US564923A - Process of refining lima or similar petroleum - Google Patents

Description

- (No Model.)

7 s Shets-$heet 1. v H. FRASGH.

PROCESS 0P REFI'NING LIMA OR SIMILAR PETROLEUM.

Nd.-564',923. Patented July 28, 1896;

(No Model.) a Sheets8heet 2.

- H. PRASGH. rnocnss 0F REFINING LIMA 0R SIMILAR PETROLEUM.

No. 564,923. Patented July 28, 1896.

(No Model.)

' 3 Sheets-Sheet 8. H. PRASOH. PROCESS OF REPINING LIMA 0B SIMILAR PETROLEUM.

No. 564,923. Patented July 28, 1896..

. is, of course, intended to be secured for all extent in States of theUnion other than Ohio.

, oleicacid, rosin, or other added agent being ing the presence of skunk 'in the oil. .The

dissolve litharge: When tested by the addi-] Lima or similar petroleum of what is known UNiTED STATES- HERMAN FRASOH, or CLEVELAND, OHIO, A'SSIGNOR To TH AT'ENT FFICE. V.

E SOLAR REFIN- ING COMPANY, or OHIO. i

SPECIFICATION forming part of Letters Application filed December 17, 1894.

To all whom. it may concern: Be it known that I, HERMAN FRASCH, a, citizen of the United States, residing at Cleve-. land, in the county of Cuyahoga and State of Ohio, have invented certain new and useful Improvements in Processes of Refining Lima or Similar Petroleum and I do declare the following to be a full, clear, and exact description of the invention, such as willenable others skilled in the art to which it appertains to make and use the same, reference being bad to the accompanying drawings, and to the letters and figures of reference marked thereon, which form a part of this specification.-

This invention relates to the removal from as skunk among workers in that class of oil, the said skunk resisting removal (as is well known) by the ordinary sulfuric-acid and alkali treatment, by which oils of the Pennsylvania class have long been satisfactorily refined; but each. part of the invention the uses to which it maybe applicable.

Skunk-bearing oils are found-not only about Lima, Ohio, (whence the name) but also in other parts of Ohio, in Canada; and to a less As they come from the well they contain a very considerable percentage of sulfur, (usually upward of one-half of one per cent.,) have a penetrating disagreeable odor, and dissolve litharge (lead oxid) in considerable proportions, the peculiar odor and the-property of dissolving litharge without the aid of believed to be characteristic of them and provburning oildistillates from ordinary distillation of skunk-bearing, petroleum, (whether given the ordinary sulfuric-acid and alkali treatment or not,) have the skunk odor, and

tion of a small quantity of an aqueous solution of plumbate of soda, they turn yellow, provided theyhave previously been freed from sulfureted hydrogen. Otherwise this latter substance causes a dark or black discoloration. On burning in lamps they give a badodor and cause a cloud on the chimney and a crust on the wick. There has, howor solution and suspension therein;

Patent No. 564,923, dated July .28, 189s. Serial No.532,077l (No specimens.)

distillate from such redistillation dissolves litharge and (if free from sulfureted hydro-' 6o gen) turns yellow withplumbateof soda solution. On burning in lamps the Canadian treated oils give a badodor, cloud the chimney, and crust the wick. By'the Canadian treatment, therefore,'the skunk is concealed, but not removed.

. 3 For the pu'rpose'of removingthe skunk from this class of oils I have heretofore devised a number of processes and apparatus. I discovered, among other things, that the skunk could be made to react with suitable substances having a basis of metal, and could thus be decomposed, with the formation of a metallic sulfur compound, easily separable from the hydrocarbons;- and I further dis; covered various modes whereby such reac tion could be brought about industrially.

I obtained very successful results by distilling" the skunk-bearing oil with the decom posing substance dissolved therein, and also 8.0 by vaporizing the oil and passing the s'kunkbearing vapors through or over an oily or resinous liquid holdin g the substance in solution Further,

I obtained useful results in the decomposition of the skunk by the substance in a solid state instead of in solution in an oily or resinous liquid, the said substancebeing in'theform of a'more or less finely-ground powder or in larger pieces or lumps. In accordance with the present invention skunk-bearin g vapors are subjected to a purificator composed of a refractoryfibrous material like woolly asbestos and a solid finelydivided skunkdecomposing substance ad- 5 herent tothe fibers of such material. It is an advantage and. a special. improvement to use'a skunk-decom posing substance having a basis of copper or like metal, (by which here and elsewhere in-this specification is meant a roo metal whose oxid is soluble in skunk-bearing 011,) because such substance e'ifects a decom- 2 i r l 564,923

position of the skunk at temperatures below those which cause a substantial decomposition of the hydrocarbons and formation of permanent gases, and which are apt to give a scorched appearance and odor to the distiloil-vapors.

