Emulsion neutralization of high total acid number (TAN) crude oil

a technology of organic acids and crude oil, applied in water/sewage treatment by neutralization, quary waste water treatment, aqueous alkali solution refining, etc., can solve the problems of corrosive equipment, many petroleum crudes with high organic acid content, and does not disclose the treatment of whole crudes or fractions boiling at 1050+°, so as to reduce the acidity and corrosivity of an acid containing corrosive

Inactive Publication Date: 2006-03-16
EXXON RES & ENG CO
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AI Technical Summary

Benefits of technology

[0015] It has been discovered that acid neutralization can be accomplished in a process that does not avoid emulsion formation and in fact practices emulsion formation and maintenance as part of the process eliminating the need for chemical demulsifiers.
[0016] The present invention is a method for decreasing the acidity and corrosivity of an acid containing corrosive crude comprising, securing an aqueous alkaline earth metal hydroxide solution or slurry, forming a water-in-oil emulsion of the aqueous alkaline earth metal hydroxide solution or slurry in a hydrocarbon carrier oil, preferably a small quantity of the same corrosive crude to be treated, the water-in-oil emulsion having an aqueous phase droplet size of between about 0.5 to 50μ, preferably between about 1 to 25μ, more preferably between about 1 to 10μ, mixing the water-in-oil emulsion with the crude to be treated in a ratio of about 0.2 to 10 volume of emulsion to 100 volumes of crude to be treated, preferably 0.5 to 5 volume of emulsion to 100 volumes of crude or fract

Problems solved by technology

Many petroleum crudes with high organic acid content, such as whole crude oils containing naphthenic acids, are corrosive to the equipment used to extract, transport and process the crude, such as pipestills and transfer lines.
U.S. Pat. No. 4,199,440 notes, however, that a problem arises with the use of aqueous solutions that contain higher concentrations of aqueous base.
Importantly, '532 does not disclose the treatment of whole crudes or fractions boiling at 1050+° F.
Since naphthenic acids are distributed through all crude fractions (many of which are not vaporizable) and since crudes differ widely in naphthenic acid content the '532 patent does not provid

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

[0040] 1-5 μm droplet size (Ca(OH)2-slurry-in-crude emulsion was prepared in the lab by mixing 5 gm Ca(OH)2, 20 cc H2O and 140 cc Gryphon crude in a beaker with a 19000 rpm batch single stage rotor / stator blender at room temperature.

[0041] Stoichiometric amount of Ca(OH)2 slurry-in-oil emulsion (29.5 ml) was then blended with (440 ml) Gryphon crude (volumetric ratio of 6.7%) and allowed to sit overnight at room temperature in a 2″ d×10″ h graduated cylinder simulating ambient temperature crude storage tank conditions. A similar experiment was done with Chad crude at 50° C. simulating a heated storage tank at 50° C.

[0042] TAN analysis next morning showed 75% and 76% TAN reduction respectively for two repeated experiments. The calcium analysis of the crude showed 80% TAN neutralization for both, which checks the TAN reduction data.

example 2

[0043] An emulsion of aqueous calcium hydroxide in Gryphon crude was prepared using a high-speed (19000 rpm) shear mixer at room temperature. A mixing time as short as 20 seconds is very effective in preparing small drop size water-in-oil emulsions giving a water droplet size distribution of 1 to 10 microns with occasional droplets up to 25 microns. A measured amount of this emulsion equivalent to 100% TAN neutralization was dispersed in the crude oil (separately Gryphon and Chad) by moderate hand shaking for less than 15 seconds. The mixture was allowed to stand overnight in a tall vessel (H / W˜6) with periodic sampling of the crude mixture. Summarized below is the effective TAN reduction vs. time for both Gryphon and Chad crudes:

(a) Gryphon Crude (TAN = 3.14) at 20° C. (room temperature) using1 to 10μ droplets: 29.5 ml of emulsion added to 440 ml of Gryphon crude(volumetric ratio of 6.7%) to achieve full stoichiometric neutralization.TAN NeutralizedSettling TimeTAN Neutralized(as...

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Abstract

This invention is a method for reducing the total acid number of organic acid containing petroleum oil comprising forming a water-in-oil emulsion comprising an aqueous Group IIA metal hydroxide solution or slurry in a hydrocarbon oil, said water-in-oil emulsion having an aqueous droplet particle size diameter of from 1 to 25μ, adding the water-in-oil emulsion to the organic acid containing petroleum oil and permitting the mixture to stand for a time sufficient to permit the neutralization of the organic acids in the petroleum oil.

Description

[0001] This application claims the benefit of U.S. Ser. No. 60 / 609,624 filed Sep. 14, 2004.FIELD OF THE INVENTION [0002] This invention relates to the neutralization of the organic acids contained in petroleum oils to reduce the acidity and corrosivity of such oils. BACKGROUND OF THE INVENTION [0003] Many petroleum crudes with high organic acid content, such as whole crude oils containing naphthenic acids, are corrosive to the equipment used to extract, transport and process the crude, such as pipestills and transfer lines. [0004] Efforts to minimize naphthenic acid corrosion have included a number of approaches. U.S. Pat. No. 5,182,013 refers to such recognized approaches as blending of higher naphthenic acid content oils with low naphthenic acid content oils. Additionally, a variety of attempts have been made to address the problem by replacing carbon or low alloy steels by more expensive, highly alloyed stainless steels, using corrosion inhibitors for the metal surfaces of equipm...

Claims

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Application Information

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IPC IPC(8): C10G19/00
CPCC02F1/66C02F2103/10C10G33/00C10G19/073C10G19/02
Inventor HSU, EDWARD CHING-SHENGPATEL, RUTTON DINSHAWBROWN, LEO DALE
Owner EXXON RES & ENG CO
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