Marathon Oil Company

Carle C Zimmerman, Jr

Mark A Plummer

Donald E Schroeder, Jr

Wayne E Luetzelschwab

John R Coleman, Jr

Henry J Pietrzak

Kent W Robinson

Petroleum sulfonates are obtained by continuously contacting whole crude oil or topped crude oil with gaseous sulfur trioxide (contains as a diluent sulfur dioxide and light hydrocarbon vapor) in a reaction zone operated at a temperature of 120.degree.-250.degree. F. and a pressure of 3-50 psia. The reaction product is then passed to a vapor-liquid separating stage where a vapor stream is separated and a portion of it is recycled back to the reaction zone; a liquid stream is separated from the separating stage and a portion of it is recycled back to the reaction zone. The remaining portion of the liquid stream is neutralized with a monovalent inorganic base to obtain the petroleum sulfonate. The petroleum sulfonates are particularly useful to recover crude oil from subterranean reservoirs.

Sulfonation of crude oils with gaseous SO.sub.3 to produce petroleum

A sour liquid hydrocarbon feedstock is desulfurized upon contact with a hydrogen gas in the presence of a catalyst to obtain a low sulfur product and a hydrogen sulfide gas by-product. The hydrogen sulfide gas is treated with an anthraquinone which is dissolved in a solvent having a polarity which is greater than 3 Debye units, to produce sulfur and oxygen. The oxygen is used to oxidize a hydrocarbon fuel and produce the hydrogen gas used in the initial desulfurization step.

Hydrocarbon desulfurization process

Petroleum sulfonates useful to impart micellar characteristics to mixtures of hydrocarbon and aqueous medium are obtained by reacting a hydrocarbon gas oil feedstock (average molecular weight 250-700; A/AP aliphatic to aromatic proton) ratio 5-50 moles/mole, 30-100% of the feedstock molecules contain aromatic portions and the A/AP ratio of the aromatic portion being about 3-20 moles/mole) with a solution of EDC (ethylene dichloride) containing 0.1-0.3 lb. liquid SO.sub.3 /lb EDC. The SO.sub.3 concentration is about 0.1-0.3 lb. of SO.sub.3 /lb of gas oil feedstock. Reaction takes place in a back-mix tubular reactor wherein at least about 4 parts of reaction products are recycled per 1 part of reaction products withdrawn and wherein the gas oil feedstock plus recycled reaction products and the SO.sub.3 /EDC streams entering the reaction zone are in turbulent flow. Velocity ratio of the feedstock plus recycled reaction products stream to the SO.sub.3 /EDC stream is at least 4:1, respectively. The withdrawn reaction products are neutralized with an aqueous basic liquid, e.g. aqueous solution, NH.sub.4 OH and thereafter the EDC is recovered from the neutralized reaction products to obtain unextracted sulfonate mix. The unextracted sulfonate mix is extracted with an aqueous alcohol solution to obtain a raffinate phase, an extract phase, and a brine phase; the extract phase is withdrawn and stripped of alcohol and water to obtain the desired petroleum sulfonate.

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Littleton, CO, United States of America

Carle C Zimmerman, Jr