late. 1 1

i The best mode of charging the asbestos with the skunk-decomposing substance is to stir the latter as a fine powder into a thin pulp of asbestos, which is then dried. The asbestos takes up the powder which adheres thereto. The powdered substance may be such as at once to act asa skunkdecomposer, (say, for example, black oxid of copper,) or it may when mixed with the pulp be in an inactive condition and require a treatment before it will decompose skunk. Thus copper sulfid does not decompose skunk, but by oxidation it becomes converted into the sulfate (provided sulfur dioxid is not eliminated) or into the oXid, (if sulfur dioxid be given off) either of which isan active decomposer of skunk in Such oxidation can be performed after the copper sulfid has been stirred int-0 the asbestos pulp and the latter dried. Further, I have discovered that the skunk-decomposing substance can be made to assume apeculiar state in which it is materially ex panded or swelled beyond the ordinary ground form of such-substance or even that of an ordinary precipitate, and in such state can be usedwhile adherent to asbestos'or asbestoslike material. i

In charging the asbestos with the skunkdecomposing substance it suffices to apply the latter in the ordinary ground condition or in the precipitated form,whether the application be by stirring thedense substance into asbestos pulp or otherwise. The swelled or expanded state can then 'be given to the adherent substance by suitable change of chemical composition under conditions of pressure and temperature adapted to the retention of such state, all as hereinafter more fully set forth. v

To support the purificator (consisting of the skunk-decomposing substance and the asbestos or refractory fibrous material, to which it is adherent) in such a manner that the oilvapors to be purified can have full access to such substance, and that they do not pass by short cuts over certain portions only of the purificator, the said purificator is placed in layers on horizontal or inclined plates or trays in a zigzag vapor-duct.

The oil-vapors being thus compelled to take a roundabout course and to pass over an extended body of the purificator are the more apt to act upon every particle of the skunk-decomposing substance and to haveevery particle of the skunk acted upon and decomposed by such substance. The best arrangement is to have at intervals in the duct a number of these plates and purificator-layers vertically superposed or made into a pile with passages between each layer and the plate or tray above.

After the skunk-decomposin g substance has become inactivethrough the union of its metal with sulfur from the oil-vapors its activity is restored by burning, or, in other words, oxidation, and this burning is best eife'cted below such a temperature as would suffice to cake the said substance, (when of a fusible nature, like copper co1npounds,) while yet sutficiently high to effect the revivification in a reasonable time. To allow the burning to proceed with the greater rapidity without raising the temperature unduly, the heat is carried off by a cooling medium as said heat is generated.

In the accompanying drawings an apparatus is illustrated which ,is considered most suitable for carrying the invention into effect.

Figure 1 is a side view or elevation of such apparatus, partly in section, with a middle portion of the still taken out in order to get the figure on the sheet. Fig. 2 is a partial plan of the same, partly broken away to'illustrate the construction in horizontal section. Fig. 3 is avertical section on line -i M of Fig. 1, and Fig. 4 is a detail view.

The still A'is shown as a cylinder-still of ordinary construction, except for the pipe- ,connections with the chamber B, which forms the jacket of the purifier-boxes O C. This chamber or jacket communicates at the bottom through the large pipe 2 with the liquidspace, and at the top through the pipe 3 with the vapor-space, of the still, so that during a run the oil stands at the same level in the said chamber or jacket as in the still. The cover 4 closes the top of the chamber vaportight. The object of this arrangement is to maintain the temperature of the purifier through the medium of the oil inthe still.

The purifier might be kept hot by any ordinary or suitable arrangement, such as a separate fire, or. the fire-gases from under the still applied directly or through an ordinary sand or liquid bath.

, In keeping up the temperature by the liquid oil such temperature would rise gradually as distillation proceeds. \Vith other heating arrangements it might be raised gradually or itmight be kept at a constant high temperature during a part.and,'if the range of gravities be not too great, during the whole of a run.

