US1865235A

US1865235A - Treating process for hydrocarbon oils

Info

Publication number: US1865235A
Application number: US119171A
Authority: US
Inventors: Cross Roy
Original assignee: CROSS DEV CORP
Current assignee: CROSS DEV CORP; CROSS DEVELOPMENT Corp
Priority date: 1926-06-28
Filing date: 1926-06-28
Publication date: 1932-06-28
Anticipated expiration: 1949-06-28

Description

Patented June 28, 1932 UNITED STATES,

PATENT OFFICE BOY CROSS, OF KANSAS CITY, MISSOURI, ABBIGNOB T GROSS DEVELOPMENT CORPORA- 'l'ION, OF WILMINGTON,'DELAWABE, A OOBPOBATION OF DELAWARE TBEATIH G PROCESS FOR HYDBOQABBON OILS No Drawing.

This invention relates to improvements in the process of refining petroleum oils such as gasoline, medicinal oil, lubricating oils, industrial naphtha, machine oils and the like.

It more particularly relates to the purification of hydrocarbon oils or oils consisting largely of h drocarbons. Among its purposes are the ollowing:

1. For removal of sulphur.

m 2. For removal of color and to produce water white products.

3. For removal of obnoxious odors.

4. For stabilizing the oil as to color and odor.

In the practice of this invention metals or the hydrides of metals of the alkali and alkali earth group are used. These metals include, in their order of usefulness and availabilitymetallic sodium, metallic calcium, metallic potassium, metallic magnesium, metallic strontium, metallic barium, metallic lithium.

, Some of the important properties in conve sidering this invention may be tabulated as an follows:

Combining Melting Specific Metal equivalent point gravity 0. Sodium 23 97.6 0.971 0alcium.. 20 805 1.54 Potassium a9. 1 ea 5 a. an

M esium 12 650 1. 70 B um 6B 850 3.78

It has been found that all of these metals and their hydrides react with petroleum oil to efiect a removal of sulphur, a removal of color, a polymerization of unsaturated compounds and a stabilization of the hydrocarbons to a more or less variable'degree. As to sulphur removal, the alkali metals, such as though magnesium and calcium are more ef- Application illed June 28,

potassium and sodium, are very active,

1920. Serial a... 119,111.

als. The method of ap lication will, of course vary in each case. n some instances it is desirable to use a combination of the metals. This is particularly well illustrated in the use of mixtures of metallic sodium and metallic potassium. Although the melting pomt of metallic sodium is approximately 97 C. and of metallic potassium approx1- mately 63 (3., a mixture of two gram molecules of potassium with 1 gram molecule of sodium has a melting point of 10 0. below zero, All intermediate temperatures can be obtained by using the appropriate percentages. In the same way mixtures of alkali metals and alkali earth metals can be used to give products of low melting point. Productsor appropriate meltin point can be made to correspond with tle temperatures at which it is desired to treat the hydrocarbon. For exam le, if it is desired to treat mm having a melting point of 0 C. may be used and the gasoline may be bubbled directly through the metal mixture, or the metal mixture may bemade to flow in opposite direction and in contact with the flow of the hydrocarbons. The sulphides or precipitates formed in the metal can then be continuously removed from the system and purified to return only the pure metal.

There is a great varietyof ways of appl ing these metals or metal hydrides for t e removal of sulphur, color and to otherwise purify hydrocarbon oils. Some of the important methods may be classified as follows:

1. The metal is contacted either hot or cold and either with the 'hot liquid or the hot vapor of the oil to be treated. A suitable method of ccntactin is to first mix the metal thorou hly wit a heated bleaching clay or other fiist'ributing material and then use this material for treating the vapors or the liquid oil. This material may be a plied either by passing the vapors throug the metal treated clay in a tower or by mixin the clay with the liquid oil and filtering o the metal mixed cla One suitable method in the treating of 1 light gasohne, a mixture of potassium so cracked gasoline is to contact the asoline fairly quickly with sulphuric acid 0 a gravity usually of from 60 to B6. The acid is. then very quickly removed, preferably by the use of a centrifuge. The gasoline is then continuously mixed with the metal coated clay which is quickl pumped through a filter press such as a weetland filter.- The product is lar ely desulphurized, has a fairly good odor an has a water white color. As a general rule, however, the higher the temperature of treatment the more complete is the sulphur removal, although it 18 not necessar to use the higher temperatures to get a go bleaching efi'ect. For complete sulphur removal it is necessary to have sufficient metal to react with all of the sul hur. It is,'of course, always important to e 1minate insofar as possible any water or steam from the oil before treating. This method of treatment applies to other oils, such as lubricating oils, painters naphtha and the like where ood color and low sulphur content are deslrable.

2. The treatment may also be applied by pumping the liquid or vapor directly over the metal in granular form. Th1s metal may be granulated by meltin and the unused metal may be recovered y remeltmg and removing the impurities, the treatment, however, being efiected on the surface of the metal in solid condition.

3. In many instances treatment may be effected by bubbling the liquid through the molten metal or mixtures of metals. This method of treatment is convenient as it can be carried out in completely enclosed contain ers, and also will allow the circulation of the metal as well as the hydrocarbon oil and in counterflow to each other. This treatment may be effected at almost any desired temperature as alloys or mixtures can be made having melting points from 10 C. below zero In the treatment of hydrocarbon oils with alkali and alkali earth metals it has been possible to remove a varying percentage of the sulphur. The sulphur exists in the oil in a number of different combinations, including such substances as-- Mercaptans, thio-alcohols or alkyl hydrosul hides=RHS lkyl disulphides=R S Sulphine or sulphonium compounds= RSSCI Sulpnones=R SO Sulphonic acids=RHSO Thio-sulphonic acids=RHS O Sulphinic acids=RHSO2 The amount of sulphur removed has varied in difi'erent types of oils from 10% to 95%. This varies also with the method of treatment and the particular metal used. Potassium and sodium metals and potassium and sodium hydrides are most efiective at lower tempercium 15 very efl'ecive. Magnesium 1s apparently least effective of all, although in some instances it is more efl'ective for color removal than the other metals.

