Compositions – Preservative agents – Anti-corrosion
Patent
1998-09-15
2000-02-08
Brouillette, D. Gabrielle
Compositions
Preservative agents
Anti-corrosion
2523891, 25238961, 208 47, 507939, C09K 300, C10G 118
Patent
active
060224940
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
The present invention relates to a process for decreasing the acidity and corrosivity of crudes and crude fractions containing petroleum acids.
BACKGROUND OF THE INVENTION
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.
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 equipment exposed to the acids, or by neutralizing and removing the acids from the oil. Some inhibitor companies have claimed that the use of specific sulfur and phosphorus based organic corrosion inhibitors can be effective in reducing corrosion by naphthenic acids. Examples of such 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), and 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 aqueous 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 heavy oils, vacuum gas oil, and petroleum residua, having acidic functionalities, with a quaternary base such as tetramethylammonium hydroxide in a liquid (alcohol or water). Additional processes using aqueous alkali hydroxide solutions include those disclosed in Kalichevsky and Kobe, Petroleum Refining With Chemicals, (1956) Ch. 4, as well as U.S. Pat. Nos. 3,806,437; 3,847,774; 4,033,860; 4,199,440 and 5,011,579; German Patents 2,001,054 and 2,511,182; Canadian Patent 1,067,096; Japanese Patent 59-179588; Romanian Patent 104,758 and Chinese Patent 1,071,189. Certain treatments have been practiced on mineral oil distillates and hydrocarbon oils (e.g., with lime, molten NaOH or KOH, certain highly porous calcined salts of carboxylic acids suspended on carrier media). Whole crude oils were not treated.
U.S. Pat. Nos. 2,795,532 and 2,770,580 (Honeycutt) disclose processes in which "heavy mineral oil fractions" and "petroleum vapors", respectively are treated. The '532 patent further discloses that a "flashed vapors" are contacted with "liquid alkaline material" containing, inter alia, alkali metal hydroxides and "liquid oil." A mixture solely of NaOH and KOH in molten form is disclosed as the preferred treating agent, however "other alkaline materials, e.g., lime, can also be employed in minor amounts." Importantly, '532 does not disclose the treatment of whole crudes or fractions boiling at 1050 plus .degree. F. (565.sup.+ .degree. C.). Rather '532 treats only vapors and condensed vapors of the 1050 minus .degree. F. (565.sup.- .degree. C.) fractions, that is, fractions that are vaporizable at the conditions disclosed in '532. Petroleum residua and other non-vaporizable (at '532 process conditions) fractions containing naphthenic acids would not be treatable by the process. 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 provide an expectation that one would be able to successfully treat a broad slate of crudes of a variety of boiling points.
In U.S. Pat. No. 2,068,979, it is disclosed that naphthenates we
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Anderson Michael Paul
Ballinger Bruce Henry
Blum Saul Charles
Gorbaty Martin Leo
Martella David J.
Brouillette D. Gabrielle
Cole Monique T.
Exxon Research and Engineering Co.
Scuorzo Linda M.
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