US951272A - Obtaining petroleum products. - Google Patents

Description

H. PRASGH. OBTAINING PETROLEUM PRODUCTS.

Patented Mar. 8, 1910.

APPLICATION FILED 00T.30. 1903.

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H. FRASGH.

OBTAINING PETROLEUM PRODUCTS.

APPLICATION FILED OUT. 30. 1903.

951,272. A Patented Mar. 8, 1910.

5 SHEETS-SHEET 2.

H. FRASGH. OBTAINING PETROLEUM PRODUCTS.

APPLICATION FILED OUT. 30. 1903. 95 1,272. Patented Mar. 8, 1910.

5 SHEETS-SHEET 3.

H. FRASGH. OBTAINING PETROLEUM PRODUCTS. APPLICATION FILED 00130. 1903.

Patented Mar. 8, 1910.

6 SHEETS-SHEET 4.

' Qwihwooao H. PRASGH OBTAINING PETROLEUM PRODUQIS Pateniied Mar. s, 1910.

APPLICATION FILED 0013.30. 1903.

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UNITED sTArps PATENT OFFICE.

HERMAN FRASCH, OF NEW YORK, N. Y., ASSIGNOR TO STANDARD OIL COMPANY, OF BAYONNE, NEW JERSEY, A CORPORATION OF NEW JERSEY.

OBTAINING PETROLEUM PRODUCTS.

Specification of Letters Patent.

Patented Mar. 8, 1910.

Original application filed October 4, 1902, Serial No. 125,967. Divided and this application filed October 30, 1903. Serial No. 179,235.

To all whom it may concern.

Be it known that I, HERMAN FRAsoH, a citizen of the United States, residing at New York city, Manhattan borough, New York county, in the State of New York, have in vented new and useful Improvements in Obtaining Petroleum Products, of which the following is a specification.

This invention relates more particularly to obtaining burning oil (kerosene) from petroleum of the nature of that obtained from the wells near Beaumont, in Jefl'erson county, Texas, hereinafter referred to as Beaumont oil or Beaumont petroleum; but it also relates to obtaining burning oil (kerosene) from other kinds of petroleum as hereinafter set forth; and it is not wholly confined to the obtainment of burning oil (kerosene).

On subjecting Beaumont petroleum to fractional distillation (with or without cracking). and subjecting the entire distillate which comes over between the ordinary temperature limits of burning oil (say, from 250 F. to 600 F.) to treatment with sulfuric acid of 66 Baum (followed by the custon'iary washing with water, and with caustic soda solution, and again with water), the resulting product will be colorless and of a mobility to climb a lamp wick (although much denser than Pennsylvania burning oil) but it will smoke when burned in ordinary petroleum (kerosene) lamps, especially if the flame should be turned low. The raw distillate shows the same smoky flame. I have discovered that such distillate is composed in part only of smoky hydrocarbons and that these and the nonsmoking hydrocarbons which accompany them in distillation can be separated from each other by the differentially solvent action of an appropriate menstruum, such as methyl alcohol or ethyl alcohol, not only to a useful extent, but suflicieutly to obtain from such smoky distillate a non-smoking burning oil (kerosene) whose hydrocarbons have the same range .of boiling points as those of said smoky distillate. And I believe the same to be true of any petroleum analogous to Beaumont 011 in possessing a smoky burning-oil fraction, to the extent atleast that such a non-smoking burning oil (kerosene) can be obtained from smoky distillate representing a part (if not the whole) of the burning Oll fraction of suchpetroleum. But said Beaumont or analogous petroleum is not the only petroleum the burning oil (kerosene) from which burns with a less clear flame than does burning oil (kerosene) from Pennsylvania petroleum or (when desulfurized) from Lima oil. Russian petroleum, for example, is of that char acter; and so I believe is any petroleum whose burning oil fraction is denser (heavier in gravity-less in degrees Baum) than that of Pennsylvania or Lima oil. I have discovered in respect to Russian petroleum' (and I believe it will hold true of petroleum of thelast mentioned description in eneral) that the burning oil fraction thereo is composed of hydrocarbons which differ in their tendency to smokiness and that said hydrocarbons can be separated from each other by a differentially solvent menstruum of the aforesaid description, with the result of improving the burning oil (kerosene) from said petroleum in respect. to the character of its flame. Moreover, an oil made from that fraction of Pennsylvania and certain other petroleum which is less volatile than burningoil (kerosene) has been used to a certain extent for illuminating purposes by burning in special lamps. Such heavier illuminatin oil fraction of Beaumont or other petro eum mentioned can also, I believe, be improved in respect to smokiness or tendency thereto by subjecting the same to the aforesaid menstruum. Further, the illuminating oil fractions (namely, the burning oil fraction and said heavier fraction) of petroleum whose burning oil fraction is of the density of that of the Pennsylvania and Lima petroleum undergo, each of them, a separation of hydrocarbons, when subjected to the aforesaid menstruum, with the result of obtaining oil in which the ratio of carbon to hydrogen (which can be ascertained by elementary chemical analysis) is less than in the oil so treated.

Based on these discoveries, the invention consists in the processes of subjecting part at least of either or both of said illuminating oil fractions of Beaumont or other petroleum, as above mentioned, to the action of a menstruum, such as methyl alcohol or ethyl alcohol, which has a different solvent upetroleum, and thereby obtaining the results stated. -The menstruum may be apaction upon the non-smoking from thatwhich it has upon the smoky hydrocarbons of said burning oil fraction of Beaumont plied to all or to any desired part of either or both of said illuminating oil fractions before or after the separation of the same from other fractions or parts of the petroleum; but the application would best be made after such separation, the oil treated being in the form of an appropriate distillate. The dis-,

tillation of the crude oil may, in any case, be performed with or without cracking.

In addition to giving an oil of less ratio of carbon to hydrogen than the oil treated, the separation which is effectedby the differentially solvent menstruum also results in an oil of greater ratio ofcarbon to hydro en; and thismore highly carbonaceous product can be utilized for burning as fuel or for other appropriate purpose.

