US487119A - Refining canadian or similar petroleum-oils - Google Patents

Description

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H. FRASGH. I

REFINING CANADIAN 0R SIMILAR PETROLEUM OILS.

Patented Nov. 29, 1892.

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OR LAB PETROL Patented FIGJII- (No Model.) I

. REFINING CANADIAN No. 487,119.

' UNITED STATES HERMAN mason, or LONDON, o

ANADA, nsstenon To TEE-"SOLAR REFINING COMPANY, OF. OHIO; BEFINING CANADIAN10R:SlMlLARlPET RCLEUM-OILS,

5 .srncmcninolv forming part of Letters Patent No.4 87,1;l9, dated November 29,1892.

Application filed February 15, 1888. Serial messiah (no specimens.) 1

- To allwltom it maly concern in the Province of Ontario, Canada, have in- Be it known that I, HERMAN FRASCH, a citi;

zen of-the United States, residing at London,

vented certain new and useful Improvements in the Process of Refining Canadian and Similar Petroleum-Oils, of which the following Canadian and a similar petroleum'such,for

.'example, as that found at Lima, in Ohio. This oil requires a difierenttreatment from the} ordinary American oil, because of the sulphur a present in these oils in considerable 'proportion, and some, at-least, of r the sulphur com-- specification is a full,- cleanand exact'descrip-- tion;

This'in-vention relates to the treatment of compounds which it contains and which give it its penetrating disagreeable odor and ren-, der it unfit for burning in lamps unless de-' prived of said compounds. The sulphur-is donsreaty, upwardof one-half of one per centum, (\f of 1%,) mostly in chemical combinapounds are essentially difier'ent from those whiclr occur in other oils and-are retained with great tenacity. T-hese peculiar sulphur,

compounds have received among the workers in the oils of this class the suggestive name of skunk. To deprive these oils of their peculiar'sulphur compounds'or skunk is the object of the present invention.

- The large proportionof sulphur will generallyd'istinguish Canadian andsimilar skunks bearing petroleum from'other oils; bill afur- -ther distinction may be found in the nature;

of the sulphurcontaining bodiesthereinl' They give to the oils the property of dissolving lead oxide, (litharga) So far as I am aware, no mineral oil, whether undistilled ordistillate other than Canadian orsimilar skunkbearing petroleum possesses this property of dissolving litharge. Ordinary petroleumcan be made to dissolve litharge by theaddition erty-of dissolving lead oxide. On distillation,

odor reappears, and-the oil; will again disfwill removepractically all the sulphurfexist invention there yet remainsin'said petroleum phur .in such form or;forms -thata repeated fails. toeliminate it or materially to reduce 'spect to the sulphur bodies-thereimsaid bodies. giving-to theskunk-bearing oil peculiar properties, as' hereinbefore mentioned, and being not removable by the refining means in common use, which do remove, the sulphur from -,American petroleum, while at the same time-means eflicient to remove skunkdo not take out sulphur bodies removable by said "refining; means-in common use on American oil,so' that theutility of certain reagents or.

mineral oils is no proofjof an ability to remove the skunk of Canadian and similar petroleum, nor does an ability to remove skunk constitute ing the place of the ordinarymeans of desulphurizing oil, r a

Heretofor'e it has'been customary in Canadian refineries (and the same treatment has been employed in parts of the United States) to take the burning-oil distillate which has been subjected to the action ot'sulphuric acid and washed with water and to treat the same witha solution of plumbate of soda in order to deodorize it,and then to add sulphur in powder in order to restore the color which the plumba'te solution has turned to a yellow or The malodor also reappears; on' b-urniug and f the lamp-chimneys become smoked. More over, while-the sulphur existing in. the'oil as skunk is not removed byjtreating the oil with sulphuric -acid and, alkali (which treatment application; of the skunk-removing; process proof of agiven process being capable of tak-v PATENT: OFFICE; 1

' however, of fmebirf rbln which". the lead has been precipitated, as-just described, the maling in Pennsylvania oil) it is also true that I after the removal of .the skunk from Canadian and similar petroleum by. the present- (now become sweet and incapable of 'dissolv- .ingrz-lead oxide even after redistilla'tion) 'sul;

its proportion, while it can: be-separatedal-- inostjentirely-bj treatment-with sulphuric acid. .Skunh bearing oil therefore is 'radically differfent from other 'mineral oils in r ef modes ofitreatmeut in desulphurizing other 1 brown and cause the precipitation of the lead,

leaving the oil above it white and clear. The solution of soda settles to the bottom. The objections to this old deodorizing process are twofold: First, an excess of sulphur is liable to be added in the second stage, which is injurious to the oil, and, secondly, the treat ment is not thonough, for it does not remove the sulphur compounds or skunk, but only renders the same inodorous and incapable of further uniting with the lead oxide of the plumbate solution. On distillation the sulphur compounds in the oil again become malodorous and the oilis discolored by the addition of the plumbate of soda solution.

