US2639260A - Process of refining oils - Google Patents

Description

y 1953 R. M. KENNEDY ET AL PROCESS OF REFININGVOILS' Filed July 14, 1950 R V: E mm m HME N 8 EN N V| V H E E NC K N Is R M M m miqsm M N $33 A E N R B mm B m mm mm A N M B E :QBRQQQ 8 o w m \mmegu w v 33.8% 4 .3 Q N w 2 33 3% $8 5k 5.53m

Patented May 19, 1953 PROCESS OF REFINING OILS Robert M Kennedy, Newtown'Square, and Abraham Schneiden'lhiladelphia, Pa., assignors to Sun Oil Company, Philadelphia, Pa., a corporation of. New Jersey 1;

Application July 14, 1950, Serial No. 173,745

This invention relates to the treatment of hydrocarbons, and more particularly to a process for the refining of hydrocarbons v Many chemical agents, including sulfuric acid, alkalies, fullers earth, boron fluoride, aluminum chloride, and the like, have been described as useful in the refining of hydrocarbonsand mixtures thereof, such as petroleum, including crude oils and the various petroleum fractions obtained' therefrom. A substantial proportion of refining operations is directed to the removal of non-hydrocarbons, such as sulfur, oxygen, and nitrogen compounds from crude oils or from various hydrocarbon fractions, such as the gasoline and lubricating oil fractions. For example, mercaptans, sulfides, disulfides, thioethers; and thiophenes are found in crude oil and the various petroleum fractions, and exert a. deleterious effect thereon, such as the formation of color and sludge. Other refining operationsare directed to the removal or adjustment of the concentration of a hydrocarbon type, such as aromatics, in a given fraction to prepare a product suitable for specialized uses, such as for useas transformer or lubricating oils. 7 For example, concentrated sulfuric acid has been used as the treating agent. Processes employing this reagent, however, have many disadvantages: a substantial quantity of the oil isconverted to a sludge from which neither the sulfuric acid nor a valuable hydrocarbon product can-beobtained, the sludge presents a serious disposal problem, serious corrosion problems are encountered, and special treating of the oil thereafter, such as by clay percolation, is required. Other processes involving the use of agents such as boron fluoride and aluminum'chlorid'e have been proposed' Such processes are subject to at least some of the above and other difliculties. For example, treatment with boron fluoride provides some improvement'in petroleum hydrocar bons, but is ineffective to secure the desired degree of refining. I I

,An object of the present invention is to provide a process for the refining ofhydrocarbons, particularly petroleum, including crude oil and the petroleum fractions obtainable therefrom. A further object is to provide a refining process wherein only a small amount of the petroleum hydrocarbons are converted to sludge and a large improvement in color, color and oxidation stability, and other properties is achieved. Another object is to provide a process for the simultaneous refining of a mixture of aromatic and non-aromatic hydrocarbons and adjustment 24 Claims. (01. 196-23) appear hereinafter.

2 of the aromatic content to a desired value. A still further object is to provide a proc'e'ss'of refining wherein the sludge formed is or' may be converted to useful products. Other objects In patent application Serial No. 38,167, filed July 10, 1948, now Patent Number 2,557,113; there is described various reactions of hydro carbons having at least onejtertiary hydrogen atom per molecule, such as alkylation, isomeriza tion, and the like, using boron fluoride and an alkyl fluoride having at least two carbon atoms per molecule as the catalytic components to initiate such reactions, the process being conducted in the absence of aromatics. 7 j

In patent application Serial No. 130,926, filed December 3, 1949, there is described the alkyla tion of alkylatable aromatics with saturates hav ing at least five carbon atoms and at least one tertiary hydrogen atom per molecule by bringing together a tertiary alkyl fluoride and BF; in" the presence of a mixture thereof, the mole ratio of tertiary alkyl fluoride. to aromatics plus satu rates being from 1:20 to 3:5, and the mole ratio of saturates to aromatics being from 1:4 to 4:1. In patent application Serial No. 173,746, filed July 14, 1950, there is described and claimed a process for the separation of aromatic hydrocarbons from saturated I non-aromatic hydrocarbons by bringing together a primary or secondary alkyl fluoride in the presence of a mixture thereof, whereby the aromatics are converted to andseparate as an insoluble sludge. L In patent application Serial No. 173,747, filed July 14, 1950, there is described and claimed a process for the. separation of non-hydrocarbons from hydrocarbonsnwhich comprises bringing together boron fluoride and a tertiary alkyl fluoride in the presence of a mixture of non-hydro-' carbons and hydrocarbons, whereby a sludge con' taining the non-hydrocarbons is formed and separates from the reaction mixture. In this process, if the quantity of alkyl fluoride used is in excess of the quantity required to remove the non-hydrocarbons, non-alkylatable aromatics are converted to and form a portion of the sludge, but only after substantially complete removal of the non-hydrocarbons. V j