It is not perfectly clear just how these metals effect so complete removal of the sulphur without destroying the molecule, but the low percentage of loss, in most cases being much less than 3%, indicates that the sulphur is extracted from the molecule and the hydrocarbon portion of the molecule either forms a new molecule or undergoes a rearrangement of the hydrogen atoms. Probable reactions may be shown by the following symbolic reactions, assuming M to represent the metal, H to represent the hydrogen and R to represent the hydrocarbon radical involved. The reacatures, although at higher temperatures caltion of a mercaptan would be approximately as follows RSH M=RH MS or, as a specific instance using ethyl mercaptan or sulphhydride,

C2H5SH Ca C H In the case of an alkyl sulphide reaction might be as follows:

RS+MH=MS+RH or, in the case ofan alkyl disulphide:

R S+M=RR+MS cracked gasoline in its raw state frequently hasfrom 0.2% to 1% of sulphur. By the ordinary methods of refining with sulphuric ac1d all of the molecule combined with the sulphur is removed, thus entailing a loss ofpften as much as 40% of the gasoline when it is desired to produce a product having less than one-tenth of one per cent of sulphur. With this method of treatment, however, the loss 1n extreme instances would rarely exceed 5 California gasoline is particularly hard to treat and by this method it has been found possible to remove in most instances from 50% to 90% of the sulphur in the gasoline without any substantial losses of volume.

I claim as my invention:

1. A method of treating petroleum, which consists in continuously passing the petroleum in intimate contact with a metal of the alkaline earth group in a liquid state, the said said oil, and removing the purifyin mamas metal caused to flow in an opposed direction to the direction of flow of the petroleum to efiect a chemical combination with said metal, continuously removinv and purifying the metal, and continuously removing and cooling the petroleum.

2. A method of treating petroleum, which consists in continuously passing the petroleum vapors in intimate contact with a liquid alkaline earth metal, the liquid metal passing in an opposed direction to the direction of flow of the petroleum to efi'ect a chemical combination with said metal, continuously removing and purifying the metal, and continuously removing and cooling the petroleum.

3. A method of treating petroleum oil which consists in continuously passing the petroleum in intimate contact with metallic calcium, the calcium being heated above its meltin point, the calcium passed in an opposed direction to that of the flow of the petroleum oil to efiect a chemical combination between the calcium and the impurities in metal and continuously removing and cooling the treated oil.

4. A method of treating petroleum oil which consists in continuously passing the petroleum in intimate contact with metallic calcium, the calcium being heated above its meltin point, the calcium passed in an opposed ireetion to that of the flow of the petroleum oil to effect a chemical combination between the calcium and the impurities in said oil, continuously removing the purifying metal and continuously removing the purified oil from the system.

5. The method of desulphurizing and de colorizing hydrocarbon oil, including the step of contacting said oil with an alkaline earth metal to effect a chemical combination between said alkaline earth metal and the sulphur compounds to be eliminated.

6. The method of desulphurizing and dccolorizing hydrocarbon oil, includin the steps of contacting said oil with an alkaline earth metal to effect a chemical combination between said alkaline earth metal and the sulphur compounds to be eliminated, continuously removing the chemical compounds thus formed.

7. The method of dcsulphurizing and dccolorizime hydrocarbon oil, including the steps of contacting said oil with an alkaline ical combination between said alkaline earth metal and the sulphur compounds to be eliminated.

9. The method of desulphurizing and decolorizing hydrocarbon oil, including the step of contacting said oil with an alkaline earth metal, incorporated with an argillaceous material, to effect a chemical combination between said alkaline earth metal and the sulphur compounds to be eliminated.

10. The method of desulphurizing and decolorizing hydrocarbon oil, includin the steps of contacting said oil with an al aline earth metal, incorporated with an argillaceous material, to effect a chemical combination between said alkaline earth metal and the sulphur compounds tobe eliminated, and continuously removing the compounds thus formed.

11. The method of desulphurizing and decolorizing hydrocarbon oil, including the steps of contacting said oil with an alkaline earth metal, incorporated with an argillaceous material, to effect a chemical combination between said alkaline earth metal'and the sulphur compounds to be eliminated, continuously removing the compounds thus formed, and subsequently removing said metal from said compound.

12. The method of desulphurizing and decolorizing hydrocarbon oil which includes the steps of continuously passing the oil in a vapor phase, in contact with an alkaline earth metal in liquid form to effect a chemical combination between said alkaline earth metal and the impurities to be eliminated from said hydrocarbon, resulting in a precipitate of said combination, and continuously removing said precipitate. V

13. A process as in claim 12 in which the hydrocarbon flows in a direction counter to the alkaline earth metal in liquid form.

14. A process as in claim 5 in which the alkaline earth metal is calcium.

15. A process as in claim 5 in which the alkaline earth metal is barium.

16. A process as in claim 5 in which the alkaline earth metal is magnesium.

17. A continuous method of purifying petroleum hydrocarbons including the steps of vaporizing the hydrocarbons and bringing the evolved vapors into intimate contact with an alkaline earth metal in a liquid state, continuouslycirculating said liquefied alka line earth metal in counter flow relation with said hydrocarbon vapor, to form polymers by chemical action, diverting saturated olymers and reactionproducts and supp ying additional unused treating metal.

ROY CROSS.