The solvent action of methyl or ethyl alcohol is greater on the smoky hydrocarbons (or those having a higher ratio of carbon to hydrogen) than on the non-smoking hydrocarbons (or those having a lower ratio) but it isevident that a menstruum having the reverse differential action might serve to separate the two kinds of hydrocarbons; and it is believed that a differential solvent in general has now for the first time been applied as indicated.

Nearly anhydrous methyl alcohol is regarded as the best menstruum; but another appropriate menstruum (differential solvent) can be used without exceeding the limits of the invention. As already indicated, ethyl alcohol can be used. I believe other appropriate menstrua toexist.

After the desired and feasible separation of the hydrocarbons from each other has been obtained, the menstruum is separated from the hydrocarbons in solution therein in order to obtain purer oil and also-to recover the valuable menstruum; and where 1t and they have sufliciently different boiling points fractional distillation would best be resorted to; but the menstruum separation might be effected in different ways which or without being'subjected to an intermedi-,

ate treatment, as may be found necessary or tion, or such separation and repeated use,

of themenstruum is a feature.

In obtaining burning oil from petroleum I have found advantage in the case of Beaumont oil,- and I believe advantage would also be found in other cases, in subjecting the heavier portion of the burning oil fraction of the oil-to the menstruum after preliminarily separating the light end of said fraction therefrom. In my experience with Beaumont oil I have found such light end sufficiently 'free from smoky hydrocarbons to be used in burning oil (kerosene) without subjection to the menstruum; but it can, if necessary or desired, be subjected thereto. Bythe preliminary separation of the light end and omission to subject it to the menstruum a saving of oil is effected; since if said light end were allowed to remain it would be deprived of utilizable constituents by the menstruum; and such a saving would result wheneveror however the heavier portion of the burning oil fraction of petroleum (after removal of the light end therefrom) should be treated by agents which would remove utilizable constituents from said light end, if applied thereto. The invention covers this feature generally.

Other or further improvements in obtaining petroleum products are also included in the invention, as herein set forth.

Another part of my present invention consists in certain new petroleum or hydro carbon oils. Oils within this part of the invention can be obtained from Beaumont petroleum by means of the improvements or processes herein set forth; and such products are more especially, although not exclusively, intended; since the invention includes oils in general having the necessary characteristics (hereinafter pointed out).

In the accompanying drawings, Figures 1 and 2,.taken together, but omitting those parts from Fig. 1 which also appear on Fig. 2, make a plan view of an oil washing apparatus or plant for carrying the invention into effect, certain intermediate portions of said apparatus being broken away in Fig. 1 in order to get the figure on the sheet; Fig. 3 isa front elevation of the same apparatus; Fig. 4; is a view in vertical section of one of the settling and decanting vessels forming part of said apparatus; Fig. 5 is a detail view on a larger scale of a form of valve considered more advantageous than that shown in Fig. A; Fig. 6 is a detail view of another valve arrangement; Fig. 7 is a side elevation, partly in section, of the apparatus or plant of Figs. 1, 2 and 3, looking to the left from the line EE of Figs. 1 and 2;

desirable. The invention includes the procthe section line being shown in elevation; 1. i

fit

r tween the valve 2 and the cap 5.

and Fig. 9 (Sheet 1) is a view of a device for skimming oil from the aqueous methyl alcohol of condensation which runs from one of the condensers employed.

In Figs. 3 7 and 8 one of the rectifying columns and its vapor pipe are shown partly broken away, in order to get the figures on their respective sheets.

The apparatus shown contains a series of mixing vessels 13 for churning together the oil and the menstruum. Each such vessel is provided with a rotary stirrer'23 (see left hand end of Fig. 8) operated by 'a belt from a pulley 24 on shaft 22; and the stufiing box for each stirrer shaft is located on top of a sleeve 26 so as to be raised above. the level of liquids in vessel 13. Thus arranged, it is less likely to allow material to escape from the vessel 13 than if it were in position to be wet by said liquids. The liquids enter each vessel 13 at the bottom through a pipe 20 and leave it at the top (see left hand end of Fig. 7) through a pipe 16. For each mixing vessel 13 there is a settling and decanting vessel 14 (Figs. 4; 7 and 8) for separating the mixture of oil and nenstruum into a lighter and a heavier component. Each such vessel 14 is provided with an inlet at the middle to which the pipe 16 leads from vessel 13 and with outlets at top and bottom respectively from which pipes 17 and 15 carry off the separated'liquids. The pipe 16 opens into an annular space between a perforated distributing plate 160 and the Wall of the vessel 14. In the vessel is ad submerged float 30 (Figs. 4 and 8) carrying a valve 31 for the upper outlet and a valve 32 for the lower outlet. In normal working both valves are'open; and their adjustments depend upon the gravity of the mixture of oil and menstruum in vessel 14; for as such mixture becomes lighter the float rises, closing the valve 31 and opening the valve 32 correspondingly; and as it becomes heavier the float falls, opening the valve 31 and closing-the valve 32. An automatic control is thus exercised on the proportions of the entering mixture which leave by pipes 17 and 15 respectively. In Fig. 5 the valve 21s placed between the outlet ports 3 and the middle of the vessel 14; so that the current does not tend to close the same. The body of the valve has holes 4 therein so that the liquid may pass into and out of the space be- At 6 are weights for loading float 30. In Fig. 6 the end of the pipe 15'is provided with a simple gate valve 155 for controlling the outflow from vessel 14 by pipe 15. It can be used instead of or in addition to either or both of the float operated valves 31, 32. The pipe 17 has a vertically adjustable end 27, the el-' uids from through the pipe 17. For each mixing vessel 13 there is also a centrifugal pump 1!) whose shaft passes through a stuffing box at top of sleeve 25 (used for the same purpose as sleeve 26) and is driven by a belt from a pulley 21 on shaft 22. The mixture of oil and menstruuln enters the pump by a pipe 10 and is fed by it to the corresponding vessel 13 through ipe 20. Further, for each vessel 13 there is a supply chamber 18 for supplying by pipe 10 (Fig. 8) to the corresponding' pump 19 the mixture of liquids which it receives (Fig; 6) from pipes 15 and 17 only the supply chamber at the lower right hand end of Fig. 2 receives liqpipes 33 and 17; whilethat at the upper right hand end of the same figure receives liquids from pipes 34 and 15. The series of supply chambers 18 is formed by partitions (Fig. 6)'in the troughs shown at top and bottom respectively of Fig. 2. These troughs as shown are closed (Fig. 6) on top to prevent evaporation of the menstruum therein; and the stems of valves 155 pass through stuffing boxes in the cover. The chamber 35 receives liquid by a pipe 17 and discharges it by a pipe 54. The chamber 36 receives liquid by a pipe 15 and discharges it by a pipe 65. A pane of glas 9 in the wall of each chamber allows observation of the interior.

