US2639262A - Process for refining oils - Google Patents

Description

or lubricating oils.

Patented May 19, 1953 PROCESS FOR REFINING OILS Robert M. Kennedy,'Newtown Square, and Abraham Schneider, Philadelphia, Pa., assig'nors to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey Application July 14, 1950, Serial No. 173,747

22 Claims.

This invention relates to the treatment of hydrocarbons, and more particularly to a process for the refining of hydrocarbons.

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 hydrocarbons and 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 nonhydrocarbons, such as sulfur, oxygen, and nitrogen compounds from crude oil 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 operations are 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 use as transformer 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 is converted to a sludge from which neither the sulfuric acid nor a valuable hydro,- carbon product can be obtained, the sludge presents a serious disposal problem, serious corrosion problems ar 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 a process for the refining of hydrocarbons, 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 nonaromatic hydrocarbons and adjustment of the aromatic content to a desired value. A still further object is to provide a process of refining wherein the sludge formed is or may be converted to useful products. Other objects appear hereinafter.

In patent application Serial No. 38,167, filed July 10, 1948, now Patent Number 2,557,113, there is described various reactions of hydrocarbons having at least one tertiary hydrogen atom per molecule, such'as alkylation, isomerization, and the like, using the present combination of catalytic components to initiate such reactions, the process being conducted in th absence of aromatics.

In patent application Serial No. 130,926, filed December 3, 1949, there is described the alkylation of alkylatable aromatics with saturates having at least five carbon atoms and at least one tertiary hydrogen atom per molecule by bringing together a tertiary alkyl fluoride and BFs in the presence of a mixture thereof, the mole ratio of tertiary alkyl fluoride to aromatics plus saturates 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. 173,745, filed July 14, 1950, there is described and claimed a process for the separation of non-hydrocarbons from hydrocarbons which comprises bringing to,- gether boron fluoride and a primary or secondary alkyl fluoride in the presence of a mixture thereof, whereby a sludge containing the non-hydrocarbons is formed. In this process, if the quantity of alkyl fluoride used is in excess of the quantity required to remove the non-hydrocarbons, the aromatics are converted to and form a portion of the sludge, but only after substantially complete removal of the non-hydrocarbons.

In patent application Serial No. 173,746, filed July 14, 1950, there'is describedand claimed a process for the separation of aromatic hydrocarbons from saturated 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 and separate as an insoluble sludge,

In patent application Serial 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 a tertiary alkyl fluoride in the presence of a mixture thereof, whereby the non-alkylatable aromatics are converted to and separate as a sludge.

It has now been discovered that by bringing together a tertiary alkyl fluoride and SP3 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 hydrocarbons are lost in the process; It has been further discovered that after selective removal of the non-hydrocarbons, the non-,allsylatable aromatics may be selectivelyremoved.

In accordance with the present invention, the combination of the present refining agents, a tertiary alkyl fluoride and boron fluoride, has been found to be extremely potent and highlyiselective for the removal of the non-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 general, sulfur, oxygen, and nitrogen compounds. After removalof the deleterious non-hydrocarbons, the combination of the present refining agents is extremely potent and highly selective for the removal of non-.alkylatable aromatic hydrocarbons. Only after removal by sludge formation of the non-hydrocarbons and aromatics do the reactions described in aforesaid patent application Serial No, 38,167 occur, and only after removal of the non-hydrocarbons and in the presence of both alkylatable aromatics and tertiary hydrogen containing isopara-flins do the alkylation reactions described in aforesaid patent application Serial No. 130,926 occur. Thus, by proper adjustment of the operating'c-onditions, particularly the concentration of the alkyl fluoride, as hereinafter described, deleterious components of hydrocarbons, and especially of crude oil or the petroleum fractions obtainable therefrom, ma be removed withoutany substantial loss of valuable hydrocarbons. bysludge formation or degradation to undesired compounds.