In patent applic'ationserial No. 173,748, filed July 14, 1950, there is described and claimed a process for separating non-alkylatable aromatic hydrocarbons from saturated non-aromatic hydrocarbons by bringing together boron fluoride and atertiary alkylfluoride in the presence of a mixture'thereof, whereby the non-alkylatabl aromatics are converted to and separate as a sludge.

It has now been discovered that by bringin together boron fluoride and a primary alkyl fluoride having at least two carbon atoms per molecule or a secondary alkyl fluoride in the presence of a mixture of hydrocarbons and non-hydrocarbons, a catalytic condition is established which is effective to remove the non-hydrocarbons, and that only a small amount of the hyand highly selective for the removal of the nony hydrocarbon components of oil which form oxidation sludge, components which impart color and cause the formation of color on standing, such non-hydrocarbon components being, in gen-- eral, sulfur, oxygen, and nitrogen compounds. After removal of the deleterious non-hydrocarbons, the combination of the present refining agents is extremely potent and highly selective for the removal of aromatic hydrocarbons. Only after removal by sludge formation of substantially all of the non-hydrocarbons and aromatics do the reactions described in aforesaid patent ap plication Serial No. 38,16? occur. The alkylation reactions described in aforesaid patent application Serial No. 130,926 do not occur with the present combination of refining agents. Thus, by

hydrocarbons are converted to and separate as an I insoluble sludge. If aromatics are present, and if the amount of alkyl fluoride employed is in excess of the amount required to remove the nonhydrocarbons, the aromatics are also converted to and separate as an insoluble sludge, the amount of conversion being dependent upon the quantity of alkyl fluoride available for the reaction. Since alkylation reactions do not occur in the present process, both alkylatable and nonalkylatable aromatics are converted without distinction, the expression .non-alkylatable being employed to indicate aromatics which are not alkylatable under alkylating conditions.

The saturated non-aromatics from which nonhydrocarbons and aromatics are removed are the paraflins, including branched chain parafiins, and the cycloparafiins, including naphthenes.

A substantial advantage of the present refining process is that both of the components of the refining catalytic combination are soluble in petroleum hydrocarbons, thus eliminating the necessity for the vigorous agitation in processes involving insoluble reagents, such as sulfuric acid, hydrogen fluoride, and aluminum chloride. The present reaction mixture forms a homogeneous 4 phase wherein reaction occurs, and on completion of which the system becomes heterogeneous due to the formation of a sludge composed of the undesirable constituents of the hydrocarbons. It is characteristic of the present process that the alkyl fluoride employed in the process is converted to the corresponding paraffin. For example, if isopropyl fluoride is employed, propane is formed therefrom and is a product of the reaction. A further advantage of the present process is the instantaneous nature of the present reaction, which occurs and is completed practically as soon as the catalytic components are brought together in the presence of the oil being treated. It follows that time is not a critical variable in the process, and no advantage is obtained by long periods of contact. For practical convenience, a contact time of from 1 to 40 minutes is suitable.

Hydrocarbons which may be refined in accordance with the present process include crude petroleum and the various. fractions obtainable therefrom, such as gasoline, kerosene, and lubricatin'g oil fractions. Other fractions may be employed, such as normally gaseous fractions, in which case the operation is performed under sufficient pressure to maintain the hydrocarbons in the liquid phase. Normally solid fractions may also be employed, in which case the temperature is maintained sufliciently high to keep the fraction in the liquid phase. Unsaturated hydrocarbons, such as oleiins, should not be present in the reaction mixture to any substantial extent, and should constitute less than 1% of the hydro-, carbon charge. By petroleum hydrocarbons, as used herein, is meant those hydrocarbons which can be obtained from petroleum and mixtures thereof; by crude petroleum. is meant petroleum which has not been separated into fractions, and which therefore contains hydrocarbons having widely varying boiling points; and by petroleum fractions, and fraction, ismeant a mixture of hydrocarbons obtained from petroleum having a relatively narrow boiling range.