Assuming that a mixture of oil and differentially solvent menstruum in the proportions in which they are to be used should yield (on settling) two liquids; of which the bulk of the menstruum should be contained in the lighter liquid, the oil would {iow through pipe 33 into what may, therefore. be regarded as the first supply chamber of the series; while the menstruuin would flow through pipe 34 into the last supply chamber of the series. ,The oil in the first supply chamber meets the liquid flowing from the top of thelsecond settling and decanting vessel of the series by pipe 17 and consisting of menstruum charged with hydrocarbons. The two liquids are then supplied by aid of the first pump 1%) to the first mixing vessel 13 of the series; and from it. they pass by pipe 16 to the first settling and decanting vessel 14; where a separation of liquids takes place, I

the once washed oil passing by pipe 15 to the second supply chamber 18. Here it meets the charged menstrulun from the third decanting and settling vessel; and the two liquids are supplied therefrom by the second pump 19 to the second mixing vessel 13; from which they pass by pipe 16 to the second settling and decanting vessel 14. The

twice washed oil then flows by pipe 15 to the third-supply chamber 18. In turn the oil passes through each set of washing appliances (composed of a supply chamber 18. a pump 19, a mixing vessel. 13 and a settling and decanting vessel 14); audit is washed 2' 'the last but one of the'settling and decanting vessels 14 and is supplied with it by the last pump 19 to the last of the mixing vessels 13; from which the mixture passes into the last of the settling and decanting vessels.

FIOHI tlIlS the menstruum with its dissolved hydrocarbons passes by pipe 17 to the next to last supply chamber 18, where it meets oil from the last. but two of the settling and.

decanting vessels 14. "The oil and menstruum are then fed by'the next to last pump 19 to the next to last mixing vessel 13; from which they pass into the next to'last' settling and decanting vessel 14. From this the menstruum with its dissolved hydrocarbon passes by pipe 17 to last but three of the supply chambers 18. Thus the menstruum passes through each setof washing appliances in inverse order to that in which the oil passes through them. From chamber 35 away bythe pipe 54.

Assuming that methyl alcohol is used' as the differentially solvent menstruum, the means shown for recovering it from the hydrocarbons carried away by it through pipe 54 consist of a series of four stills 0 d e k (Fi s. 1, 7 and 8), two of them (0 d) heated'by dry heat only and provided with rectifying column 7, dephlegmator 746 and condenser 9 common to the two stills, and the other two of them (e is) having means for subjecting the liquid therein to free steam and provided with a condenser m common to both. In each still 0 d e there is a tight steam drum 50 (Fig. 8) with tubes- 51 open at both ends and extending through the drum for circulation of liquid. The steam inlet for each of these drums is marked .52; and the outlet for each for the water of condensation ismarked 53 (Figs. 7 and 8). The pipe 54 leads to still a; and the residual liquid passes from it by pipe 55 into stilld. The vapors from the latter enter still 0 by pipe 73 and passwith the vapors evolved in still 0 through the column f-and dephlegmator 746 and pipe 742 (Fig. l) tothecondenser g. The column; f has a perforated floor 74, it. may be ofany desired form, and is provided with a filling 740 of (most advantageously) brokengran- 'ite of from an inchto, three inches in diameter. As shown (Fig.8) a disk 74 of wire cloth rests upon a perforated plate 743 which in turn rests upon -I beams 744 supported at the ends'j-by the ring 745 fastened to the walls of the column. The dephlegmator consists of upright vapor tubes 747 set between heads 748 and surrounded by it passes water introduced by the pipe 749 (Fig. 3) and escaping by pipe 750. The water supply may be so regulated as to have a temperature of about 120 F., more or less, at the outlet 750. The condensate formed in the dephle 'inator and in the column f returns to t e still 0 and in its return is brought thoroughly into contact with the rising vapors. The condensate from condenser 9 passes by "pipe 75 to menstruum storage tanks 76 or (proper cocks being closed) by the pipe 75, by-pass 77 and pipe 34 to the last supply chamber 18 of the series, as before mentioned. From the storage tanks 76 the menstruum can be delivered by the ump 78 through pipe 34 to said supply cliamber. The stufling box for the piston rod of the pump 78 is elevated,

as described for those around the stirrer shafts of the mixing vessels 13. The same pump 78 will serve (on occasion) for exausting the contents of vessels l3 and 14 through pipe 780 (Fig. 8) and for delivering the same through pipe 79 (Figs. 2 and 3) into still e (the valve in pipe 34 being closed and that in pipe 79 being opened for the purpose). Between the condenser g and the pipe 75 is a box 80 with glass sides and movable slide so that the flow of condensate can be observed and a test sample taken, if desired. The residual liquid from still d passes by pipe 56 into still 6 and into it free steam is introduced in small quantity by pipe 501. The yapors (including the steam) pass by pipe 730 to the condenser m, along with the vapors from still 70.

This still receives the residual liquid by pipe 57 (Figs. 1 and 7) from still 0 and as shown consists of a long tube 70 inclosed for the greater part of its length by a jacketing tube 58 which is closed at the ends and provided with a steam inlet 59 at one end on top and an exhaust 60 at the opposite end underneath. The tube 70. is provided at its oil outlet with a free steam inlet pipe 61 and at its oil inlet end with a vapor escape pipe 62. The vapors (including the steam) pass by said pipe 62 to the plpe 730 and so to the condenser m. The residual liquid (oil) from which the menstruum (methyl alcohol) has been recovered vpasses to and through a cooling pipe 63 immersed in water in the box 64 and thence to a storage tank, not shown. It consists of the hydrocarbons which were washed out of the oil inthe vessels 13, 14 by the methyl alcohol.