Underneath the chamber or jacket B are flues 5, (see Fig. 2,).conveying the products of.

combustion from the space beneath the still to the chimney, whose position is shownat 6. They supply heat to keep up the temperature of the jacketing fluid. The maintenance of the purifiers temperature by the liquid oil could be secured by having the purifier within the still instead of within a communicating chamber or jacket. p The purifier-boxes C 0 rest on posts 7, which in turn rest on the bottom of the jacketing-chamber B. Two of these boxes are shown, but the number is' not essential. XVithin each box are supports, to wit, crossbars 8 and brackets 9,for supporting the floorwoolly asbestos, to the fibers I plates 10, bywhich the box isdivided into a vapor-duct c c, respectively,-=-rising in a zigzag fashion from the bottom of the box. At each end of the box every alternate floor terminates at .a distance from the end wall the box, so as to make the duct run back and forth lengthwise of the box. On the several floors are piles of many trays D, each provided with a layer E of the purificator composed of the skunk-decomposing substance and .the of which such substance adheres. l

Preferably a thin pulp of asbestos is made with water and the finely-divided substance (in an active or an inactive condition) stirred,

into it. The pulp is then dried. 'Du ring the admixture the substanceis kept suspended.

I I It adheres to the asbestos fibers like a dye.

If a cupreous substance is used, as is preferred, black oxid of copper from any convenient source, ground, say fine enough to pass through a bolting-cloth having one hundred meshes to the inch, will answer, but it .is better to use copper oxid procured from carefully roasting theresidue resulting from using an oily solution-of copper oxid in a skunk-removing operation.

Finely-ground copper sulfid or sulfate can be used. Precipitated copper compounds, as sulfid or hy- The mention of these intended to exclude the use droxid, can be used. is not, of course,

of other forms. A layer E of the purificator, prepared as just described, is placed on each tray.

The trays are shown as held apart by sepsleeves 11, Fig. 4, so as to form passages over the purificator E. Bolts 12 pass through the trays D and sleeves 11 and clamp the charged trays of each pile together. The piles of trays are separated from one another and the two end walls of the boxes by spaces F, forming the chambers in the duct. The tops' of the boxes 0 O are removable, and the floor-plates and piles of trays are introduced through the top. First the bottom is supplied with piles above and below,

of charged trays, (the same as indicated on the third floorabove in Fig. 3 of the drawings,) then the floor-plates and piles of charged trays of the floor next above are in troduced, and then those of higher and higher floors. Finally the top is put on. Other suitable constructions could be used. The trays might be inclined instead of horizontal, if preferred.

The purifier-boxes O O are fastened to each other and to the walls of the chamber or jacket B by stays 13. The top of the vapor-duct in .box 0 is connected with the bottom of the vapor-ductin box 0' by means of the pipe 14. The pipe 16 leads from the vapor-space of the chamber B to the vapor-duct at the bottom of box 0 and the pipe 16 from the vapor-duct at top of box 0 to the condenser. (Not shown.) The pipe 15 might of course lead from the vapor-space of the still A. In either case it distillate, but; crude oil is preferable.

' Without ing a metallic sulfur chambers would receive the vapors fromboth the still A and chamber B. k

The vapor-pipes 3 and 16, as shown, are severally provided with a removable section 3 and 16, respectively, for breaking the still and condenser connections when desired. A plate (not shown) may be bolted to the flange 2, so as to close the inlet of pipe 2 whenever it is desired to cut the chamber B off from the still A. A similar'plate maybe bolted to the flange 15 when it is desired toclose the pipe 15.

with a water-supply pipe 18, and a draw-01f 19. The boxes 0 C have air-inlet pipes 20 and side. floor. It can be closed with a removable plate or plug, and when open can, if necessary, have the inlet-openings adjusted by means of perforated plates, or reducers, or the like. The boxes also have each a draw- ofi 22 and 23, respectively, with a stop-cock therein, as shown for the box 0 in Fig. 3. In case oil should leak into the boxes, the drawolfs serve to remove it, but it is intended to have the boxes tight. The boxes C 0, being charged with thepurificatordisposed in thin layers E on the trays D, are closed, and if the skunk-decomposing ficator is in an active condition (say copper substance of such puri- The chamber B is further provided -With, manholes 17,

21, extending through the jacket B to the out- There is one of these pipes for each.

oxid) the said boxes are put into communii cation with the still A by the pipes 3 and 15, and with the condenser (not shown) by the pipe 16. The jacketing-chamberB is also put in communication with the still through the pipes 2 and 3. The watervpipe 18, ,the drawolf'19, the air- inlet pipes 20 and 21, and the draw-oifs22 and 23 are all closed.