. Hydrocarbons and mixtures thereof obtained from sources other than petroleum may-be separated from non-hydrocarbons in accordance with the process of the present invention, and likewise may be separated from aromatics. For example, hydrooarbons prepared by the Fischer- Tropsch synthesis maybe separated from nonhydrocarbon constituents, such as oxygen compounds. By the term oil, as used herein, is meant the fractions, hydrocarbons, and hydrocarbon mixtures Which may be refined in the present process, as above defined.

Petroleum fractions, such as the lubricating oil, kerosene, and gasoline fractions, are preferred materials refined in the present process. In these oils, the concentration of non-hydrocarbons, principally sulfur, oxygen, and nitrogen compounds, is usually from 0.05 to 2%, although higher concentrations, up to about 5%, may be present in crude oils, and good results obtained therewith. The aromatic content is usually from 1% to 30% by volume, although smaller amounts may be removed, as may larger amounts, in the process. I

The alkyl fluorides Which may be employed in the present process are the primary and secondary alkyl fluorides which have at least two carbon atoms per molecule. By primary and secondary alkyl fluorides is meant those alkyl. fluorides which have a fluorine atom attached to a primary and a secondary carbon atom, respectively.

As specific examples of, primary fluorides which can be used iii-practicing the process, the following may be mentioned by way of illustration: ethyl" fluoride; l-fluoropropane l-fluorobutane; l-fluoro-2.-methylpropane; l-fluoropentane; lfluoro-2-methylbutane; and similar derivatives of hexanes, heptanes, octanes, and the like. As specific illustrations of secondary fluorides, the following can be used: isopropyl fluoride; 2-fluorobutane; 2-fluoro-3-methylbutane; Z-fluoropentane; and 2-fluoro-3,3-dimethylbutane. It will be understood that the specific compounds named above are given merely by way of illustration, and that any primary or secondary alkyl fluoride (with exception of methyl fluoride) will produce anoperative catalytic combination with BF: in accordance with the present invention.

In carrying out the process of the present invention, it is preferred to first dissolve the desired amount of alkyl fluoride in the oil, and then add the BFa, such as by bubbling it into the solution. It is permissible, however, to simultaneously but separately introduce the refinin agents, or to first dissolve BE; in the oil followed by the addition of the alkyl fluoride. It is also permissible to dissolve the alkyl fluoride and BE; in separate portions of the oil and then admix the portions, thus bringing together the refining agents in the presence of the oil. It is not permissible to premix the alkyl fluoride and BFs since, in such case, the catalytic condition required to Ice-exerted in the presence of the hydrocarbons being refined is immediately dissipated. By the expression bringing together, and terms of similar import, as employed herein in conjunction with the use of the present refining agents, is meant the actual contacting thereof, which in the present process is always performed in thepresence-of the oil being refined, i. e., the

present refining. agents, a primary or secondary alkyl fluoride :and boron fluoride, are contacted only when they arealso in contact with the ,oil being'refined.