For recovering the menstruum (methyl alcohol) which accompanies the washed oil, a series of two stills 71, Z with a condenser 7' common to both stills '71. Z is-shown. The pipe 65 delivers thewashed oil into the still h (Fig. 8), which is of the same construction as still 6; and thevapors generated therein, with free steam trom pipe 502, pass over by pipe. 81 to the condenser j. The

residual oil flows by pipe 66 to still Z, which has a steam jacket 69 corresponding with the jacket 59 of still 7.: (as shown for latter in Fig. 8) and having on top a steam inlet 7 0 (Fig. 1) and outlet 71 underneath for the water of condensation. The still Zalso has a pipe 67 (Figs. 1 and 3) corresponding with the pipe 61 (Figs. 1, 3 and 8) for the still A: for introducing free steam into the still Z. The vapors generated-in still Z, with the so introduced steannpass over by pipes 68 and 81 to the condenser j. The washed oil, freed from methyl alcohol, passes through a cooling coil 72 (Fig. 2) in water tank 64 to a storage tank, not shown. The condensate from condenser j consists of methyl alcohol diluted with water and accompanied by some oil. It flows into box 82 (Figs. 1, 7 and 9) (of known form with glass sides and a slide to allow a sample of condensate to be taken) and then into the inverted siphon 901. The oilrises and .overflows by pipe 902, which conducts it to still Z; while the dilute methyl alcohol flows over the top of the adjustable pipe section 903 in chamber 904 and is introduced by pipe 83 into the column g 1" s. The condensate from condenser m also consists of methyl alcohol diluted with water and accompanied by some oil. It flows into box 84 (Figs. 1 and 7) and then into the inverted siphon 905 (Fig. 7) (similar to-that marked 901 in Fig. 9) the oil rises and is conveyed by pipe 906 (Figs. 1, 3, 7 and 8) to tubular still 7.1; while in chamber 907 the dilute methyl alcohol flows over the top of an adjustable pipe section (similar to'that marked 903 in Fig. 9) and is thence conveyed by pipe 85 to the column q '1' 8. Each of the inverted siphons is provided with a valve pipe 908 for emptying it and the corresponding condenser ywhen desired. The

' lower section (I of column q r s (Fig. 8) has at its bottom a perforated floor in the form gravel which is best a little finer than that' in the col umn- 9; say, gravel which will pass through a sieve of two meshes to; the linear inch and not through one of three inchesto thelinear inch. The upper section 8 consists of a 7 number of vertical pipes 88 open at both ends and inclosed in a water box 87 The bottom ends of the pipes are set in the sheet which closes the top of section 1'; and their it per ends are joined to a manifold 89; rom

which the vapor pipe 90 leads to condenser t (Fig. 1). The water box 87 has a water inlet 91 and overflow 92 which may be so would best be as follows. mont oil is distilled with cracking (in appacated at the top regulated that the water in the box has a temperature of about 19.0 F, more or less, at the overflow. The column 9 r .9 surmounts the still a, which is a plain box provided with a close steam coil 86. "The dilute methyl alcohol is fed into the top of secti on g; which acts as a distilling column as well as a rectifier of the vapors formed in it and in the still n. These vapors are further rectified in sections 1- and 8, being deprived of nearly all the then remaining water in the section 5. They pass over into condenser t; and the resulting condensate passes by way of box 100 and pipes 101 and 5 (Figs. 7 and 1) into the menstruum storae tanks 76, or by way of box 100 and p1pes 101, 75, 77 and 34 into the oil washing ap aratus. The poor liquid flows from still it y pipe 96 to'the tubular still p (having a closesteam jacket 92 with steam inlet at 94 on top .and an outlet 95 for water of condensation underneath) and in it the last traces of methyl alcohol are expelled. The residual liquid flows by pipe 98 to a barrel 99 which may have a sewer connection. The vapors pass by pipe 97 to the still a and ascend the column q 'r s with whatever vapors may be generated in still a. a

To prevent loss of methyl alcohol by escape of the vapors thereof from the difi'erent portions of the apparatus, ventilating pipes can be provided, as shown at left of Figs. 7 and 8, which pipes'would lead to absorbing apparatus, such as a coke tower wherein water would flow over coke in the well known manner.

Assuming that a non-smoking burning oil (kerosene) is to be obtained from the smoky burning oil fraction of Beaumont petroleum by the aid of methyl alcohol as the diflerentially solvent menstruum, the procedure The crude Beauratus not shown), cracked oil equal to about 82 per cent. by volume of the charge of crude oil being collected as distillate, namely, about 30 per ccnt.'before cracking commences and 52 per cent. afterward. This. cracked oil is then distilled in a fire heated 'still in the ordinary way, except that the still should have arectifying column (say, one similar to column 7 without the water cooled dephlegmator 746). When a'temperature of about 350 F., more or less, is indiof the column, the previously collected distillate (amounting, say, to about 7 percent. more or less, by volume of the charge of crude oil) represents the light end of the burning oil fraction,with whatever naphtha may be yielded by the crude oil. The delivery of distillate from the condenser is then changed to another receiver; and the distillation is continued preferably until all the burning oil fraction is off. The distillate collected after the change of receiver (amounting, say, to'about 48 per cent, more or less, by volume of the charge of crude oil) repfesents the heavier portion of the burning oil fraction and constitutes the oil to be subjected to the hydrocarbon separating inenstruum.