In a priorapplicationfiled February 21 1887, and oflicially serially numbered '228,403, (on which Patent No. 378,246 was granted me February 21, 1888,) I have described apro' cess not open to these objections for refiningoil of the Canadian or Lima class by distilling the same with suitable oxides or compounds mixed with or dissolved in the oil under treatment. The present invention is, as it were, a supplement to or complement of that process. I have discovered that the refractory sulphur compounds or skunk of Canadianaud similar oils are decomposed by the metallic oxides or compounds without nec essarily having such an oxide or compound dissolved in or mixed with the oil in distillation by subjecting. the vapors after leaving the liquid oilto the action of a suitable liquid holdingin solution or solution'and suspension one or more of the said oxides or their com- .pbunds. The vapors may be brought into contact in any ordinary or suitable way with the liquid holding in solution or solution and suspension one or more-of the oxides or com-- pounds. The vapors may bubble through a body of the liquid, or they may pass through a shower or spray of the same, or they may come in contact with theliquid in both these or in other .ways.-

In my divisional application, Serial. No. 378,818, filed January 23, 1891,,1 have claimedv that process or improvement which consists generallyin subjecting the vapors of skunkcontaining petroleum after leaving the oil in distillation to the action of suitable oxides or compounds, for it is possible (although much less effective) to employ. oxides or compounds otherwise than in solution or solution and suspension in a suitable liquid, and there are advantages incident to the carrying on of the purification outside the oil in distillation which are not restricted to the use of a liquid, as above set forth, although very great and V important special advantages attend such use.

Suitable oxides are those of the more common heavy metals which give up their oxygen with comparative readiness,and are generally those of metals which form sulphides convertible into oxides by roasting and oxidation. The oxides of lead, bismuth, cadmium, mercury, copper, and silver are well suited to the purpose, also binoxide of manganese, except for the difliculty of'revivification; but the ferric, stannic, and antimonic oxides, cuprous oxide, and the oxides of nickel, cobalt, and zinc are less energetic and are more useful inconnection with those first mentioned, among which is to be included manganese binoxide, than when used alone. The lower oxides of manganese and the oxides of palladium and rhodium may be used. The oxides of manganese are more useful when employed in connection with lead oxide than when used alone. 7

Suitable compounds are the readily-decomposable oxygen compounds-such, for example, as the carbonates of metals-which give up their oxygen with comparative "readiness and.the oxygen salts in general of metals which are precipitated by hydrogen sulphides in acid solutions, such as the inanganates,

chromates,borates, sulphates, and the like of said metals,

Suitable liquids are those of an oily or resinous 'nature,aud especially those oily liquids compounds dissolved in or mixed with said liquid. The vapors from one still mayin fact be passed through the liquid in another still, in which. latter the oil under treatment is mixed with or holds in solution one or more suitable metallic oxides or compounds. In

plying and maintaining the oxide or compound in excessof the solvent capacity of said liquid, so asto have the solution saturated with ,undissolved oxide or compound mixed therewith in solid form, for the oxide is in the most active condition when dissolved, and as the reaction with the sulphur compounds or skunk takes place metal is precipitated from the solution in chemical combination or from which the vapors have been generated as in proceeding according to the specification of my aforesaid patent, is improved in respect to the rapidity with which it can be carried on by the use in connection with the metallic oxides or compounds of one or more of the acid hydrocarbons, such as oleic acid, stearic acid, margaric acid, colophonic v acid, (rosin,) and-other fatty or resinous acids. Theacid may be'mixed with the oxide or compound or be in chemical combination ate, oleate,or the like. The liquid condensed from the vapors which'havethoroughly been brought into contact with the oxide or compound, so as to} give it opportunity to. act

upon all the sulphur compounds or skunk, will stand the plumbate-of-soda test. I find,

-however, that the condensed liquid or distildate purified from skunk, although it will stand theplumbate-of-soda test, yet contains sulphur'compounds, which I believe to be pe-,

culiar to oil treated in this way and which impair the value of the oil by causing a chimney-de'posit when burned in a lamp. These products, like the. similar or identical ones from distilling the oil with the. purifying oxide or compound mixed' 'with or dissolved in" the-same, are essentially difierent from skunk .and are, as I-haveidiscovered, removable by treatment with sulphuric acid, washing with water, and neutralizing, as customary inre- 'fining American-petroleum.