The degree of refining, i. e., the quantity of non-hydrocarbons, and subsequently of the aromatics, removed in the process of the present invention is substantially dependent upon the quantity of alkyl fluoride employed. The quantity of boron fluoride to employ is not critical, so long as a quantity sufficient to establish the necessary catalytic condition is employed. Since the concentration iof sulfur, oxygen, and nitrogen compounds varies according to the origin of the material being'treated, and upon prior treatments, if any, it is preferred to determine the optimum concentration of alkyl fluoride for each application, such value being readily determina ble in view of the present specification. If it is desired to remove'only the non-hydrocarbons, the quantity .of alkyl fluoride may be adjusted to so operate, and Hit is further desired to remove all or a portion of the aromatics, a correspondingly. higher concentration of the alkyl fluoride should be used. In general, a concentration of alkyl fluoride greater than required to remove all of the aromatics, or of all of the non-hydrocarbons in the event that aromatics are not present in the reaction mixture, should not be used because, in such case, the reactions of the tertiary hydrogen containing isoparaffins which may be present occurs, which reactions may materially alter the composition and properties of the hydrocarbons being treated. A concentration of alkyl fluoride of from 0.5 to 2 weight percent is usually sufficient to remove substantially all of the nonhydrooarbons of a petroleum fraction. If it is 6. desired to subject the fraction to amore drastic treatment in order to remove aromatics, a greater quantity of the alkyl fluoride should be employed, say from 2 to 20 weight percent although in some instances as much as 30 weight percent may be employed. The quantity of alkyl fluoride in excess of that required to remove the non-hydrocarbons, which is required to remove a desired quantity of aromatics, should be determined for each application. In general, it has been found that 1% by weight of alkyl fluoride in excess of the amount required to remove nonhydrocarbons will convert about 20% of the aromatics present, anda similar excess of 2.3%. will convert about 50% of the aromatics, in both instances using an excess of boron fluoride. The separation of such large amounts of aromatics with only small quantities of alkyl fluoride is considered a significant advantage of the present process. Equal molar quantities of the various alkyl fluorides within the scope of this invention remove substantially the same quantity of arcmatics from a given mixture.

As. above stated, the concentration of boron fluoride to employ is not critical, the requirement being that a quantity sufiicient to establish the catalytic condition be employed. In general; from 0.1 to 400 weight percent, based on the weight of alkyl fluoride employed, is suflicient to cause completion of the present refining process to the desired extent, which, as above described, is determined by the quantity of alkyl fluoride employed.

The present reaction is conducted in the liquid phase. Super-atmospheric pressure is preferred so that the desired amount of boron fluoride readily dissolves in the reaction mixture. Pressures of from atmospheric to 500 p. s. i., depending on the concentration of boron fluoride desired, is suitable in the case of normally liquid hydrocarbons, whereas higher pressures, up to 1,000 p. s. i., may be employed with normally gaseous fractions in order to maintain such fractions in the liquid state.

The operable temperature range varies considerably and depends largely on the particular ma.- terial being treated. A temperature sufficiently high to maintain the hydrocarbons in a fluid, i. e., non-viscous, state is preferred. In general, temperatures of from 20 C. to 150 C. are employed, and all primary and secondary alkyl fluorides, except methyl fluoride, in combination with boron fluoride give good results within this range. If it is desired to operate at lower temperatures, such as in the refining of liquefied normally gaseous hydrocarbons, the lowest temperatures 'at which secondary fluorides can be employed is C., and the lowest temperature at which primary fluorides can be employed is 10, C. An exception is ethyl fluoride, which has been found to be somewhat more inert than the alkyl fluorides having 3 or more carbon atoms per molecule, and which requires a temperature of about +20 C. to be operable in the present process.

As above describe-:1, the present refining agents are soluble in the present oils, and on completion of the reaction a sludge separates to form a heterogeneous phase. As already described, only a small. amount of hydrocarbons are converted to sludge in the removal of non-hydrocarbons, and hence the total quantity of sludge formed is small. If aromatics are also converted to sludge, the quantity thereof increases in accordance with the amount of conversion of the aromatics. The

accuses sludge maybeseparate'd by any convenient or 'desir'ed means, such as by filtering, centrifuging or decanting. The oil, after sludge removal, is advantageously washed with water or an aqueous solution of an alkali, such as sodium hydroxide, or it may be treated with ammonia. The refined product is obtained by separating the heterogeneous phase of this last treatment, and is preferably dried if necessary or desirable. Treatment of the oil with clay, such as is usually required after sulfuric acid refining, is not required, but of course may be employed if desired, as may other process steps as known to the art.

Boron fluoride and hydrogen fluoride are easily recoverable from the separated sludge by heating or applying a vacuum, or both. For example, heating to about 199 C. under a slight vacuum drives ofi hydrogen fluoride and boron fluoride, which may be recovered, the boron fluoride being recycled to the process and the hydrogen fluoride being used to prepare additional alkyl fluoride, such as by an addition reaction with an appropriate olefin, as lrnownto the art. the resulting allcyl fluoride being then employed in the process.

