US2133452A - Process for refining hydrocarbon distillate oils with boron fluoride - Google Patents

Description

Patented Get. 18, 1938 UNITED STATES PROCESS FOR DISTILLATE ORIDE REFINING OILS WITH BORON FLU- HYDROCARBON Amiot P. Hewlett, Cranford, N. J., assignor to Standard poration of Delaware No Drawing.

Oil Development Company, a cor- Application December 30, 1933,

. Serial No. 704,765

1 Claim.

This invention relates to the treatment of hydrocarbon oils belonging to the kerosene, gas oil and lubricating oil ranges with boron fluoride or other halides of similar chemical properties. The

oil tobe treated may be a kerosene distillate or a heavier distillate from petroleum. It may be a shale oil boiling within the kerosene range or higher. Other oils of similar boiling range produced by low temperature carbonization of coal,

in or by hydrogenation of coal, may be treated according to the present invention, although the best results are obtained when the invention is applied to the treatment of petroleum distillates of the boiling ranges specified. The treating 15 agent is boron fluoride or any of the other halides of boron, such as-boron chloride, bromide, iodide, halides of titanium, such as titanium tetrachloride, and halides of silicon such as silicon fluon'de.

20 One object of the present invention is to remove undesirable constituents from the distillates submitted to treatment.

Another object is the production of nitrogen bases from the sludge removed by the treating 5 agent from certain distillates, especially those boiling within the kerosene range.

I have found the halides mentioned above to be very good selective refining agents by removing undesirable constituents from the treated hydro- 30 carbon oil. When burning oils, such as kerosene,

are treated their burning characteristics are improved. The improvement in lubricating oils manifests itself in an increase of gravity and also in an improved (increased) viscosity index.

5 The viscosity index is a method of evaluating lubricating oils described in an article by E. W. Dean and G. H. B. Davis, in vol. 367, No. 10, October, 1929, of Chem. and Met. Engineering. A viscosity index of 100 designates a good grade 40 Pennsylvania lubricating oil. Kerosenes, lubricating oils or other oils have also a greatly improved color after the treatment.

The treating consists in agitating the hydrocarbon distillate with the treating agent, settling 5 and separating the sludge. The treating agent may be added directly to the distillate to be treated, as, for example, by introducing boron fluoride gas into kerosene, or it may be first dissolved in strong,.say substantially 100% sulfuric acid, and

50 the distillate treated with the sulfuric acid solution of the halide, this last method being especially advantageous when lubricating oils are treated. After the settling of the sludge, the hydrocarbon distillate may be filtered in order to 55 eliminate the last traces of sludge and. then washed, neutralized with alkali, and redistilled or finished in any manner well known to the art.

Boron fluoride and other halides of similar chemical characteristics are also very effective in refining cycle gas oils from petroleum cracking 5 operations for the production of high quality domestic and industrial heating oils. Unrefined cycle gas oils are in many ways unsatisfactory for heating purposes inasmuch as they contain certain undesirable constituents which may become highly corrosive during storage, attack metal parts of the burner installation and result in clogged screens and. strainers. Certain undesirable constituents of unrefined cycle gas oils also result in the formation of carbonaceous residues on burning. These objectionable characteristics are eliminated by refining the cycle gas oil according to the present invention.

The amount of treating agent used varies with the nature of the treating agent and also with the oil to be refined. Usually very small quantities such as 0.1-0.4 pound of boron fluoride per barrel of oil give satisfactory treating results, while much higher quantities such as 1-5 lbs. of titanium tetrachloride have to be used for the same degree of refinement. The amount of treating agent used may vary within broader limits than those just given for illustration.

Certain petroleum and shale oil distillates, especially those boiling within the kerosene range, contain nitrogen bases which are valuable in the manufacture of drugs, special chemicals, dyes and the like. These bases can be efiiciently separated by the use of small quantities of boron fluoride or similar compounds. The distillate is treated as usual with the boron fluoride or the other agent, and the sludge separated and hydrolyzed in order to liberate the nitrogen bases. Hydrolysis of the sludge may be effected by intimately mixing the sludge with water (hot water preferred) followed by neutralization with caustic. If preferred a caustic solution may be used instead of water for hydrolysis. The oil containing the liberated nitrogen bases may be further treated by dissolving the bases with. an aqueous mineral. acid, separating the acid solution from the remaining insoluble oil and then adding sodium hydroxide or other alkali until an alkali reaction results whereby the nitrogen bases are precipitated and can easily be separated from the aqueous solution. 1

The following example will illustrate the present invention: A sample of heating oil consisting of a cycle stock obtained in cracking gas oil and having gravity of 29 A. P. 1., final boiling point 600 F. and color 8 Robinson is treated with two What I claim is: 4 ounces per barrel of boron fluoride. The color An improved process for refining hydrocarbon is improved to 12 Robinson and the total copper distillate oils having initial boiling points at least ple given for illustration, but only by the followboron fluoride and separating the resulting sludge ing claim in which it is my intention to claim all from the oil.

10 novelty inherent in the invention. v AMIOT P. HEWLETT.