The methyl alcohol to be used as the menstruum should be'nearly anhydrous and of a density equal to or less than 44 B., and

may have a boiling point between 146 F i and 150 F'. Practically crude wood alco-- hol, or the 97 per cent. methyl alcohol of commerce, can be used effectively when dehydrated by distillin and rectifying the same in column 9 r 8 Figs. 7 and 8) herein above' described. What is considered the best ratio of oil to methyl alcohol in washing is one volume of the'former to six of the latter. The general principle recommended to be followed is to use as little methyl alcohol asWill yield a satisfactory non-smoking oil. The oil and the methyl alcohol are introduced in these proportions by the pipes 33 and 34 respectively;fand they travel in opposite directions through the oil washing apparatus; the ,oil and the methyl alcohol belng mixed in each vessel 13 and allowed to separate (with the constituents extracted by each from the other) in each settling and decanting vessel 14. The washed oil which runs from the chamber 36 by pipe 65 is freed from the portion of the menstruum (methyl alcohol) which accompanies it by heating and subjection-to free steam in the stills :70 Z. On leaving still Z it is cooled in pipe 72 (Fig. 2). -Z. The oil obtained (amountinmto about 24% per cent.,,more or less, by volume of the crude oil) and the preliminarily separated light end (amounting to 7 per cent. of the crude oil) are mixed together, giving 31% per cent. of non-smoking I oil of the burning oil fraction. The so oband with solution tained oil is'finished for sale or use as burning oil .(kerosene) by treatment with sulfuric acid of 66 B. and washing with water of caustic soda and again ,with water; or, in other words, it is finished by the well known sulfuric acid treatment. If not. of proper fire test it is brought thereto in the knownway. This burning oil (as also the oil before finishing by the sulfuric acidtreatment) has had arefractive index below 1.4600 (say, 1.4545); it has had the proper mobility for combustion in ordinary petroleum (kerosene) lamps; it has distilled j almost wholly between 250 F. and 600 F.

( tween 275 F. and 600 F.); the port-ions distilling over in 25 F. between 300 F. and 550 F. have ranged from about 52 B. for the lightest-to about 31 B. for the heaviest of these ten portions; the portions distilling over in 25 F. intervals between 800 F. and 400 F. have contained on an average a larger percentage of hydrocarbons per cent. by volume coming over be- 400 F. and 500 F. or 550 have exhibited an average bromin absorbing capacity of more than six per cent. (say, between twelve and thirteen per cent.) and the oil has necessarily possessed the characteristics of an oil obtained out of burning oil distillate from petroleum by subjecting such distillate to a differentially solvent menstruum; in

contradistinction to oil of like refractive index, mobility, boiling point and gravity obtained out of burning oil distillate from pctroleum by subjecting such distillate merely to sulfuric acid of 66 B. or to fuming sulfuric acid (ten per cent.- anhydrid). The average gravity of the four portions distilling over in 25 F. between 400 F. and 500 F. has been about 364 B. and their average refractive index below 1.4590 (say,

In addition to the washed oil which runs from the oil washing apparatus by the pipe 65, another oil accompanies the hydrocarbon separating menstruum which runs from chamber 35 by pipe 54, the same having been washed by the nienstruum out of the Oil supplied by pipe 33, as before mentioned. The menstruum (methyl alcohol) is distllled off from this oil mainly in stills 0 d by dry heat and as to the remaining part in stills e is by heat and subjection to free steam. The oil leaving still 7: iscooled in pipe 63 (Figs. 2 and 7). It has amounted to about 23}, per cent, more or less, of the crude oil and has had a ratio of carbon to hydrogen of more than seven parts by weight of the former to one of the latter (say, 87% parts of the former to 124; parts of the latter) 1ts viscosity has been less than 25 per cent. greater than that of water (say, 38% seconds for the oil as compared with 34 seconds for water) it has distilled almost wholl withm the temperature limits of burning 011 (to wit, 250 F. to 600 F.) (97%% by volume coming over between 400 and 575 F.) the portions distilling in 25 F. lntervals between 400 F. (the commencement of distillation) and 550 F. have ranged from about 34 B. for the lightest to about 23 B. for the heaviest of these six portions; and. the oil has necessarily possessed the characteristics of the more highly carbonaceous "of the two-011s obtained out of burning Oll distillate from petroleum by si'ibjecting such distillate to.a differentiallysolventmenstruum in contradistinction to oil obtained by distillation from gas tar and the like or by addition of water or by steaming from acid sludge from treatment of petroleum,'and having the like percentage of carbon to hydrogen, viscosity, boiling point and gravity. The main part of the menstruum (methyl alcohol) is recovered in a nearly anhydrous state by the evaporation of the same from the oil by dry heat alone (no free steam) in stills 0 cl with rectification of the vapors in column f and dephlegmator 746 and condensation of the so rectified vapors in condenser g. The rest of it is recovered first in a state of dilution with water by the distillations with introduction of free steam into the liquidin stills e h and above the liquid in stills Z, with condensation of the vapors in condensers m and j, and then in a nearly anhydrous state by distilling the aqueous condensate from condensersm j- '(after' separation of oil in the lnve'rted siphons 901 and 905, Figs. 7, 8 and 9), the distillation being performed in section (1 of column q r s and in stills n and j), with recti fication of the vapors in column (1 1 s and condensation of the nearly anhydrous vapors in condenser t. The so recovered menstruum is returned to the oil washing apparatus by pipe 3 1-, with or without intermedlate storage tanks 76 as may be necessary orbe thought proper; and it is used over and over again, with such replenishment (if any) as may be necessary.

A slightly modified mode of obtaining the same burning oil (kerosene) and the same highly carbonaceous oil is to distil the before mentioned cracked oil (representing 82 per cent. by volume of the crude Beaumont oil) until the entire burning oil fraction (55, per cent. of the crude oil) is off and to separate the light end (7% by volume of the crude oil) from the heavier portion of said fraction in a steam heated still with rectification of the vapors. Said heavier portion would then be subjected to the menstruum; and the washed oil would be mixed with the light end and finished by the sulfuric acid treatment, the menstruum being recovered and the oil of higher ratio of carbon to hydrogen being collected.

When considered necessary or desirable, the preliminarily separated light end can be subjected to the hydrocarbon separating menstruum; and the latter can be removed from it, or from other oil, in any appropriate Way. The oil which is to be subjected in whole or in part to the differentially solvent menstruum can be subjected to any desired preliminary. treatment without exceeding the limits of the invention.