Attention is now directed to the accompanying flow diagram which illustrates an embodiment of the present invention, and is primarily directed to the removal of non-hydrocarbons. principally sulfur compounds, from a saturate petroleum fraction. The hydrocarbons to be refined, such as a petroleum fraction containing non-hydrocarbons, is introduced. into the process through line I, and isopropyl fluoride, used to illustrate the various allzyl fluorides which may be employed. is introduced into the system through line 2. 'A mixture of the petroleum fraction and isopr'cpyl fluoride passes through line 3 into heat exchanger l wherein the temperature of the mixture is adjusted to the desired value, usually from C. to 150" C. The mixture then passes through. line 5 into mixer E, into which the BFI-l is introduced through line 5. Means to provide mild agitation in mixer 3 may be supplied if desired, but may be omitted if the turbulence of how is suf ficient to secure substantially uniform mixing. On introduction of the B512 reaction begins and proceeds rapidly to completion with formation of a sludge composed largely of the deleterious components of the petroleum fraction. The sludge-containing fraction passes through line 8 into separator iii, sludge being removed there from through line i! and the refined fraction through Propane formed from the isopropyl fluoride is removed from the separator through line E3. The refined fraction passes into tower 14 wherein it is treated. to remove any entrained acid gases such as by washing with water. the water being introduced into tower l4 through line i5. Refined product is removed through is and the used water through line it. The refined product may be dried and further treated as desired. Sludge from separator 50 passes through line ii into distillation zone l8, and BF; and HF are evolved therefrom. EFs is recycled to the process through lines 29 and 8. HF passes through line 2! into reactor 22 wherein it is reacted. with propylene supplied through line 2 1 to form isopropyl fluoride, which is introduced into the process through lines 25 and 2. Residue from distillation zone I9 is removed through line 26 and may be employed as fuel Or as a component of compositions useful, for example, in paving roads, and the like.

The quantity of reactants to employ and the 8 various operating conditlohs are ad'v'antagebusi maintained as hereintoforc described' The following example illustrates a preferred embodiment of the present invention: r It was desired to prepare an oil suitable'for use in transfonners from a petroleum fraction obtained from East Texas crude, the fraction having a viscosity at .F'aof 59 Saybolt Universal; a flash point of 280 F2, and at 10 mm. of mercury an initial boiling point of 2 4 F., 9.50% distillation point at 361 F., and an endpoint "of 495 F. The aromatic content of the fraction was composed. substantially entirely of nonalkyb atable aromatics. One hundred parts by Weight of the described petroleum fraction and 2.3 parts by weight of 'tertiary' cutyl fiuoridewere introduced intoa'reactor and the temperature adjusted to and maintained at 25 C; byimm'ersion in a water bath; 5.? parts by weight of boron fluoride-we're introduced' into the stirred mixture'resultin'g in'a final pressure of 132 p. s. i. 'Contact"was"con-'- tinucd for 40 minutes. The oil was then filtered, treated with ammonia and refiltered to give the final product.

It was found that the sulfur content had been reduced from 0.17% to 0.03%, and that the arc-'- matic content had been reduced from 19% to 14%. The product exhibited enhanced properties; for example, the slight oxidation value was reduced from 39.5 to 1. Physical propertieso'f the product were substantially the sam'e'as for the charge stock, except for a small increase in vis coslt'y "and decrease in refractive index.

"vhen a'p'riinary alkyl fluoride having at least two carbon atoms per molecule or a secondary alkyl fluoride is substituted for t-butyl fluoride substantially identical results are" 'obtained/ In another embodiment of the present raves": tion, an oil especially stable against oxidation prepared by subjecting a portion of a fraction, to the action of the present refining agents, and then blending the so-treated portion with the untreated portion. If desired, the untreated nor tion may be given a light refining treatment, such as by bringing together coronfluoride and a relatively small proportion of a primary or seccndary fluoride in the presence thereof, or by treatment with boron fluoride as the sole refining agent. From 0.1 to 10 parts of the "treated oil may advantageously be blended with .1 partof untreated or lightertreated portion. I j