Thus, in accordance with thev present invention, when a tertiary alkyl fluoride and boron fluoride are brought together in a mixturev of nonhydroo'arbons and non-aromatic saturated hydrocarbons, the non-hydrocarbons are converted to and separate as an insoluble sludge. If nonalkylatable aromatics are present, and if the amount of alkyl fluoride employed is in excess of amount required to remove the non-hydrocarbons, the non-alkylatable aromatics are also converted and separate as an insoluble sludge, the amount of conversion being dependent upon the quantity of alkyl fluoride available for the reaction. In the higher boiling petroleum fractions, particularly the lubricating oil fractions, the aromatics present are substantially all non-alkylatable, and

operation of the present process with such fractions forms a preferred embodiment of the present invention. By thev expression non-alkyla-table aromatics, as employed herein, is meant the or are composed of highly condensed aromatic rings with substituents thereon, and the wide variety of aromatics occurring in petroleum which are readily removable in the present process illustrates the versatility thereof. For example, among the aromatics that occur in petroleum are the substituted aromatics of the benzene, naphthalene tetralin, anthracene, and phenanthrene series, which are removed in accordance with the present process, as may other aromatics, such as the unsubstituted homologues of the mentioned series, as above described.

The present process is also operable in the presence of alkylatable aromatics. Thus, in accordance with the present process, with alkylatable aromatics present in the aforesaid mixture to be refined, the non-hydrocarbons are first selectively removed, and only after their removal do the alkylation reactions as described in patent application Serial No. 130,926 occur, and then only when a quantity of tertiary alkyl fluoride in excess of that required to remove the nonhy-droc-arbons is employed. When such an excess of the fluoride is used, on completion of the alkylation reactions, the so-fcrmed non-alkylatable aromatics are removed as above described. Hence, by proper adjustment of the operating conditions, particularly the concentration of tertiary alkyl fluoride, as hereinafter fully described, it is possible to remove non-hydrocarbons, or to remove non-hydrocarbons, convert any alkylatable aromatics to non-alkylatable aromatics, and then remove all or a desired proportion of such aromatics, together with any non-alkylatable aromatics initiallly present in the reaction mixture. It should be further noted that in the absence of tertiary hydrogen containing saturates, no alkylation is observed, and alkylatable aromatics are converted to sludge the same as non-alkylatable aromatics.

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

A substantial advantage of the present refining process is that both of the components of the refining catalytic combination are soluble in hydrocarbons, thus eliminating the necessity for the vigorous agitation inv processes involving insoluble reagents, such as sulfuric acid, hydrogen fluoride, and aluminum. chloride. It is evident that the present reaction mixture forms a homogeneous phase wherein reaction occurs, and on completion of which the system becomes heterogeneous due to the formation of a sludge composed of theiun'desirable constituents of the hydrocarbons. It is characteristic of the present process that the alkyl fluoride employed in the process is converted to the corresponding paraflin.

For example, if t-butyl fluoride is employed, isobutane 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, a tertiary alkyl fluoride and boron fluoride, are brought together in the presence of the oilbeing 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 min.- utes is suitable.

Hydrocarbons which maybe refined in accordance with the present process include crude petroleum and the various fractions obtainable pentane and other t-octyl fluorides.

therefrom, such as gasoline," kerosene, and lubrihydrocarbons 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, is meant a mixture of hydrocarbons obtained from petroleum having a relatively narrow range of boiling points.

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, hydrocarbons prepared by the Fischer-Tropsch synthesis may be separated from non-hydrocarbon constituents, such as oxygen compounds. By the term oil, as used herein, is meant the hydrocarbons and mixtures thereof which may be refined in the present process, as above The concentration of non-hydrocarbons in the oils refined in the present process is usually from 0.05 to 2%, although higher concentrations, up to about 5%, may be present in crude oils, and good results obtainedtherewith. When nonalkylatable aromatics are present, the concentration thereof is usually from 1%to 30% by volume. Alkylatable aromatics should not exceed about %"by volume because, in such case, excessive quantities of alkyl fluoride are required to convert them to non alkylatable aromatics,

.and a prohibitive quantity of alkylating hydrocarbons are lost.

The'alkyl fluorides which can be employed in the present process are the tertiary alkyl fluorides, i. e., t-hose alkyl fluorides wherein the fluorine atom is attached to a tertiary carbon atom.

A few specific examples of preferred tertiary fluorides are: -2-fluoroe2-methylpropane t-butyl dimethylbutane and other t-hexyl fluorides; theptyl fluorides; and 2-fluoro-2,4,4-trimethyl- It will be understood that the specific compounds named above are given merely by way of illustration, and

that any tertiary alkyl fluoride will produce an operative catalytic combination with BE; 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 BFs, such as by bubbling it into the solution.