The still Ais filled to the usuallevelwith, say, crude Lima oil, either containing the rod naphtha, or from whichthe naphtha has been separated. .It might be supplied with distillate, either burning'oil or naphtha, or other The oil flows through the pipe 2 into the chamber B and stands therein at the same level as in the still. The fire is started under the still and the oil heated to the distilling temperature. The skunk-bearing vapors pass by the pipe 15 into the portion of the vapor-duct c at the bottom of box 0. Here, and in the duct above each floor 10,the volume of vapors is divided into numerous small streams flowing in the same horizontaLdirection between adjacent trays D over thecorresponding thin layers of asbestos and finely-divided skunkdecomposing substance,maintained by the oil at a temperature to prevent condensation danger of overheating the vapors.

At each pile of trays the vapors are divided.

The skunk reacts with the substance, formcompound, which re- Other products of the pass OE With the oil-vapors. In he F in the duct the vapors of the dif mains on the trays. treaction in box at the bottom of said box. ,pass up through such duct, being divided reepeatedly into numerous small parallel streams 4 j y A v ferent streams have an opportunity to [mingle-doefore they are dividedagain into small streams by the next pile of trays.

After traversing the tortuous vapor-duct c,

flowing horizontally over the thin layers of {asbestos and skunk-decomposing substance, 8 v and they escape with the volatile products of the skunk decomposition by the pipe 16 to the condenser. They are thereby reduced to a liquid which may be subjected to any fur.- ther operation which may be desired. The burning-oil fraction would be finished by the well-known sulfuric -'acid and alkali treat ment. The naphtha (if not previously removed, as it preferably would not be)would also have its skunk decomposed and would be finished in the usual way.

During the distillation lighter vapors of course first pass OE and then the heavier vapors, and the heavier the vapors the higher becomes the temperature in the still A,chamber B, and purifier-boxes C O. The vapors generated in still A enter the jacket B by the pipe 3 and pass with the vapors from theoil therein into the purifier C G by the pipe 15. The distillation would ordinarily be stopped and the residuum drawn oif after the removal of the burning oil, although heavier fractions could be freed from skunk in accordance with r the invention.

After the skunk-decomposing substance has become sulfured and inactive, or as much so as is thought proper, and at the end of a run when the residuum has been drawn 01f from still A and chamber B, the communication of the still and condenser with the purifier and its jacket'is out off by applying a plate to the flange 2 over the end of pipe 2 and by removing the pipe-sections 3 and 16.

The outer end of that portion of pipe 3 which.

is attached to the jacket B, and also the upper end of pipe 15, is closed, and the outer end of the part of pipe 16 which is attached to thebox O is left open or is connected, as

desired. The chamber B is next supplied with-water at ordinary temperature by the pipe 18 to a little below the level of such pipe, after which no further supply of water-is necessary, at least under ordinary conditions. One or more of the air- inlet pipes 20 and 21 are opened and a draft is established, as, for example, by an aspirating steam-jet, (indicated at 16 The skunk-decomposing substance spontaneously ignites and burns with an active combustion; Preferably all the air-inlets are left open, so that the combustion is maintained on all floors at the same time. Owing to the thinness with which the skunk-decomposing substance is disposed on its sppports, the combustion is readily conadmission of air through the air-inlet pipes and by the cooling. effect of the water in the jacket B. The use of adjustable covers or of perforated plates or reducers at the outer end of each branch will serve to regulate the air admissions, or the pipesmight have the right bore to be left fully open. The disposition of the skunk-decomposing substance on its supports allows the air access without raking, and theproducts of combustion pass through the vapor;- duct to escape by the pipe 16.

A practical test is so to adjust the air ad-- mission that the combustion goes on actively enough to boil the water in the jacket B vigorously without going beyondthe production of a dull redness in the dark, as seen through the air-inlet at the early part of the operation. Such glow would soon disappear, and it is not necessary for it to appear even in the early part of the combustion. With a proper air admission the copper-sulfur compound burns without flame and is soon con- -vertedinto a mixture (in greater or less proportions) of copper sulfate and copper oxid.

" Sulfur dioxid 's given off and may be detected in the gases from the pipe 16 by its odor. When the water in jacket B ceases to boil, the revivification may be considered complete, the air-inlets closed, and the purifier, with its contents, allowed 130-0001.