Modifications in the described procedure will be apparentto those skilled intlie art; the pres ent. process maybe adapted to batch or continuous operation. 1., The separation of aromatic from nonaromatic hydrocarbons in the absence of non-hydrocarbons is not included within the scope of the present claims, but is described and claimed in aforesaid copending application Serial No. 173,746, filed July 14, 1950. The invention claimed is: Process 0f refining ydrocarbons which com prises reacting a mixtur of hydrocarbons and non-hydrocarbons with boron fluoride and an alkyl mono-fluoride selected from the group consisting of primary alkyl mono-fluorides having at least two carbon atoms permoleoule and second ary alkyl mono-fluorides as the sole refining agents, said boron fluoride and said alkyl monofluoride being brought together only in the presence of said mixture of hydrocarbons and nonhydrocarbons, whereby said non-hydrocarbons ges a eo -areconverted' to a sludge, and separating said sludge from the reaction mixture.

said boron fluoride and said alkyl mono-fluoride being brought together only in the presence of said petroleum containing non-hydrocarbons,

whereby said non-hydrocarbons are convertedto a sludge, and separating said sludge from the reactio'nm ixture. V t e 3. Process for reflning a petroleum fraction containing non-hydrocarbons which comprises reacting said petroleum fraction containing nonhydrocarbons with boron fluoride and an alkyl mono-fluoride selected from the group consisting of primary alkyl mono-fluorides having at least two carbon atoms per molecule and secondary alkyl mono-fluorides as the sole refining agents, said boron fluoride and said alkyl mono-fluoride being brought together only in the presence of said petroleum fraction containing non-hydrocarbons, whereby said non-hydrocarbons are converted to a sludge, and separating said sludge from the reaction mixture.

4. Process according to claim 3 wherein the quantity'of alkyl fluoride employed is from 0.5 to 2 percent by weight.

. 5. Process according to claim 3 alkyl fluoride is isopropyl fluoride.

6. Process according to claim 3 alkyl fluoride is 2-fluorobutane.

, 7. Process according to claim 3 alkyl fluoride is 2-fluoropentane.

8. Process according to claim 3- alkyl fluoride is 3-fluoropentane.

9. Process according to claim 3 wherein alkyl fluoride is 2-fluoro-3-methylbutane.

10. Process for the refining of a lubricating oil fraction containing non-hydrocarbons which comprises reactin said lubricating oil fraction containing non-hydrocarbons with boron fluoride and an alkyl mono-fluoride selected from the group consisting of primary alkyl mono-fluorides having at least two carbon atoms per molecule and secondary alkyl mono-fluorides as the sole refining agents, said boron fluoride and said alkyl mono-fluoride being brought together only in the presence of said lubricating oil fraction containing non-hydrocarbons, whereby said non-hydrocarbons are converted to a sludge, and separating said sludge from the reaction mixture.

11. Process according to claim wherein the quantity of alkyl fluoride is from 0.5 to 2 percent by weight.

12. Process according to claim 10 alkyl fluoride is isopropyl fluoride.

13. Process for refining a kerosene fraction containing non-hydrocarbons which comprises reacting said kerosene fraction containing nonhydrocarbons with boron fluoride and an alkyl mono-fluoride selected from the group consisting of primary alkyl mono-fluorides having at least two carbon atoms per molecule and secondary alkyl mono-fluorides as the sole refining agents, said boron fluoride and said alkyl mono-fluoride being brought together only in the presence of said kerosene fraction containing non-hydrocarbons, whereby said non-hydrocarbons are conwherein the wherein the wherein the wherein the the wherein the verted to a sludge, and separating said sludge from the reaction mixture.

by weight.

15. Process according to claim 13 wherein the alkyl fluoride is isopropyl-fluoride.

16'. Process for refining a gasoline fraction containing non-hydrocarbons which comprises reacting said gasoline fraction containing non-hydrocarbons with boron fluoride and an alkyl mono-fluoride selected from the group consisting of primary alkyl mono-fluorides having at least two'c'arbon atoms per molecule and secondary alkyl mono-fluorides as the sole refining agents, saidboron fluorideand said alkyl mono-fluoride being brought together only in the presence of said gasoline fraction containing non-hydrocarbons, whereby said non-hydrocarbons are converted to a sludge, and separating said sludge from the reaction mixture.