. 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 BF: since, in suchcase, the catalytic condition requiredto be 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 the presence of the oil being refined, i. e., the present refining agents, a tertiary alkyl fluoride and boron fluoride, are contacted only when they. are also. 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 of 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, a such value being readily deter.- minable in view of the present specification. It is desired to remove only the non-hydrocarbons, the quantity of alkyl fluoride may be adjusted to so operate, and if it 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, reactions of the tertiary hydrogen containing 'isoparaflins which may be present occur, 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 suflicient to remove substantially all of the non-hydrocarbons of a petroleum fraction. If it is desired to subject the fraction to a more drastic treatment in orderto 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, 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 non-hydrocarbons will convert about 20% of the aromatics present, and a 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 amounts of alkyl fluoride is considered a significant advantage of the present process. Equal molar quantitie of the various alkyl fluorides within the scope of this invention remove substantially the same quantity of aromatics from a given mixture.

As above stated, the concentration of boron fluoride to employ is not critical, the requirement being that a quantity suflicient to establish the catalytic condition be employed. In general,

from 0.1 to 400 weight percent, and preferably small.

7 from :1 to 200 weight percent, based on the weight of alkyl fluoride employed, is suificient 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, aresuitable in the case of normally liquid hydrocarbons, whereas a higher pressure, 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 material being treated. A temperature sufiicient- 1y high to maintain the hydrocarbons :in a fluid, i. e., non-viscous, state is'preferred. In general, temperatures of 20 C. to 150 C. may be em- .ployed, and all tertiary alkyl fluorides 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 liquified normally gaseous hydrocarbons, the lowest temperature at which the present fluorides can be employed is 120 C.

As above described, the refining agents are soluble in the present oils, and on completion of the reactions a sludge separates to form a heterogeneous phase. As already described, only a small amount of hydrocarbons are converted to asludge in the removal of non-hydrocarbons, and hence the total quantity of sludge formed is if aromatics are also converted to sludge, the quantity thereof increases in accordance with the amount of conversion of the aromatics. The sludge may be separated by any convenient or desired 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 sludge by heating or applying a vacuum, or both. For example, heating to about 190 C. under a slight vacuum drives ofi hydrogen fiuoride 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 known to the art, the resulting alkyl 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, a petroleum fraction containing non-hydrocarbons "being-used as illustrative, are introduced into the process-through line I and tertiary butyl fluoride, used to illustrate the various alkyl fluorides which may be employed, is introduced into the system through line :2. .A mixture .of the 'petroleum'iraction and tertiary butyl fluoride passes through line 3 into heat exchanger 4 wherein the temperature oftheimixture is adjusted to the desired value, usually from.20 C. to 150 C. The mixture then passes :through .line :5 into mixer 6, into which the BFs is introduced through line 8. Means "to provide mild agitation in mixer 6 may be supplied .if desired, but may be omitted if the turbulence of flow is :suificient to secure substantially uniform mixing. On introduction of the BFs 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 9 into separator in, sludge being removed therefrom through line H and the refined fraction through line I2. I50- butane formed from the tertiary butyl fluoride is removed from the separator through line 13. The refinedfractionpasses into tower I 4 wherein it is treated to remove any entrained acid gases such as by washing with water, the water being introduced into tower I4 through line I5. Refined product is removed through Hi and the used water through line [8. The refined product may be dried and further treated as desired. Sludge from separator 10 passes throughline H into distillation zone t9, and BE; and HF are evolved therefrom. BF: is recycled to the process through lines 2-0 and 8. HF passes through line 21 into reactor .22 wherein it is reacted'with isobutylene supplied through line 24 to form tertiary butyl 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 f-uel'or as a'component of compositions useful for example, in paving roads and the like.

The quantity of reactants to employ and the various operating conditions are advantageously maintained as heretoforedescribed.

The following examples illustrate preferred embodiments of the present invention:

It was desired to prepare an .oil suitable for use in transformers from a petroleum fraction obtained from East :Texas crude, .the fraction having a viscosity at of 59 Saybolt Universal, .a :flash point of 280 E, and at 10 2mm. of mercuryaninitia'liboiling point :of 274 F., 'a.50% distillation point at :3 61 .F., :and 2.11 .end point of 495 F. .The aromatic .content of :the fractionrwas composed substantially entirely of non-.alkylatable aromatics.