For a purifier havtrollable by regulating, when necessary, the H ing a tortuous vapor-duct. whose cross-section is three feet wide and seventeen and a half inches high, with ten piles of trays to each floor of the duct, with thirty-six trays to a pile, and with anoriginal quarter-inch'layer of a skunk-decomposin g purificator, prepared as hereinbefore described, on each tray, one air-inlet pipe may be used for each floor with an inlet-opening two inches in diameter, that diameter of opening being maintained without change throughout the revivification, a quarter-inch jet of steam, under a boilerpressure of sixty pounds per square inch, being maintained at 1 6 in the ten-inch pipe 16. With such air-inlets the temperature will not rise too high if the substance has become fully charged with sulfur, and active combustion will go on satisfactorily when the substance has become sulfured only to a comparatively small extent.

After the revivification the apparatus is restored to the first-described state, the still A andjacket B filled with crude oil, and one or more additional runs made, until the skunkdecomposing substance is ready for another revivification. If the revivified material is a mixture of oxid and sulfate of copper, sulfur dioxid and vwater accompany the petroleum-vapors to the condenser, which should preferably be lead-lined. sulfurous acid may be removed and utilized.

So far as I am aware, there is no limit to the number of times which the same charge The sulfur dioxid or of substance can be revivified and reused;

indefinitely.

p tion, (say as copper sulfid,) it is made active (for example, by active combustion, as in the undergoes under conditions of temperature consequent fullest activity of the purificator tion, but may require two or more such turns ditions of heat, and pressure, without re- 7 moval of said purificator from the apparatus due to the alterations in chemical composiperature is meant one below that which but, on the contrary, my experience leads me to think that the same charge can be used If the purifier is charged with the skunkdecomposing substance in an inactive condi revivification described) before the skunkbearing vapors are passed over it.

During the skunk decomposition and revivification the skunk decomposing substance on the asbestos undergoes a change of state, indicated by aswollen expanded condition and attended by an increased activity of skunk decomposition. It is believed to be tion which the skunk-decomposin g substance and pressure favorable to the retention of such an increase or expansion as may be caused 'by such changes. Further, it has been found that this peculiar state and the may not be attained completely as the result of one skunk decomposition and revivificafor their attainment.

The particular dimensions of a purifier, the particular depth of the layers of purificator, and other details are given abovemerely by way of illustration in order the better to. enable those skilled in the art to practice the invention. They are not of the essence of the invention, and may be varied without departing'from the spirit thereof.

Ina number of the claims following reference is made to a non-caking temperature and an absence of compacting pressure. To avoid explanation of the expressions repeatedly in the diiferent claims, it may here be, said, once for all, that by non-caking temwould cause a union or agglomeration of the particles of the skunk-decomposing substance, and, that by an absence of compacting pressure is meant a freedom from raking, grinding, or other operation sufficient to unite the particles by compression.

I claim as my invention or discovery- 1. The continuous process of removing skunk from Lima or similar petroleum, consisting in exposing a purificator composed of a refractory fibrous material like woolly asbestos anda comminuted oxid of salt of copper or like metal adherent to the fibers of such material to the vapors of such oil and (when the substance is charged with sulfur) to air so as to revivify the substance by oxidation of the metal and sulfur, all under the conditions of a non-caking temperature and an absence of compacting pressure so as to induce or retain a'swelled or expanded state of extreme subdivision in the substance which adheres to the refractory fibers, and repeating the described operations under said condecomposing substance, substantially as de- 1 scribed.

The improvement in the art of removing skunk from Lima or similar petroleum, consisting in exposing a purificator composed of a refractory fibrous material like woolly asbestos and a finely-divided skunk-decomposing substance adherent to said refractory fibrous material to skunk-bearin g vapors and vSo to a gaseous revivifying agent under the conditions of a non-caking temperature and an absence of compacting pressure, so as to induce or retain in said substance a swelled or expanded and extremely-subdivided condi-' tion, the said substance being exposed repeatedly in its swelled or expanded and extremely-subdivided condition and while the same is still adherent to the said fibrous ma-' terial to the skunk-bearing vapors and the gaseous revivifying agent under the aforesaid conditions of a non-caking temperature and an absence of compacting pressure, substantially as described.