17. Process according to claim 16 wherein the quantity of alkyl fluoride is from 0.5 to 2 percent by weight.

18. Process according to claim 16 wherein the alkyl fluoride is isopropyl fluoride.

19. Process for refining a petroleum fraction containing saturated non-aromatic hydrocarbons, non-hydrocarbons, and aromatic hydrocarbons which comprises reacting said petroleum fraction with boron fluoride and an alkyl mono-fluoride selected from the group consisting of primary alkyl mono-fluorides having at least two carbon atoms per molecule and secondary alkyl monofluorides as the sole refining agents, said boron fluoride and said alkyl mono-fluoride being brought together only in the presence of said petroleum fraction, whereby non-hydrocarbons and aromatic hydrocarbons are converted to a sludge, and separating said sludg from the reaction mixture.

20. Process according to claim 19 wherein the quantity of alkyl fluoride employed is in excess of that required to remove the non-hydrocarbons, and is less than the quantity required to remove all of the aromatics.

21. Process according to claim 20 wherein the quantity of alkyl fluoride employed is from about 0.2 to 30 percent by weight.

22. Process for the preparation of a refined petroleum fraction stable against oxidation which comprises dividing a petroleum fraction and reacting a portion thereof with boron fluoride and an alkyl mono-fluoride selected from the group consisting of primary alkyl mono-fluoride having at least two carbon atoms per molecule and secondary alkyl mono-fluorides as the sole refining agents, said boron fluoride and said alkyl mono-fluoride being brought together only in the presence of said portion of said petroleum fraction, whereby non-hydrocarbon components of said portion are converted to a sludge, separating the so-formed sludge from said portion, and blending the so-treated portion with the untreated portion of said fraction.

23. Process for the preparation of a refined petroleum fraction stable against oxidation which comprises dividing a petroleum fraction and reacting a portion thereof with boron fluoride and an alkyl mono-fluoride selected from the group consisting of primary alkyl mono-fluorides having at least two carbon atoms per molecule and secondary alkyl mono-fluorides as the sole refining agents, said boron fluorid and said alkyl mono-fluoride being brought together only in the presence of said portion of said petroleum fraction, whereby non-hydrocarbon components of said portion are converted to a sludge, separating the so-formed sludge from said portion, subjecting the remaining portion of the fraction to a similar but lighter treatment, and blending the two so-treated portions.

24. Process for the refining of a lubricating oil fraction containing non-hydrocarbons which comprises reacting said lubricating oil fraction containing non-hydrocarbons with boron fluoride and isopropyl fluoride as the sole refining agents, said boron fluoride and said isopropyl fluoride being brought together only in the presence of said lubricating oil fraction containing non-hydrooarbons, whereby said non-hydrocarbons are converted to a sludge and said isopropyl fluoride is converted to propane, and separating said sludge and said propane from the reaetion mix- References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,162,682 Terres June 13,1939 2,267,730 Grosse et al Dec. 30, 1941 2,343,744 Burk Mar. 7, 1944 2,343,841 Burk Mar. 7, 1944 2,357,495 Bloch Sept. 5, 1944 2,378,762 Frey June 19, 1945 2,408,173 Matuszak Sept. 24, 1946 2,472,908 Linn June 14, 1949 2,507,499 Cade May 16, 1950

Claims (1)

1. PROCESS OF REFINING HYDROCARBONS WHICH COMPRISES REACTING A MIXTURE OF HYDROCARBONS AND NON-HYDROCARBONS WITH BORON FLUORIDE AND AN ALKYL MONO-FLUORIDE SELECTED FROM THE GROUP CONSISTING OF PRIMARY ALKYL MONO-FLUORIDES HAVING AT LEAST TWO CARBON ATOMS PER MOLECULE AND SECONDARY ALKYL MONO-FLUORIDES AS THE SOLE REFINING AGENTS, SAID BORON FLUORIDES AND SAID ALKYL MONOFLUORIDE BEING BROUGHT TOGETHER ONLY IN THE PRESENCE OF SAID MIXTURE OF HYDROCARBONS AND NONHYDROCARBONS, WHEREBY SAID NON-HYDROCARBONS ARE CONVERTED TO A SLUDGE, AND SEPARATING SAID SLUDGE FROM THE REACTION MIXTURE.

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