The foregoing description will also enable those skilled in the art to subject to'the differentially solvent menstruum the heavier illuminating oil fraction of Beaumont petroleum and either or both the illuminating oil fractions of other petroleum as herein above set forth. I

The oil can be Washed with the menstruum as often as may be necessary to accomplish the desired and feasible separation of hydrocarbons. The ratio of menstruum to oil can be varied. Good results with the burning oil fraction of Beaumont petroleum have been obtained by distilling the before mentioned cracked oil (equal to 82 per cent. by volume of the crude oil) with collection separately of a light end (equal as before to 7 per cent. of the crude. oil) and a heavier portion of the burning oil fraction equal to 35 per cent. of the crude oil and by subjecting this latter to four times its volume of the nearly anhydrous methyl alcohol, with subsequent separation of the latter, admixture of the Washed oil with the light end,

and treating the mixture with sulfuric acid of 66 13.; but the yield of burning oil was less and its quality little (if any) better than that of the oil obtained by washing with six volumes of methyl alcohol, the cut representing 48 per cent. of the crude oil and composed of .the heavier portion of the burning oil fraction after the light end (equal to 7 per cent. of the crude oil) had been separated therefrom. Y

The composition of-the two oils obtained from the burning oil fraction of petroleum by the separating action of the differentially solvent menstruum will depend (1) upon the kind of crude petroleum whose burning oil fraction is subjected thereto, (2) upon the particular composition of the crude petroleum of the kind treated, (3) upon the particular points at which cuts are made in the fractional distillation, (4) upon the condition of the oil as cracked or uncracked, (5) upon whether all or part only of said fraction is subjected to the menstruum, (6) upon the particular character of the menstruum employed, (7) upon the ratio in volume of the menstruum to the oil subjected thereto, SE13) upon the mode of washing, (9) upon t e number of timesthe Washing is performed, and possibly (10) upon other conditions. The smoky oil, for example, could be run again through said apparatus and be separated intotwo oils, one of which would have a higher ratio of carbonto hydrogen than the other. Moreover, oils of various compositions could be obtained by admixture with other oil; and in some cases, at least, such mixed oil might be recognizable as composed in part of one or other of the new or improved oils of the present invention.

-To determine whether a givenoil of the burning oil fraction of petroleum is smoky or non-smoking, the same may be burned in a common fiat flame lamp with the wick projectinv between an eighth and a quarter of an inc above the cone and with a porcelain dish supported between a half inch and an inch above the'top of the lamp chimney, so as not to interfere with the draft. If substantially no soot should be deposited on the dish in half an hour, the oil may be rerefra-ctometer.- An index of 1.4545 -'would indicate a non-smoking" oil; ,onefoii 1.4600 would indicate a smoky oil. A burning oil (kerosene) would probably practically I 1O non-smoking with a refractivexindex of 1.4500 and may possibly be so with'anindex 1 somewhere between 1.4560 and 1.4600.

To determine the proportion of an oil which is readily attacked by fuming sulfuric acid (ten per cent. anhydrid) tl 1e acid can "be applied in-small lots to asa-mple-of the,"

oil until aftersettling and decan'tatio'n the acid continues to fume.

withdrawn by the acid represents the peri .20 centa-geof hydrocarbons readily attacked by fuming sulfuric acid. 7 I

Thestatement of certain omissions, additions orother modifications herein is not intended to exclude other omissions, addi- 'tions and substitutions Within the spirit of.

' the invention.

The present application is a division and continuation of my' application' of October 4., 1902, No. 125,967, which latter included claims toapparatus as well as to process and product and has'be'en'divided in consequence of official requirement.

The petroleum of the hereinafter written. process cla1ms is primarily Beaumont or analogous petroleum as hereinabove defined; but it is not exclusively so, except in claim 1. In-the remaining process claims other petroleum having a burning oil fraction denser 4 than that of- Pennsylvania or Lima petro Beaumont or analogous zpetroleum; while in process claims numbered 3 and following other petroleum in general is by further extension included also. Y

The burning oil fraction or the illuminating fraction of .the petroleum is primarily to be treated in the form of' burning distillate or an illuminating oil distillate; but it is intended by extension to include the treatment of-the same in other forms. also.

-. The: expression illuminating oil fraction applies -to either the burning oiljfraction or :the -next heavier fraction. of petroleum or to bons distilling over within the temperature limitsof one or other or of both of said fraccracked; except in claim 8,'which. recites cracked oil exclusively.

The mensguum primarily intended is one which has -a-fgreater solvent action on the smoky than it has on the non-smoking hy- 35 drocarbons which compose the burning oil likewise lower in refractive index. possible, therefore, to compare the improve- The total mou t ment in refractive index effected by treatleumis by extension included .along with spect to smokiness or tndencytherto, substantially as described.

both oft-hese'ffractions taken together; and. 'an F illuminating oil distillate is-one com-' ,non smoking from that which it has on the I"? posed mainly (if not'wholly) of hydrocartions. The distillate may be cracked or un fraction of Beaumont petroleum; but -it is also'intended to include a menstruum in action on the smoky and non-smoking hydrocarbons respectivelyof said burmng Oll fraction of Beaumont petroleum.

: 5 Oil from, which hydrocarbons having a greater ratio of carbon to hydrogen than the oil itself have been separated has a lower refractive'index and is a so lighter 1n grayi-ty thanin its untreated state; and, at least as a general proposition, the burning o1l fraction of petroleum which is naturally lighter in gravity than that of another is so It is ing oils of different gravities orby mixing treatedand untreated oils of like boiling point and different gravities only by makin an allowance in the refractive index for dif ference of gravity. In, claims 15, 16 and 17 allowances, estimated as reasonable,=are.

recited.

f I claim as my invention or discovery;

'L-The process of treating Beaumont or analogous petroleum, by subjecting part at least of the smoky burning oil fraction of suchpetroleum to a menstruum which has a different sol-vent action upon the non-smok ing from that which it has on the smoky hydrocarbons of the burning oil fraction of Beaumont oil, and thereby effecting a suflicient separation of such hydrocarbons from each otherfor the obtainment of a nonsmoking burning oil (kerosene), substanti'ally-as described.