The procedure employed'was as .follows:

The fraction and tertiary butyl fluoridewereintroduced into a reactor .and the temperatureadjusted to and maintained at C. by immersion :in a water bath. Boron fluoride under pressure was introduced into the :stirred solution to an initial pressure of 1501p. s. i.,.and-two to four subsequent additions thereof were made to give a final pressure as indicated 'in Table '1. On completion 'thetoil was filtered, treated with ammonia and refiltered to give the final product. Oil :ad hering to the contactor was recovered and included in the final product.

Quantities of reactants, operation variables, and properties of products are included in'Table 1. All runs were made at 25C. In each run the alkyl fluoride was converted to the corresponding 'parafiin, namely, isobutane. In all tables parts means parts by weight.

Table 1 Aromatic t-Butyl Contact Refined Sludge Sligh 1 Oxrdatwn O. D ggg fluoride 5 Time z gs Oil formed Oxidation z ffi Sludge Color D (parts) p (minutes) (parts) (parts) Value Value days) Percent) 7. 80 Y 30 80 97. 6 3. 90 9. 3 19 4. 50 40 140 96. 2 3. 80 4. 16 5. 70 40 132 1. 5 14 9.13 40 135 91. 0 17.0 0.2 9 l. 98 36 99. O 0. 25 18. 9 23 1. 16 85 99. 8 0.91 23 2. 40 50 120 97. 5 0. 94 17. 9

l Methoddescrlbed in Oil and Gas 1., 24, No. 2, 125, 135 (1925). I Determined by ASIM D670-42'l, Method B a Method described in Ind. Eng. Chem., Anal: Ed., vol. 6, 23 (1934); measures the absorbance at 525 mu. Values given are absorbanceXlOO 4 Sulfur content of starting material was 0.17%, and of treated product was 0.03%.

These data demonstrate that a great improvement in stability and color of the oil is obtained when treated in accordance with the present process, with only a slight amount of concomitant loss by sludge formation, that with relatively small amounts of alkyl fluoride the aromatic content is substantially unchanged'whereas with relatively large amounts the aromatic content is significantly decreased. The data also include several experiments with BFs as the sole refining agent, and while some improvement in the oil was obtained, the results are not comparable to those obtained with the combination BF's-alkyl fluoride.

The small amount of sludge formed with the relatively small amounts of alkyl fluoride is composed largely of compounds of the non-hydrocarbon constituents of the oil, with the polymers of non-alkylatable aromatics included therein when relatively large amounts of the alkyl fluoride are employed.

It should be further noted that, using oxidation sludge value as the criterion, it is possible to overtreat the oil, and in such case, it is advantageous, where oxidationstability is desired, to blend untreated stock with the overtreated oil. It is especially advantageous to add stock which has been given a light treatment, such as with boron fluoride'and a small amount of alkyl fluoride, or with boron fluoride alone, to the overtreated oil. Good oxidation stability may also be obtained by adding an inhibitor to the overtreated material, which has been found to give excellent response to the known oxidation inhibitors; an example of such inhibitors are the polyalkyl phenols, e. g., 2,6-ditertiarybutyl-4- methylphenol.

In order to illustrate the value of blending, 25% by volume of the material having an oxidation sludge'value (Table 1) of 0.085 was blended with by volume of the material having a value of 0.129. The oxidation sludge value for the blend was 0.075, which is lower than for either of the constituents. In general, it is advantageous to blend from about 0.1 to 10 parts of treated oil with 1 part of untreated, or lighter treated, oil.

EXAMPLE 2 The procedure of Example 1 was followed in the refining of a cable oil stock. The temperature employed was 75 C., at which temperature the reaction mixture is in a fluid state.

The cable oil stock consisted of the highest boiling fraction of a vacuum distillation of the lubricating oil range of East Texas crude petroleum, having a viscosity of 931.3 centistokes at 100 F. and 22.99 at 210 F., and a viscosity index of -55.

The details of preparation are shown in Table 2, and the properties of the products, and blends thereof, in Table 3. In each run the alkyl fluoride was converted to the corresponding paraffin.