The metallic sulphur compounds which are formed by thereaction with the sulp ht'1r-co1r,- taining impurities .Of-the; v'apors, as above set. forth, can be reviviiied by roasting and oxida tion and these revivified residues can be eIn-L ployed suceessfullyto treat new vapor-sot Qanadian. or Lima or similar skunk-bearing oil.

illustrationand example. I

In the drawings,-Figure:1is a sectional view:

of an oil still' andxpurifiersuitablefor,use in carrying the invention into efie'ctfi-F-ig. II is .a similar vie'w' of a -slightly-. mcdifiedform ofthe same apparatus,.and Fig. IIIis a-similar view of another form-of; apparatus.

Referringito Eigs'I and lLanordil-iarystill A is provided with'a colunin B, whichih'as baf fle-plates or trays and stirrer s,-a s common, or at'leas't known,'.in various chemical arts. In Fig. I the ,ba file-pl ates 2am in the fOI'm' :0f circular disks, which. are mounted horizontally on an upright central shaft 3,.and the baflie plates4 arein theform of rings fastened to the walls of the colu mnB and projectingiiiwa'rd between the disk plates 2. In Fig. 11 the trays 5 are fastened to the walls of thecolum-n, and.

the openings for the passage of the vapors are formed at the opposite sides of alternate trays; and the shaft 6 is provided with stirrers which 7 dip intothe trays. In both figuresthe top of the still A is conue'cted'by a vapor-pipe 7 with the' column B, and at the top of the latterithere.

is; a pipe '8 for conveying the ,purified vapors the column. .The still A' and the column B to the condenser. (Not shown). A pipe 9 leads from the base of the column B to the pump-C and a pipe 10 from -.the said pump 0 to the top 'of said column. The shafts 3 and 6 are rotated by bevel-gear, and the column .B, which restson a pillar 11, is heated by'the products of combustion from, the fire-chamber D under; the still on-their way to the chimney E. The column B should be of such size as to bring the vapors sutficientlyinto contact with the purifying material. If the still be. such as commonly used to' distill-a charge ofijone hundred barrels of'oil, the column B maybe, say, ten feet high andlfour feet in diameter, with the baflierplates or trays about six inches apart. p In operation the still ,is charged-with, say, one hundredbarrels of oil composed of, say, fifteen .pei' centumof heavy oil of from 36 to 398 Baum, and the remainder burning-oil distillate boiling at 2129f Fahrenheit orov'er.

The column is suppliedjwith, s y, five b'arrels of heavy impure Orskunk-bearing (Danadian or similar. oil mixed with, say,,one'baroxide, (litharge,).'onethousand poundsof'cm rel. of resin, -fi-ve hundred pounds of pln'rnbic' pricoxide,.-(black oxide,)j and one thousandpounds of plaster-'of-paris, the oxides and plaster being finely .g'round and bolted. 'Therosin and part of. the oxides dissolve in. theoil and therestot theoxidds' and plaster are kept in the bafile plates or trays, which trays'become -filled, and collects-in the bottom of the column suspension therein.- The oil,.with-the"matter. ,insolution and suspension therein, flows over B. After or before the oil is introduced the 'pum'p is'started which drawsfpfi through the pipe 9, the oil holding the oxide in solution and suspensionwherein"and returns. it to the top of,-th e column B through the-pipe 10-5 m.

shaft. 3 in the column 'is also rotated; The

uid and solids 'ofi onto the rings 4,'from which they descend to the next, disk by gravity, the flow of the'lijq-uids being 'sufiicienttofsweep.

away the solid particles; but, if desired, me-. 'chanical devices or scrapers could be em-.-

ployed to sweepior scrape thesurfaces'of the being charged'and the pump 0 and shaft 3 (or 6-). incol'ulnn B being started, the still A rotation of the disks 2,-- Fig I, throws th etliq r I 5 ratu s,wherein gases orvapors are to be thought 3 I cjles in suspension therein. The rotation of' in the bottom'of thecolumn B by means of andcolumn B are heated, the former to -evaporate the burning-oil therein and'thelatter to prevent'or diminish th'econdensation of .the vapors from the still. The vapors pass through the pipe 7 into 'the lower part of column Bf.

