US1681638A - Refining hydrocarbon oils - Google Patents

Description

Patented Aug. 21, 1928. a

\ UNITED STATES v 1,681,638 PATENT OFFICE.

EIRAM J. HALLE, OF NEW YORK, N. Y., ASSIGNOR TO UNIVERSAL OIL PRODUCTS GOI- PANY, OF CHICAGO, ILLINOIS, A. CORPORATION OF SOUTH DAKOTA.

. anrmme HYDROCARBON one.

No Drawing. Application filed llay 12, 1920, Serial No. 380,762. ,Renewed February 12, 1927.

My invention relates toa process of refining hydrocarbon oils for'the production of marketable gasoline and hydrocarbon sulfonic acids.

Among the salient objects of my invention are to provide a process for the production of water white gasoline or light oils; to provide a process for the production of sulfonic acids of the series of hydrocarbons in cracked oils, straight run oils from crude petroleum and thermal decomposition of coal oil shales and lignites.

The process consists essentiall of distilling the hydrocarbon oil throug a column of hot sulfuric acid of varying strengths (depending upon the type of hydrocarbon oil to be treated) while the hydrocarbon material is in vapor form.

A typical method of o erationis to charge the still with the h rocarbon oil to be treated, the vapor out et of the still passing to the bottom of the column of sulfuric acid which is maintained at a slightly higher temperature at times than the vapor coming off the still. The sulfuric acid reacts with part of the hydrocarbon forming sulfonic acids of latter, while the oil vapors pass on through water and caustic soda for neutralization, ielding marketable gasoline.

A typicai hydrocarbon oil such as a California cracked oil will illustrate my process, as to products, yields and losses.

. I have successfully treated California oil in the manner hereinbefore mentioned with sulphuric acid with concentrations of 20, 55,. 70, and 95%. With a concentration 0 20% a charge-of 400 cc. was distilled and. yielded a gasoline percent of 52.1 of a Baum gravity of 61.1. A similar quantity of oil when distilled with a 40% solution ofsulphuric acid yielded 51.2 gasoline with a' Baum gravity of 61.8 with a 55% solution a gasoline yield of approximately 50% was obtainable of a Baum gravity of 60.6.

p Greater quantities of sulphuric acid did not produce such high ields of gasoline and for instance, we foun that with a 70% solution a gasoline percentage of 41.0 could be obtained with a gravity of 64.5.

The sulfuric acid sludges varied in color from light reddish to deep black as'a function of the concentration'of the acid used.

The. ercentage and type of sulfonic acids varie also as a function of the acid concentration. The concentrated sulfuric acid roduced a deep black tar which upon coolmg was highly viscous and asphaltic in character showing a highly polymerizing effect upon the hydrocarbons, producing sulfonic acids of high. molecular weight whereas the less concentrated acid produced relatively simple molecular weight sulfonic acids of part of the hydrocarbons of the starting hydrocarbons.

Another set of tests were carried out using hydrochloric acid instead of sulfuric acid, in a similar manner. The products formed were water white gasoline from the reaction (after neutralizing the oil layer) and chlorides of hydrocarbons in the hydrochloric acid sludge which was of a cherry red color at the end of the tests, depending upon the concentration of acid used. The Water from the acid distilling over with the hydrocarbon vapors from the acid converter was of y a yellow to orange color. The chloridesas well as the sulfonic acids hydrocarbons can be readily converted into alcohols and'acetates by well known organic reaction. I

I claim as my invention: Y

1. A refining process consisting in passing oil vapors through a column of heated sulphuric acid maintained at a temperature at least equal to the temperature of the oil vapors, said acid being in excess of concentration of 20% and not exceeding 55%, and in subjecting the vapors of said acid treatment to a neutralizing treatment to produce gasoline. 1

2. A process for refining hydrocarbons which comprises introducing hydrocarbon oil to a still, in subjecting oil in the still to a temperature sufiicient to vaporize substantial portions thereof, and passing vapors thus formed through a column of sulphuric acid in excess of concentration of 20% and not exceeding 55% and in subjecting the vapors of said acid treatment. to a neutralizing treatment to produce gasoline.

3. The step in a process for refining hydrocarbons which comprises passing the hydrocarbons being treated while in vaporous form through a sulphuric acid solution in excess of concentration of 20% and not 106 exceeding 55%.

HIRAM J. HALLE.