2. The process of treating petroleum having a denser burning oil fraction than that of Pennsylvania or Lima petroleum, by subjecting part at least of an illuminating oil fraction of such petroleum to a menstruum .which has a different solvent action upon the non-smoking from that which it has on the smoky hydrocarbons of the burning oil fraction of Beaumont oil, and thereby effecting auseful amelioration of said-fraction 1n re- 3. The process of treating petroleum, by

. subjecting part at least of'anilluminating oil fraction-of the petroleum to amen'struum. which has a different solvent action upon the smoky hydrocarbons of the burning oil fraction of Beaumont oil, and thereby obtaining an oil of such fraction which has a less ratio illuminating oil fraction of'the petroleum 130 with a menstruum which has a different solvent action upon the non-smoking from that which it has on the smoky hydrocarbons of the burning oil fraction of Beaumont oil, separating the two resulting 'liquids from each other, and separating the menstruum from the hydrocarbons in solution therein, substantially as described.

5. The process of treating petroleum with repeated use of the same body of hydrocarbon separating menstrnum,by'mixing .an oil containing part at least of an illuminating oil fraction of the petroleum withamenstruuni which has a different solvent action upon the non-smoking from that which it has on thesmoky hydrocarbons of the burning oil fraction of Beaumont petroleum, separating the two resulting liquids from each other, separating and recovering the menstruum from the hydrocarbons in solution therein, subjecting other oil of the same description to the so recovered menstruum, and so continuing, substantially as described.

6. In obtaining burning oil from petroleum, the improvement consisting in subjecting the less volatile portion of the burning oil fraction of the petroleum to a treatment whereby the removal therefrom is effected of. hydrocarbons which are readily attacked by fuming sulfuric acid, and mixing the so treated portion with a more volatile portionof the same petroleum which has not receivedsuch a treatment, substantially 'as described. 35 b 7. For obtaining burning oil from petroleum, "the process of threesteps whereof one step consists in distilling the light end from the heavier portion of part at least of the burning oil fraction of said petroleum, another step in'subjecting said heavier ortion after removal of said light end there rom to a menstruum which has a different solvent action upon the smoky from that which it has upon the non-smoking hydrocarbons of the burning oil fraction of Beaumont oil, and the third step in mixing said lighter end with the so treated heavier portion, substantially as described.

8. For obtaining burning oil from petroleum, the process of two steps whereof the first consists in distilling the crude oil wlth 'cracking, and the second in subjecting cracked oil so obtained and containing part at least of the burning oil fraction of the etroleum to a menstruum which-has a diferent solvent action upon the non-smoking from that which it has on the smoky hydrocarbons of the burning oil fraction ofBeauinont petroleum, thereby; obtaining oil of said fraction which has a less ratio of carbon to hydrogen than that possessed before treatment by the crackedoil from which it has been so derived, substantially as de-.

scribed. p I

9...A new or'improved petroleum or hyscribed.

an average in the portions distilling over 25 F. intervals between 300 F. and 400 F.

drocarbon oil havin a refractive index less than that of oil 0 like boiling point obtained from Beaumont petroleum by fractional distillation and treatment with sulfuric acid of 66 Baum', having a mobility sufficient for burning oil (kerosene), distilling lar ely at leastv within the temperature limits of burning oil (kerosene) in part below and in part above 400 F., and containing on an average the portions distilling over in 25 F. intervals between 300 F. and 400 F. a larger percentage of hydrocarbons which are readily attacked by fuming sulfuric acid than in the portions distilling over in such intervals between 400 F. and 500 F. or 550 F., substantially as de- 10. A new or improved petroleum or hydrocarbon oil havin a refractive index less than that of oil 0 like boiling point obtained from Beaumont petroleum by fractional distillation and treatment with sulfuric acid of 66. Baum, having a mobility sufficient for burning oil (kerosene), distilling largely at least within the temperature limits of burning oil (kerosene) and in part at least above 400 F. and exhibiting to a recognizable extent the characteristics ofan oil which has been obtained out of burnin oil distillate from petroleum by which has a different solvent action upon the non-smoking from that which it has on the smoky hydrocarbons of the burning oil fraction of Beaumont oil, that is to say, ex-

hibiting said characteristics to such extent that the oil examined can thereby be distinguished from oils having a like refractive index, like mobility and like boiling point obtained out of burning oil distillate from petroleum by agitatin such distillate with sulfuric acid of 66 aum or with fuming sulfuric acid (ten per cent. anhydrid), and removing the resultant acid sludge, substantially as described.

11. A new or improved petroleum or hysubjectmg such distillate to a menstruum drocarbon oil havin a refractive index less than that of oil 0 like boiling point obtained from Beaumont petroleum by fractional distillation and treatment with sulfuric acid of 66 Baum, having a mobility sufficient for burning'oil (kerosene), distilling lar ely at least within the temperature limits of burning oil (kerosene)1n part below and in part above 400 F. exhibiting in the larger number at least of the portions distilling over in 25 F. intervals a 'greater.

exhibited by those dist-111mg over in the same temperatureintervals from density than is Pennsylvania petroleum, and containing on than in the portions 'disti ling over in such burning oil (kerosene), and in part atleast above 400 F., exhibiting in the larger number at least of the portions distilling over in 25 F. intervals a greater density than is ex hibited in those distilling over in the same temperature intervals from Pennsylvania petroleum, and also exhibiting to a recognizable extent the, characteristics of an oil which has been obtained out of burning oil distillate from petroleum by subjecting such distillate to a menstruum which has a difi'erent solvent action upon the non-smoking from that which it has on the smoky hydro-' carbons of the burning oil fraction of. Beaumont oil, that is to say, exhibiting said characteristics to such extent that the oil examined can thereby'bedistinguished from oils having a like refractive index, like mobility and like boiling point obtained out of burning oil distillate from petroleum by agi-- tating such distillate with sulfuric acid of 66 Baum or with fuming sulfuric acid (ten per cent. anhydrid), and removing the resultant acid sludge, substantially as described.