through which they then; pass upward, and are in their'passage brought into intimate con.-

tact with the liquid holding the oxides in solution and suspension, said liquid, with the oxides, flowing in the opposite direction over the battle-plates or trays and falling from one to the other through the rising vapors. The vapors escape by the pipe 8 to the condenser. The passage of the vapors through or over the liquid enables the oxides to act on the skunk in said vapors with the formation of metallic sulphur compounds which remain in the liquid and certain new bodies which pass off with the vapors. A constant stream of the oil having the oxides dissolved and suspended therein is introduced at the top of the column B and drawn ed at the base. The liquid drawn oii is returned to the column, the whole or a portion of the precipitated or solid matter in suspension being removed and replaced by fresh oxides at each round or from time to time. As the metal of the oxides in solution .combines with the sulphur of the skunk and.

becomes insoluble fresh oxide enters the solution, the same being supplied from the mat- V ter in suspension. The still is or may be supdensed vapors must be taken care of eitherby returning them to the still or otherwise. If solid matter is allowed, in the still either by entering in that state from the column B or by precipitation in the still, the latter should be provided with an agitator to keep it from settling.

' The plumbic or the cupric oxide could .be used alone-say thirty-three hundred pounds of plumbic oxide or twelve hundred pounds of cupric oxide,-or one or both could be re placed by or used in connection with another or others of the specified agents. The plaster and therosin may be omitted.

It is not necessary to use heavy oil in the puritier'column, although such oil is preferable to a lighter petroleum, because it does not volatilize in the column; nor need the oil inthe said purifier-column. contain the sulphur compounds which enable it to dissolve the oxides, for the solubility of the oxides might be seen red by other means-such as the use of a fat acid-or the oxides, if simplyheld in suspension in an oily menstrum not originally a solvent of the oxides, willbecomedissolved by reason of theskunk brought over by the vapors from the still; nor need petroleum be used at all, as rosin alone would answer.

According to another plan of working (see Fig. III) the still A is provided inside with a large pipe E, which communicates with the interior of the still through the opening 15 and also with a small column G, such as used in rectifying alcohol on top of the still, and with a small vessel or receiver 16 inside the still. A steam-injector or steam-jet aspirator and compressor H sucks the vapors from the upper part of the still A and forces them through the pipe F into the bottom of the column G. The injector H also forces into the pipe F and among the vapors therein the purifying oxide or compound finely divided and dissolved in or mixed with an oilyliquid. As shown, there is a reservoir K, provided with a stirrer 17, from which the injector H draws a supply of oxide or compound in suspension or in solution and suspension in the oily liquid. More or less of the oxide is forced with the vapors into the column. What does not so pass is carried into the small vessel or receiver 16, the object of which is to keep the sediment from the bottom of the still. This material could be allowed to run into the still; but in that case the latter should have an agitator, or it could be discharged outside of the still to be returned or otherwise disposed of. The column G has an overflow at thebottom, which discharges into the receiver 16. The oil or condensed vapor in this receiver is volatilized again and passes in vapor form into the pipe F and then into the column G. The large pipe F may have an opening into the vaporspace at each end, so as to circulate the vapors through the pipe as well as force them into the column G. The steam-jet to force the vapors could be used in the arrangements described with reference to Figs. I and II. Other modes of bringing the vapors into contact with the purifying agents have been indicated in the first part of this specification.

The larger the proportion of skunk in the oil the more thoroughly should the vapors be brought into contact with the purifying agents, and if the process is carried on by batches-that is, without a constant renewal of the oxide or compoundcare should be taken to have the amount of purifying agent larger than necessary to decompose all the skunk. The weight of oxides given would be ample for one hundred barrels of oil containing about one-half of one per centum of sulphur.

The vapors from the purifying apparatus are received in a condenser (not shown) andthe condensed liquid is washed with sulpliuric acid, or it may be used without such washing.

The solid sulphur-containing residue from the above operation or from an analogous operation is roasted and oxidated and after grinding and bolting is used like fresh oxide.

In order to revivify the purifying agent or agents, the solid residue is or ordinarily would be so arated by straining or otherwise from the o'ly or resinous liquid with which it is mixed'and is then thrown into the front part of a roastingrfurnace a portion ata time and ignited. The oil adhering, in connection with the sulphur and metal, furnishes all the heat necessary for roasting. The air will supply the oxygen, so as to effect the revivification at one operation. As each fresh portion is added, the portions previously introduced are transferred to the furnace.

pushed back until the,whole charge has been The mass becomes red-hot and is-thoroughly roasted and oxidated. The due division of the powder and its composition insure a perfect and quick roasting. It is stirred until below'red heat and is. then discharged to be reground for use again. The oily or resinous liquid is used again with fresh purifying agents.

