Mineral oils: processes and products – Refining – Organic acid or phenol contaminant removal
Patent
1998-08-03
2000-04-25
Myers, Helane
Mineral oils: processes and products
Refining
Organic acid or phenol contaminant removal
C10Q 1700
Patent
active
060540427
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
The present invention relates to a process for neutralizing petroleum acids in order to lower their corrosivity and increase their value.
BACKGROUND OF THE INVENTION
Whole crudes with high petroleum acid content such as those containing naphthenic acids are corrosive to the equipment used to extract, transport and process the crudes.
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 using corrosion inhibitors for the metal surfaces of equipment exposed to the acids, or by neutralizing and removing the acids from the oil. Examples of these technologies include treatment of metal surfaces with corrosion inhibitors such as polysulfides (U.S. Pat. No. 5,182,013) or oil soluble reaction products of an alkynediol and a polyalkene polyamine (U.S. Pat. No. 4,647,366), or by treatment of a liquid hydrocarbon with a dilute aqueous alkaline solution, specifically dilute aqueous NaOH or KOH (U.S. Pat. No. 4,199,440). U.S. Pat. No. 4,199,440 notes, however, that a problem arises with the use of aqueous solutions that contain higher concentrations of base. These solutions form emulsions with the oil, necessitating use of only dilute aqueous base solutions. U.S. Pat. No. 4,300,995 discloses the treatment of carbonous materials particularly coal and its products such as coal liquids, vacuum gas oils, and petroleum residua having acidic functionalities, with a dilute quaternary base such as tetramethylammonium hydroxide in a liquid (alcohol or water).
While these processes have achieved varying degrees of success there is a continuing need to develop more efficient methods for treating these acidic crudes, whole crudes and fractions thereof.
SUMMARY OF THE INVENTION
The present invention provides for a process for decreasing the acidity of an acidic crude oil comprising: contacting a naphthenic acid-containing crude oil at an elevated temperature with an effective amount of overbased detergent dispersed in oil to produce a treated crude oil having a reduced acidity. Preferably the overbased detergent is a calcium sulfonate or phenate. The amount of overbased detergent should be effective to decrease the acidity of the crude and preferably can range from 0.025:1 to 10:1 moles of calcium to acidic functionality in the crude oil.
The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed.
DETAILED DESCRIPTION OF THE INVENTION
Some whole crude oils and fractions thereof contain organic acids that contribute to corrosion or fouling of refinery equipment. These organic acids generally fall within the category of naphthenic and other organic acids. Naphthenic acids alone or in combination with other organic acids such as phenols can cause corrosion at temperature ranges of about 65.degree. C. (150.degree. F.) to 420.degree. C. (790.degree. F.).
The crudes that may be used are naphthenic acid-containing crude oils or acid-containing fractions thereof including whole and topped crudes, that are liquid or liquefiable at the temperatures at which the present invention is carried out. Whole crudes are unrefined, undistilled crudes.
Applicants have discovered that acidic crudes, i.e., those containing naphthenic acids may be treated by contacting the crude with an effective amount of an oil (hydrocarbon) dispersible basic reagent to produce a treated or final crude having a reduced or essential absence of acidity. This is accomplished by neutralizing in whole or in part the acidity of the crude. The naphthenic acids may be present either alone or in combination with other organic acids, such as phenols. The oil-dispersible basic reagents are called overbased detergents and are further described below. The acidic crudes are preferably whole c
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Anderson Michael Paul
Ballinger Bruce Henry
Blum Saul Charles
Gorbaty Martin L.
Martella David J.
Exxon Research and Engineering Co.
Myers Helane
Scuorzo Linda M.
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