Table 2 t-Butyl Contact Finished Sludge Test Number 2 2 fluoride 23 Time g g Oil Formed p (parts) p (minutes) (parts) (parts) 100 2. 61 3. 78 40 75 100 2. 53 3. 72 40 92. 2 100 2. 66 4. 03 40 95. 8 5. 5 5. 20 40 93. 6 100 5. 68 4. 70 65 110 91. 6 100 5. 86 2. 41 40 1 8o. 1 100 6. 07 4. 69 40 105 z 100 6. 32 2. 93 145 85 97. 2 2 100 6. 40 2. 44 6O 70 93. 2 100 7. 0 3. 37 90 65 96. 3 100 10. 9 9. 35 30 87. 9 100 1].. 0 9. 10 40 125 1 65. 1 100 11. 1 6. 73 40 75 1 64. 7 100 11. 1 9. 70 40 105 72. 0

1 Some loss of product occurred.

5 Process carried out in a .Table 3 Resistivi ty l Refractive (ohms/cm.

Viscosity Power Factor (centistokes) I NPA Color Index m Initial :Aged r 1 Numbersrefer to the product prepared, or blends thereof, under the 2 Table l,-footnote 3.

3 Aged 96 hours in an open beaker at 115 C.

4 Untreated stock.

The data of Tables 2an'd 3 show the value of the present process for the production of oils having excellent electrical properties. The ini- 2 tial and aged resistivity and power factor, for untreated oil (stock) could not be measured because of its extreme unsuitability as electrical oil; the resistivity thereof is very low and power factor very high.

EXAMPLE 3 A lubricating oil, grade, was treated with 0.53% by weight of tertiary butyl fluoride and an excess of boron fluoride at a temperature of 75 (3., the procedure being in accordance with Example f1. I p

I To both treated and untreated oil was added /2 by weight of acommercially available oxidation inhibitor. Both of the inhibited oils were admixed with an iron oxidation catalyst and heated for 24* hours at F. Properties of the oils before and after the heating" were compared.

It was found that the average percent viscosity increase of the untreated oil was 52 ascompared to 38.5 for the treated oil; the average percent of n-pentane insoluble material of untreated oil was 1.98 as compared to 1.10 for the treated oil; and that deposition from the untreated oil was heavy as compared to light depositionfrom the treated oil.

The process of the present invention isespecially suitable for the preparation of petroleum oils intended for purposes which require high stability, 1. e., non -sludging properties. Oils which require high stability include electrical oils such as transformer, capacitor, and cable oils, and the other oils such as motor, turbine, and refrigerator oils. The present process may be operated using batch or continuous operation.

The separation of aromatic from non-aromatic hydrocarbons in the absence of non-hydrocarbons is not included within the scope ofthe present claims, but is described and claimed in aforesaid copending application Serial N 0. 173,748, filed July 14, 1950.

The invention claimed is:

1. Process of refining hydrocarbons which comprises reacting a mixture of hydrocarbons and non-hydrocarbons with boron fluoride and a tertiary aikyl mono-fluoride as the sole refining agents, said boron fluoride and said tertiary alkyl mono-fluoride being brought together only in the presence or said mixture of hydrocarbons and non-hydrocarbons, whereby said non-hydrocarb'ons are converted to a sludge, and separating said sludge from the reaction mixture.

2.- Process for the separation of non-hydrocarbone from petroleum containing the same which comprises reacting petroleum containing non hydrocarbons with boron fluoride and a tertiary corresponding testnumber of Table 2 (first colmn) alkyl mono-fiuoride as the sole refining agents, said boron fluoride and said tertiary alkyl monofl'uoride being brought together only in the presence of said petroleum containing non-hydrocarbons, whereby said non-hydrocarbons are converted to a sludge, and separating said sludge fromthe; reaction mixture.-

3*. Process for refining a petroleum fraction containing non hydrocarbons which comprises reacting saidpetroleum fraction containing non-hydrocarbons with boron fluoride and a tertiary alkyl mono fluoride as the sole refining agents,- said boron fluoride and said tertiary alkyl monofluoride being brought together only in the presence of said petroleum fraction containingnonhydrocarbons; whereby said non hydrocarbons are convertedto a sludge, and separating said sludge from the reaction mixture.

4. Process according to claim 3 wherein the quantity of the alkyl fluoride employed is from o.5 to 2 percent by weight.

5. P'rocess. according to claim 3 wherein the alkylfluoride is a tertiary butyl fluoride.

6. Process according to claim 3 wherein the alkyl fluoride is 2-fiuoro-2-methylbutane.

'7. 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 a tertiary alkyl mono-fluoride as the sole refining agents, said boron fluoride and said tertiary alkyl mono-fluoride being brought together only 0 in the presence of said lubricating oil fraction containing non-hydrocarbons, whereby said nonhydroca'rbons are converted to a sludge, and separating said sludge fromthe reaction mixture.

