# US 2022/0033725 A1 · Phosphorous-free oil soluble molybdenum complexes for high temperature naphthenic acid corrosion inhibition

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- Number: US 2022/0033725 A1
- Document ID: US20220033725A1
- Status: Published application
- Kind: A1
- Application number: 17/443,591
- Filed: 2021-07-27
- Published: 2022-02-03
- Earliest claimed: 2020-07-29
- Assignees: Ecolab USA Inc.
- Applicants: Ecolab USA Inc.
- Inventors: Oussama Zenasni; Philip Andrew Thornthwaite; Maria DeJesus Marquez; John Nathan Scholz
- Web page: https://patentgrep.com/patent/US20220033725A1

## CPC

- C10G 75/02: by addition of corrosion inhibitors
- C09K 8/54: Compositions for in situ inhibition of corrosion in boreholes or wells
- C10G 7/10: Inhibiting corrosion during distillation
- C23F 11/04: in markedly acid liquids
- C23F 11/16: Sulfur-containing compounds
- C09K 2208/32: Anticorrosion additives
- 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
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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

## Abstract

Disclosed are sulfur-containing molybdenum complexes used in compositions and methods for inhibiting or reducing high temperature corrosion in petroleum refineries.

## Claims

### Claim 1

A method of inhibiting corrosion comprising:
introducing into a fluid source containing corrodents a sulfur-containing molybdenum complex having the general formula selected from Formula I or II:
Mo2—(S—R)n Formula I
Wherein R represents an oxygen, nitrogen or carbon-containing compounds such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; n is 4-10.
R and R′ each represents an oxygen, nitrogen or carbon-containing compounds such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; and X represents oxygen or sulfur and can be the same or different but where at least one X in the formula is sulfur.

### Claim 2 (depends on 1)

The method of claim 1, wherein the fluid source is in contact with distillation columns, strippers, trays, or piping.

### Claim 3 (depends on 1)

The method of claim 1, wherein the fluid source comprises a liquid hydrocarbon fraction.

### Claim 4 (depends on 1)

The method of claim 1, wherein the corrodents comprise naphthenic acid, sulfur or combinations thereof.

### Claim 5 (depends on 1)

The method of claim 1, wherein the fluid source comprises a TAN of 0.2 to 20 or the fluid source temperature is about 175° C. to 600° C.

### Claim 6 (depends on 1)

The method of claim 1, wherein the sulfur-containing molybdenum complex has the general formula III:
Wherein R represents an oxygen, nitrogen or carbon-containing compounds such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; n is 2-6.

### Claim 7 (depends on 1)

The method of claim 1, wherein the R, R′ comprise each disulfides, dithiolates, dithiocarbamates, dithiocarbonates, dithioacids, inorganic polysulfides, organic polysulfides, polymers thereof and mixtures thereof.

### Claim 8 (depends on 7)

The method of claim 7, wherein the organic polysulfide has the general formula IV:
R2—Sx—R3 Formula IV
Wherein R2 and R3 each represents an oxygen, nitrogen or carbon-containing ligands such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; and R2 and R3 can be the same or different.

### Claim 9 (depends on 1)

The method of claim 1, wherein the sulfur-containing molybdenum complex comprises the following:
Wherein the arcs represent alkyl chains (linear, branched and cyclic) with or without saturation or heteroatoms or both; thiolates, sulfides, thiocarbamates, thiocarbonates, thioacids, aromatic rings with or without substituents, organic polysulfides, or inorganic polysulfides.

### Claim 10

A composition comprising a sulfur-containing molybdenum complex to inhibit corrosion in a fluid source containing corrodents and in contact with a metal containment, the sulfur-containing molybdenum complex comprising the formula selected from Formula I or II:
Mo2—(S—R)n Formula I
Wherein R represents an oxygen, nitrogen or carbon-containing compounds such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; n is 4-10.
R and R′ each represents an oxygen, nitrogen or carbon-containing compounds such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; and X represents oxygen or sulfur and can be the same or different but where at least one X in the formula is sulfur.

### Claim 11 (depends on 10)

The composition of claim 10, wherein the composition further comprises one or more, asphaltene inhibitors, paraffin inhibitors, dispersants, emulsion breakers, or any combination thereof.

### Claim 12 (depends on 10)

The composition of claim 10, wherein the fluid source is in contact with distillation columns, strippers, trays, or piping.

### Claim 13 (depends on 10)

The composition of claim 10, wherein the fluid source comprises at least a liquid hydrocarbon fraction.

### Claim 14 (depends on 10)

The composition of claim 10, wherein the corrodents comprise naphthenic acid, sulfur, or combinations thereof.

### Claim 15 (depends on 10)

The composition of claim 10, wherein the fluid source comprises a TAN of 0.2-20 or the fluid source temperature is 175° C. to 600° C.

### Claim 16 (depends on 10)

The composition of claim 10, wherein the sulfur-containing molybdenum complex has the general formula III:
Wherein R represents an oxygen, nitrogen or carbon-containing compounds such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; n is 2-6.

### Claim 17 (depends on 10)

The composition of claim 10, wherein the R, R′ comprise each disulfides, dithiolates, dithiocarbamates, dithiocarbonates, dithioacids, inorganic polysulfides, organic polysulfides, polymers thereof and mixtures thereof.

### Claim 18 (depends on 17)

The composition of claim 17, wherein the organic polysulfide has the general formula IV:
R2—Sx—R3 Formula IV
Wherein R2 and R3 each represents an oxygen, nitrogen or carbon-containing ligands such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; and R2 and R3 can be the same or different.

### Claim 19 (depends on 10)

The composition of claim 10, wherein the sulfur-containing molybdenum complex comprises the following:
Wherein the arcs represent alkyl chains (linear, branched and cyclic) with or without saturation or heteroatoms or both; thiolates, sulfides, thiocarbamates, thiocarbonates, thioacids, aromatic rings with or without substituents, organic polysulfides, or inorganic polysulfides.

### Claim 20

A treated metal containment comprising:
a metal containment comprising a metal surface and a fluid source comprising the sulfur-containing molybdenum complex having Formula I or II and wherein at least a portion of the metal surface is contacted by the fluid source:
Mo2—(S—R)n Formula I
Wherein R represents an oxygen, nitrogen or carbon-containing compounds such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; n is 4-10.
R and R′ each represents an oxygen, nitrogen or carbon-containing compounds such as alcohols, alkyl, alkenyl, amides, amines, or aryl groups; and X represents oxygen or sulfur and can be the same or different but where at least one X in the formula is sulfur.