13. A new .or improved petroleum or hydrocarbon oil having a refractive index less than that of oil of like boiling point ob tained from Beaumont petroleum by fractional distillation and treatment with sulfuric acid of 66 Baum, having a mobility.

suflicient for burning oil (kerosene dis.-

tilling largely at least within the te perature limits of burning oil (kerosene) in part below and in part above 400 F., exhibiting in the portions distilling over between 400 F. and 500 F. or 550 F. an average bromin absorbing capacity of not less than six per cent.,'and containing on an average in the ortions distilling over in 25 F. intervals etween 300 F. and 400 F. alarger per-' centage of hydrocarbons which are readily attacked by fuming sulfuric acid than in the portions distilling over in suchv intervals between 400 F. and 500 F. or 550 F., sub.-

. stantially as described.

14. A new or improved petroleum orhydrocarbon oil having a refractive index less than that of oil of like boiling point obtained from Beaumont petroleum by fractional distillation and treatment with sulfuric acid of 66 Baum, having a mobility sufiicient for burning oil (kerosene), distillin largel at least within the temperature units 0 burning oil (kerosene) and in part at least above 400 F., exhibiting in the portions distilling over between 400 and 500 F. or 550 F. an average bromin absorbing capacity of not less than six per cent., and also exhibiting to a recognizable extent the characteristics of an oil which has been obtained out of burning oil distillate from petroleum by subjecting such distill-ate to a menstruum which has a different solvent action upon the non-smoking from that which it has on the smoky hydrocarbons of the burning oil fraction of Beaumont oil, that is to say, exhibiting said characteristics to such extent that the oil examined can thereby be distinguished from oils havin a like refractive index, like mobility and like boiling point obtained out of burning oil distillate from petroleum by agitatin such distill-ate with sulfuric acid of 66 aum or with fuming sulfuric acid (ten per cent. anhydrid), and removing the resultant acid sludge, substantially as described.

15. A new or improved petroleum or hydrocarbon oil having a mobility sufiicient for burning oil (kerosene), distilling largely at least within the limits of burning oil (kerosene) in part below and in part above 400 F., exhibiting in the portions distilling over in 25 F. intervals between 400 F. and 500 F. an average refractive index not more than 1.4590 for an avera 'e gravity of 364 B. with a deduction of fifteen ten thousandths for each degree Baum, which said average gravity may be lighter than 364 B. and with an addition of twenty ten thousandths for each degree Baume, which said average gravity may be heavier than -86-}- B., and containing on an average in the portions distilling over in 25 F. intervals between 300: F. and 400 F. a larger percentage of hydrocarbons which are readily attacked by fuming sulfuric acid than in the portions distilling over in such intervals between 400 F..and500 F. or 550 F., substantially as described.

16. A new or improved petroleum or 11y drocarbon oil having a mobility suflici'ent for burning oil (kerosene), distilling largely at least within the limits of burning Oll (kerosene) in part below and in part above 400 F., exhibiting in the portions distilling over in 25 F. intervals between 400 F. and 500 F. an average refractive index not more than 1.4590 for an average gravity of 364 B. with a deduction of fifteen ten thousandths for each degree Baum, which said average gravity may be lighter than 364 B. and with an addition of twenty ten thousandths for each degree Baum, which said average gravity may be heavier than 364 B., and also exhibiting to a recognizable extent the characteristics of an oil which has been obtained out of burning oil distillate from petroleum by subjecting such distillate to a. mentruum which has a different solvent action upon the non-smoking l a different solvent action upon the nonfrom that which it has on the smoky hydro carbons of the burning oil fraction of Deanmont oil, that is to say, exhibiting said characteristics to such extent that the oil examined can thereby be distinguished from oils having a like refractive index, like mobility and like boiling point obtained-out of burning oil distillate from petroleum by agitating such distillate with sulfuric acid of66 Baum or with fuming sulfuric acid (ten per cent. anhydrid), and removing the resultantacid sludge, substantially as described.

17. A new or improved petroleum or hydrocarbon oil, having a mobility suflicient for burning oil (kerosene), distilling largely at least within the limits of burning oil (kerosene) and in part at least above 400 F., and exhibiting in the portions distilling over in 25 F. intervals between 400 F. and 500 F. an average density not less than about 35 B. nor more than about 38 B. and a refractive index not more than 1.4590 for an average gravity of 36 B. with a deduction of twenty ten thousandths for each degree Baum, which said average gravity may be lighter than 36-}- B. and with an addition of twenty ten thousandths for each degree Baum, which said average gravity may be heavier than 36% B. and also an average bromin absorbing capacity of not less than six per cent., substantiall 3 as described.

tions distilling over in 25 F. intervals-be. -tween 400 1*;

and 500 F1 or 550 F. a density heavier by ,not less than ten degrees Baum than the portions distilling over in the same temperature intervals from Pennsylvania petroleum, and also exhibiting t0 a recognizable extent the characteristics of oil which has been obtained out of burning oil distillate from petroleum by subjecting such distillateto a menstruum which has smoking from that which it has on the smoky hydrocarbons of the burning oil fraction of Beaumont oil, that is to say, exhibiting said characteristics to such extent that the oil examined can thereby bedistinguished from oils of like ratio of carbon the temperature limits of burning oil (kerosene) and in part at least above 400 F., exhibiting in thelarger number at least of the portions distilling over in 25 F. intervals between 400 F. and 500 F. or 550 F.

a density heavier by not less than ten, normore than twenty degrees Baum than the portions distilling over in the sametemperature intervals from Pennsylvania petroleum, and also exhibiting to a recognizable extent the characteristics of oil which has been and by'agitating the acid sludge of petroleum refiners with Water or by steaming it, substantially as described.

In testimony whereof I have signed my name to this specification in the presence of two subscribing witnesses.

HERMAN FRASCH.

.to hydrogen, like mobility, and like boiling

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