-3. The improvement in removing skunk from Lima or similar petroleum, consisting in exposing a purificator composed of a refractory fibrous material like woolly asbestos and a finely-dividedskunk-decomposing substance adherent to said refractory fibrous material to skunk-bearing vapors and to air under the conditions of a non-caki'ng temperature and an absence of compacting pressure, so as to induce or retain in said substance a swelled or-expanded and extremely-subdr vided condition, the said substance being exposed repeatedly in its swelled or expanded and extremely-subdivided condition and while the same is'still adherent to the fibrous material to skunk-bearing vapors and air under the aforesaid conditions of a non-caking temperature and absence of compacting pressure, substantially as described.

4. The improvement in the art of removing IIO skunk from Lima or similar petroleum, consisting in exposing a purificator'composed of a refractory fibrous material like woolly asbestos and a finely-dividedskunk-decomp0sing substance in the form of an .oxid or salt of copper or like metal adherent to said refractory fibrous material to skunk-bearing vapors and to air under the conditions of a non-caking temperature and an absence of compacting pressure, so as to induce or retain in said substance a swelled or expanded and extremely-subdivided condition, the said sub stance being exposed repeatedly in its swelled or expanded and extremely-subdivided condition and while the same is still adherent to the said fibrous material to the skunk-bearing vapors and air under the aforesaid conditions of a non-caking temperature and an absence of compacting pressure, substantially as described;

5. The process of preparing a purificator,

asbestos, and while the said substance is so adherent subjecting it .to skunk-bearing vapors and tea gaseous revi vifyin g agent under the conditions of a non-caking temperature and an absence of compacting pressure, so-as to induce or, retain a swelled or expanded state of extreme subdivision in said substance, substantially as described.

6. The process of preparing a purificator, consisting in cau'sing a skunk-decomposing substance to adhere in afinely divided state to a refractory fibrous nateriahlike woolly asbestos, and while the said substance is so adherent subjecting it to skunk-bearing vapors and to air under the conditions of anoncaking temperature and an absence of compacting pressure, so as to induce or retain a swelled or expanded state of extreme subdivision insaid substance, substantially as described. I v 7. The process of preparing apurificator, consisting in causing" a skunk-decomposing substance having a basis of copper or like metal to adhere in'a finely-divided state to a refractory fibrous material like woolly asbes tos, and while the said substance is so adherent subjecting it to skunk-bearingvapors and ,to air under the conditions of a .non-caking temperature and an absence of compacting pressure, so as to induce ,or retain a swelled or expanded stateof extreme subdivision in said substance, substantially as described.

8-. The improvement in the art of removing. skunk from Lima or similar petroleum bya continuous process, consisting in passing the skunk-bearing vapors in small horizontallyfiowing streams over layers of a purificator composed of a refractory fibrous material and a finely divided skunk decomposing substance adherent to the fibers of said material, and revivifying such substance by passing over said layers similarstreams of air or gaseous revivifyingagent so as to leave the said substance adherent to said fibers in a finelydivided condition for repeated action, sub stantially as described."

9. The improvementiu the art of removing skunk from Lima or similar petroleum, conscribed, is

sisting in causing a skunk-decomposing substance in a solid finely-divided state to adhere .to a refractory fibrous material, supporting the so-produced purificator in a way to give aeriform fiuid access to said substance with- 1 out disturbing the purificator, passing the J skunk-bearing vapors over the so-supported purificator when the substance is in the active condition, and effecting revivification by an active combustion of the so-adherent spent substance, which combustion oxidized both the sulfur and the metal and leaves the revivified substance, in a solid finely-divided condition adherent to the refractory fibers, substantially as described.

10. The method of revivification, consist. ing in producing an activecombustion'of the sulfured substance, while this is adhering to a refractory fibrous material and isso supported as to give the air access thereto with out raking or similar disturbance, and controlling such combustion by the aid of a cooling medium at a temperature indicated by dull redness or blackness, substantially as described. l 1

11. The improvement in the art of removing skunk from Lima or similar petroleum, consisting'in-vaporizing the oil, and subjecting the vapors to a purificator composed of a re fractory fibrous material and a finely-divided skunkdeco mposing substance, the temperature of which purificator is maintained bythe heated oil in distillation, substantially as de- 12. Theimprovement' in the art of removing skunk from Lima or similar petroleum, consisting in vaporizing the oil, and passing the vapors innumerous horizontally flowing streams over layers of a purificator which'is composed of a refractory fibrous material and a finely-divided skunk decomposing substance adherent theretoand whose temperature is maintained by means of the heated oil in distillation, substantially as described. In testimony whereof I aflix my signature in presence of two witnesses.

HERMAN FRASCH. VVitnesse's:

F. W. LOTHMAN, G. W. Bounmor.

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