8. Process according to claim '7 wherein the quantity of the alkyl fluoride employed is from 0.5 to 2 percent by weight.

9. Process according to claim 7 wherein the alkyl fluoride is tertiary butyl fluoride.

10. Process for refining a kerosene fraction containing non-hydrocarbons which comprises reacting said kerosene fraction containing nonhydrocarbons with boron fluoride and a tertiary alkyl mono-fluoride as the sole refining agents, said boron fluoride and said tertiary alkyl monofluoride being brought together only in the presence of said kerosene fraction containing nonhydrocarbons, whereby said non-hydrocarbons are converted to a sludge, and separating said sludgeirom the reaction mixture.

11. Process according to claim 10 wherein the quantity of alkyl fluoride employed is from 0.5 to 2 percent by weight.

12. Process according to claim 10 wherein the all z'yl fluoride is a tertiary butyl fluoride.

13. Process for refining a gasoline fraction con taining non-hydrocarbons which comprises reacting said gasoline fraction containing nonhydrocarbons with boron fluoride and a tertiary alkyl mono-fluoride as the sole refining agents, said boron fluoride and said tertiary alkyl monofluoride being brought together only in the presence of said gasoline fraction containing nonhydrocarbons, whereby said non-hydrocarbons are converted to a sludge, and separating said sludge from the reaction mixture.

14. Process according to claim 13 wherein the quantity of alkyl fluoride employed is from 0.5 to 2 percent by weight.

15. Process according to claim 13 wherein the alkyl fluoride is tertiary butyl fluoride.

16. Process for refining a petroleum fraction containing saturated non-aromatic hydrocarbons, non-hydrocarbons, and aromatics which comprises reacting said fraction with boron fluoride and a tertiary alkyl mono-fluoride as the sole refining agents, said boron fluoride and said tertiary alkyl mono-fluoride being brought together only in the presence of said etroleum fraction, whereby said non-hydrocarbons and said aromatics 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 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.

18. Process according to claim 17 wherein the quantity of alkyl fluoride employed is from about 2 to 30 percent by weight.

19. 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 a tertiary alkyl mono-fluoride as the sole refining agents, said boron fluoride and said tertiary 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.

20. Process for the preparation oi. a refined petroleum fraction stable against oxidation which comprises dividing a petroleum fraction and reacting a portion thereof with boron fluoride and a tertiary alkyl mono-fluoride as the sole refining agents, said boron fluoride and said tertiary 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.

21. 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 a tertiary alkyl mono-fluoride as the sole refining agents, said boron fluoride and said tertiary 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 the action of boron fluoride as the sole refining agent, separating sludge formed by the latter treatment, and blending the two sotreated portions, whereby a refined petroleum fraction of enhanced oxidation stability is produced.

22. Process for the refining of a lubricating oil fraction containing non-hydrocarbons which comprises reacting said lubricating oil fraction with boron fluoride and tertiary butyl fluoride as the sole refining agents, said boron fluoride and said tertiary butyl fluoride being brought together only in the presence of said lubricating oil fraction containing non-hydrocarbons, whereby said non-hydrocarbons are convertedL to a sludge and said tertiary butyl fluoride is converted to isobutane, and separating said sludge and said isobutane from the reaction mixture.

ROBERT M. KENNEDY. ABRAHAM SCHNEIDER.

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 a1 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 2,507,599 Cade May 16, 1950

Claims (1)

1. PROCESS OF REFINING HYDROCARBONS WHICH COMPRISES REACTING A MIXTURE OF HYDROCABON AND NON-HYDROCARBONS WITH BORON FLUORIDE AND A TERTIARY ALKYL MONO-FLUORIDE AS THE SOLE REFINING AGENTS, SAID BORON FLUORIDE AND SAID TERTIARY ALKYL MONO-FLUORIDE BEING BROUGHT TOGETHER ONLY IN THE PRESENCE OF SAID MIXTURE OF HYDROCARBONS AND NON-HYDROCARBONS, WHEREBY SAID NON-HYDROCARBONS ARE CONVERTED TO A SLUDGE, AND SEPARATING SAID SLUDGE FROM THE REACTION MIXTURE.

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