Compositions and methods of removing contaminants in refinery desalting
It has been discovered that contaminants such as metals and/or amines can be transferred from a hydrocarbon phase to a water phase in an emulsion breaking process by using a composition that contains water-soluble C5-C12 polyhydroxy carboxylic acids, ammonium salts thereof, alkali metal salts thereof, and mixtures of all of these. The composition may also optionally include a mineral acid to reduce the pH of the desalter wash water. The method permits transfer of metals and/or amines into the aqueous phase with little or no hydrocarbon phase under-carry into the aqueous phase. Resolving the emulsion into the hydrocarbon phase and the aqueous phase occurs in a refinery desalting process using electrostatic coalescence. The composition is particularly useful in treating crude oil emulsions, and in removing calcium and other metals therefrom. The polyhydroxy carboxylic acid additionally inhibits metal corrosion of metal pipe or other equipment used in a crude unit.
1. A method of transferring contaminants from a hydrocarbon phase to a water phase in a refinery desalting process comprising:
adding to a wash water an effective amount of a composition to transfer contaminants from a hydrocarbon phase to an aqueous phase, the composition comprising a water-soluble component selected from the group consisting of polyhydroxy carboxylic acids having 5 to 12 carbon atoms selected from the group consisting of glucaric acid, iduronic acid, galacturonic acid, glucuronic acid, digalacturonic acid, and combinations thereof, and where the polyhydroxy carboxylic acid does not include gluconic acid, ammonium salts thereof, alkali metal salts thereof, and mixtures of any of these, where the wash water has a pH of 6 or below;
mixing the wash water with crude oil to create an emulsion; and
resolving the emulsion into the hydrocarbon phase and the aqueous phase in a refinery desalting process using electrostatic coalescence, where at least a portion of the contaminants are transferred to the aqueous phase.
2. The method of claim 1 where the contaminant is selected from the group consisting of metals, salts, solids other than salts, amines, and combinations thereof.
3. The method of claim 2 where the contaminant comprises a metal selected from the metals in a Periodic Table Group selected from the group consisting of IA, IIA, IVA, IB, IIB, VB, VIB, and VIII.
4. The method of claim 3 where the metal is selected from the group consisting of calcium, magnesium, iron, zinc, nickel, chromium, lead, cadmium, copper, and combinations thereof.
5. The method of claim 1 where the polyhydroxy carboxylic acid is present in an amount to additionally inhibit metal corrosion of metal pipe or other equipment used in a crude unit, and the method additionally comprises inhibiting metal corrosion.
6. The method of claim 5 where the polyhydroxy carboxylic acid forms a molar 1:1 salt with the contaminant.
7. The method of claim 1 where in the adding of the composition, the composition additionally comprises a mineral acid.
8. The method of claim 7 where the amount of mineral acid is sufficient to lower the pH of the wash water to 6 or below.
9. The method of claim 1 where in the adding of the composition, the polyhydroxy carboxylic acid is present in the emulsion in an amount ranging from about 1 to about 2000 ppm, based on the crude oil.
10. The method of claim 1 where the composition additionally comprises at least one additional component selected from the group consisting of a water or alcohol solvent, a corrosion inhibitor other than the polyhydroxy carboxylic acid, a demulsifier, a scale inhibitor, metal chelants, wetting agents and mixtures thereof.
11. The method of claim 5 in an absence of a different added corrosion inhibitor.
12. A method of transferring contaminants from a hydrocarbon phase to a water phase in a refinery desalting process comprising:
adding to a wash water an effective amount of a composition to transfer contaminants from a hydrocarbon phase to an aqueous phase, the composition comprising a water-soluble component selected from the group consisting of polyhydroxy carboxylic acids having 5 to 12 carbon atoms selected from the group consisting of glucaric acid, iduronic acid, galacturonic acid, glucuronic acid, digalacturonic acid, and combinations thereof, and where the polyhydroxy carboxylic acid does not include gluconic acid, ammonium salts thereof, alkali metal salts thereof, and mixtures of any of these, where the wash water has a pH of 6 or below;
mixing the wash water with crude oil to create an emulsion; and
resolving the emulsion into the hydrocarbon phase and the aqueous phase in a refinery desalting process using electrostatic coalescence, where at least a portion of the contaminants are transferred to the aqueous phase;
where the effective amount of the composition additionally inhibits metal corrosion of metal pipe or other equipment used in a crude unit, and the method additionally comprises inhibiting metal corrosion, in an absence of a different added corrosion inhibitor.
13. The method of claim 12 where the contaminant is selected from the group consisting of metals, salts, solids other than salts, amines, and combinations thereof.
14. The method of claim 13 where the contaminant comprises a metal selected from the metals in a Periodic Table Group selected from the group consisting of IA, IIA, IVA, IB, IIB, VB, VIB, and VIII.
15. The method of claim 14 where the metal is selected from the group consisting of calcium, magnesium, iron, zinc, nickel, chromium, lead, cadmium, copper, and combinations thereof.
16. The method of claim 12 where the polyhydroxy carboxylic acid forms a molar 1:1 salt with the contaminant.
17. The method of claim 12 where in the adding of the composition, the polyhydroxy carboxylic acid is present in the emulsion in an amount ranging from about 1 to about 2000 ppm, based on the crude oil.
18. The method of claim 12 where the composition additionally comprises at least one additional component selected from the group consisting of a water or alcohol solvent, a demulsifier, a scale inhibitor, metal chelants, wetting agents and mixtures thereof.
19. A method of transferring contaminants from a hydrocarbon phase to a water phase in a refinery desalting process comprising:
adding to a wash water an effective amount of a composition to transfer contaminants from a hydrocarbon phase to an aqueous phase, the composition comprising a water-soluble component selected from the group consisting of polyhydroxy carboxylic acids having 5 to 12 carbon atoms selected from the group consisting of glucaric acid, iduronic acid, galacturonic acid, glucuronic acid, digalacturonic acid, and combinations thereof, and where the polyhydroxy carboxylic acid does not include gluconic acid, ammonium salts thereof, alkali metal salts thereof, and mixtures of any of these, where the wash water has a pH of 6 or below;
mixing the wash water with crude oil to create an emulsion; and
resolving the emulsion into the hydrocarbon phase and the aqueous phase in a refinery desalting process using electrostatic coalescence, where at least a portion of the contaminants are transferred to the aqueous phase;
where:
the contaminant is selected from the group consisting of metals, salts thereof, iron-based solids, and combinations thereof, where the metal is selected from the group consisting of calcium, magnesium, iron, zinc, nickel, chromium, lead, cadmium, copper, and combinations thereof; and
the polyhydroxy carboxylic acid forms a molar 1:1 salt with the contaminant.
20. The method of claim 19 where the polyhydroxy carboxylic acid is present in an amount to additionally inhibit metal corrosion of metal pipe or other equipment used in a crude unit, and the method additionally comprises inhibiting metal corrosion.