is a steel containing at least about 5 to about 40 wt. % chromium, ε is a chromium enriched oxide (M3O4 or M2O3 or mixtures thereof) formed on the surface of the steel ζ, wherein M is a metal containing at least 5 wt. % Cr based on the total weight of the metal M, and δ is a top layer formed on the surface of the chromium-enriched oxide ε, comprising sulfide, oxide, oxysulfide, and mixtures thereof. The top layer δ comprises iron sulfide (Fe1-xS), iron oxide (Fe3O4), iron oxysulfide, iron-chromium sulfide, iron-chromium oxide, iron-chromium oxysulfide, and mixtures thereof. The metal M of the chromium enriched oxide (M3O4 or M2O3 or mixtures thereof) may comprise Fe, Cr, and constituting elements of the steel ζ. The steel ζ may be selected from low chromium steels, ferritic stainless steels, martensitic stainless steels, austenitic stainless steels, duplex stainless steels and precipitation-hardenable alloys.

## Claims

### Claim 1

A method of providing sulfidation corrosion resistance and corrosion induced fouling resistance to a heat transfer component surface, the method comprising:
providing a steel surface containing at least about 5 to about 40 wt. % chromium;
forming a chromium-enriched oxide layer (M3O4 or M2O3 or mixtures thereof) on the surface of the steel, wherein M is a metal containing at least 5 wt. % Cr based on the total weight of the metal M, wherein the layer having a uniform surface roughness of less than 40 micro inches; and,
forming a surface protective layer on the surface of the chromium-enriched oxide layer, comprising sulfide, oxide, oxysulfide, and mixtures thereof.

### Claim 2 (depends on 1)

The method of claim 1, wherein the chromium enriched oxide layer (M3O4 or M2O3 or mixtures thereof) is formed on the surface of the steel by exposing the steel to a low oxygen partial pressure environment at a temperature of from about 300° C. to I 100 ° C. for a time sufficient to effect the formation of the chromium enriched oxide layer (M3O4 or M2O3 or mixtures thereof) on the surface of said steel.

### Claim 3 (depends on 2)

The method of claim 2, wherein a time sufficient to effect the formation of the chromium enriched oxide layer (M3O4 or M2O3 or mixtures thereof) on the surface of the steel ranges from 1 min to 100 hrs.

### Claim 4 (depends on 2)

The method of claim 2, wherein the low oxygen partial pressure environment is formed from gases selected from the group consisting CO2, CO, CH4, NH3, H2O, H2, N2, Ar, He and mixtures thereof.

### Claim 5 (depends on 2)

The method of claim 2, wherein the low oxygen partial pressure environment is a gas mixture of CO2 and CO.

### Claim 6 (depends on 2)

The method of claim 2, wherein the low oxygen partial pressure environment is a gas mixture of H2O and H2.

### Claim 7 (depends on 2)

The method of claim 2, wherein the low oxygen partial pressure environment is pure hydrogen or argon, wherein the atmosphere of the low oxygen partial pressure environment having an dew point of less than −40° C.

### Claim 8 (depends on 2)

The method of claim 2, wherein the low oxygen partial pressure environment is vacuum.

### Claim 9 (depends on 1)

The method of claim 1, further comprising imparting a vibrational force to the heat transfer component surface.

### Claim 10 (depends on 1)

The method of claim 1, further comprising feeding a fluid adjacent to the heat transfer component surface and imparting a pulsed force to the fluid.