I do not claim herein the apparatus described. It forms the subject of my application, Serial No. 289,746, filed November 1, 1888 nor doI claimherein the revivification of the residue of the revivified residues, as such matter forms the subject of my application, Serial No;12 ,84,830, filed September 7, 1888; but the use-of the revivified residues, as herein described, is included in the present invention. g

The expression vaporizing the oil and subjectingthe sameto the action as employed in the second, fourth, and-fifth clauses of claims following is intended to apply' as well to the action which occurs within the oil when the latteris distilled with the purifying agent dissolved therein or mixed therewith as to an action on the oil vapors after they have been given on: from the body of the liquid oil undergoing distillation.

The advantages which are secured by the carrying on of the process of purification of the vapors of distillation outside the oil in or from which .the same have been generated are not confined to the use of a liquid solvent,

but toja greater or less degree extend to the use of the oxides in adry state, and thisgeneral feature of my invention-namely, the carrying on of the purification outside theliquid in ,or from which the vapors have been generated-is made the subject of. my divisional application, Serial No. 378,818, filed January 23, 1891.

I claim herein as my invention or discovery 1. The process of removing the sulphur compound termed skunk from Canadian and similaripetroleum, which consists in vaporizing the oil and subjecting the vapors after they are given on? from thebody of the oil to the action of' an oily or resinous liquid holding in solutioh or solution and'suspension one or more metallic oxides soluble in said oil, including the decomposable compounds of such oxides, and condensing such purified vapors, substantially as described.

2. The process of removing the sulphur compound termed skunk from Canadian and similar petroleum, which consists .in vaporizing the oil and subjecting the same to the action of a solution in an oily or resinous liquid composed of one or more metallic oxides soluble in said oil, including the decomposable compounds of such oxides, and maintaining an excess of the soluble but as yet undissolved purifying agent in suspension in said solution, whereby the said liquid is kept saturated, substantially as described.

3. The process of removing the sulphur compound termed skunk from Canadian and similar petroleum, which consists in vaporizing the oil, subjecting the vapors after they are given off from the body of the oil-to the action of films, showers, or sprays of an oily or resinous liquid holding in solution or solution'and suspension one or more metallic oxides soluble in said oil, including the decomposable compounds of such oxides, and condensing such purified vapors, substantially as described.

4. The process of removing the sulphur compoundtermed skunk from Canadian and similar petroleum, which consists in vaporizing the oil and subjecting the same to the action of purifying material, composed of or containing one or more of the metallic oxides soluble in said oil,including their decomposable compounds, and one or more fatty or resinous acids, such as oleic, stearic, margaric, colophonic acids, substantially as described.

5. The process of removing the sulphur compound termed skunk from Canadian and similar petroleum, wh'ich consists in va-- porizing the oil and subjectingthe vapors to the action of a metallic 'oleate, colophonate,

-or other metallic salt of a fatty or resinous acid, substantially as described.

- 6. The process *of removing the sulphur compound termed skunk from Canadian and similar petroleum, which consists in vaporizing the oil and subjecting the vapors after they are given off from the body of the oil to the-action of an oily or resinous liquid containing said sulphur compound termed ,fskunk, and one or more metallic oxides soluble in skunk-bearing oil, including the decomposable compounds of such oxides, and condensing such purified vapors,substan tially as described. i

7: Theprocess of removing the sulphur compound termed skunk from Canadian andsimilar petroleum, which consists in vaporizing the oil and subjecting the vapors after they are given off from the body of the oil to the action of an oily or resinous liquid holding in solution or solution and suspension one or more metallic oxides soluble in said oil, including their decomposable compounds, condensing such purified vapors, and washing the condensed liquid with sulphuric acid, substantially as described.

In testimony whereof I have signed this specification in the presence of two witnesses.

' HERMAN FRASCH.

Witnesses:

J. W. VAN DYKE, W. B. RICHIE.

' It is hereby certified that in Letters Patent No. 487,119 granted November 29, 1892, upon the application of Herman Frasch, of London, Oanada, for an improvement in Refining Canadian or Similar Petroleum Oils, an error appears in the printed specification requiring correction as follows In line 61, page 5, the word composed should be stricken out; and that the Letters Patent should be read with this correction therein that the same may conform to the record of l the case in the Patent Office. I

Signed, oountersigned, and sealed this 24th day of January, 1893.

[SEAL] CYRUS BUSSEY,

I Assistant Secretary of the Interior, Oountersigned W; E, SIMONDS,

Commissioner of Patents.

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