US378246A - Herman erasch - Google Patents

Description

. full, clear, and exact description.

- oil-requires a different treatment from the-ortribute'd mainly to the existence in the oil of .taining' compounds are essentially different centum, (i 0f1%,) mostly in chemical combibut a further distinction may be found in the .(litharge,) or may be converted by ordinary obtained from the Pennsylvania oil districts,)

been subjected to the action of sulphuric acid UN TE STATES PATENT ()FFICE... I

HERMAN rR'AscH, orronnon, ONTARIO, CANADA." 7

L'REIFIININ'VG CANADIAN AN-D SIMILAR PETROLEUM-OILS.-

SPECIPICATION forming part of LettersPatent'No. 378,246. dated February 21, 1888.

Application filed February 21,1887.

To all whom it may concern:

Be it known that I, HERMAN FRASCH, a citizen of the United States, residing at London, in the Province of Ontario, Canada, have invented certain new and useful Improvements in Refining Canadian and Similar Petroleum- ,Oils, of which the followingspecification is a This invention. relates to the treatment of Canadian and similar petroleu-msuch, for ex-. ample, as that found at Lima, in Ohio. ,This

dinary Americanoil, because of its penetrating disagreeable odor when burned and of its giving ofi products which smoke and cloud the lamp-chimneys. These bad qualities are atsnlphur, which is converted on burning into sulphuric acid, that collects on the chimney and causes nitrogen products-such as am- The sulphur is present in these oils in considerable proportions-say upward of one-half of one per nation-end some, at least, of thesulphur-confrom the sulphur compounds which occur in other oils'as, for example, in coal or shale oils-and are retained with-greattenacity. The large proportion of sulphur will generally distinguish these from other petroleum-oils;

nature of the sulphur-containing bodiesnamely, that they or some of them give the oils the property of dissolving oxide of lead,

distillation, for example, into bodies which impart that property to the oils. To deprive these oils of the sulphur and other injurious compounds, and thus make them burn as well as American oil, (that is, oil such as generally is the object of the present invention.

"Heretofore it has been customary in Cana-. dian refineries (and the same treatment has been employed in parts of the United States) to talgethe burning oil distillate which has and washed with water and to treat the same with a solution of plumbate of sodaiin order Serial No. 228,403. (No specimens.)

to deodorize it, and then to add sulphur in powder in order to restore the color which. the plumbate solution has turned to a yellow or. brown, and cause the-quick precipitation of the lead, leaving the oil above it white and clear. The solution of soda settles to thebottorn.- Before adding the sulphur it is customary to remove asmallportion of the oil under treatment, and after sulphuring down this portion (that is, after throwing down the lead sulphide byaddition of sulphur) to test it with fresh plumbate solution. If it remains unchanged, it is considered that suflicient of the plumbate solution has been added to the main body of ;oil, and the workman then. adds the sulphur to it; but if the small portion tested is changed more of the plumbate solution is added to the main'body until a removed portion will stand the test. old deodorizing process are twofold -first, an

The objections to this excess of sulphur is liable to be added in the second stage,which is injurious tothe oil, and,

secondly, the treatment. is not thorough, for

if the oilbedistilled after it has been so treated as to stand the test, with or without sulphur ing down, the distillate will not stand the test,

but will be discolored by the addition of the plumbate-of-soda solution. Only the moreeasily acted upon portion of the sulphur compounds is therefore removed by this process.

I have discovered that by distilling theoil with suitable metallic oxides or suit-able compounds of such oxides dissolved in or mixed with the oil not only may the rapid separation be effected of those sulphur compounds which the old plumb'ate of soda and sulphuring-down process would remove, but if the supply of oxide or its compound be kept up during distillation, by the use of a sufficiently large proportion of the oxide or compound at the start or by additions during the operation, the removal may be effected of allxor. of practically all the sulphur compounds, even those which wouldremain in the oil after. the old treatment, so that this distillate may be redistilled and still stand the plumbate-o f-soda test. other words, there is generally presentin the oil a certain amount of sulphur in such chemical combination that it will be bound by the lead of the plumbate solution and an additional portion which the latter, although inexcess, will not act upon; but the oxide or its compound in my improved process may be effectively employed in excess of the quantity requisite to-bind the firstnamed portion of sulphur, and such excess may be sufficient to bind the whole of the sulphur present.

When the oxide or compound is used in the still insolid state, it is preferably in as fine a powder as practicable in order to bring about a more ready diffusion, and it is also advantageous to use in admixture therewith a substance specifically lighter, such as plaster; but it is not necessary to employ it. The admixture of the oxide or compound with the oil is or may be secured by suitableagitating means, such as steam-jets or a mechanical stirrer or stirrers. The introduction of the purifying agents during the'distillation may be efl'ected in large or small quantities by' injecting the same in solution or in solid form into. the va-' por-space of the still or into the-oil direct, or other suitable means of introducing it could be employed.

give up their oxygen with comparative readiness, so that they may serve as oxidating agent's toward the sulphur compounds, and are especially those of metals which form sulphides convertible into oxides by roasting and oxidation. The oxides oflead, bismuth, cadmium,

mercury,- copper, and silver are wellsuited to the purpose, also the binoxide pf manganes except for the difficulty of revivification; but

,the ferric, stannic, and antimonic oxides,

-. rated therewith. The vapors given oil from pounds are broken up and sulphur-is precipi tated as a sulphide or sulphides. As distillation and precipitation proceed, fresh quantities of the oxides can be taken up by the oil and should be supplied from the original charge or from material introduced during the operation, so as to keep the oil always satuthe oil or solution are or may be condensed in anyordinary or suitable way, and if the distillation be properly conducted the condensed liquid. ora distillate will stand the test with plumbate ofsoda throughout the operation.

,I'have also discovered that the distillates from the preceding operation, although standing theplumbateof-soda test, yet contain com-'- pounds products of that operation which impair somewhat thequality of the.oil,.and that these ingredients are. removed by treatment with sulphuric acid, washing with water, and neutralizing as customary in refining American petroleum;- but it is not necessary to treat the still as the result of the distillation with I I charge. Suitable oxides are those of metals .which the distillates with sulphuric acid in order to secure a useful result. Without such treat ment they are far superior to the oils heretofore produced from Canadian and similar petrolenm. 1

I have further discovered that a sulphide precipitate or deposit-such as accumulates in oxides, as before described, revivified by roasting and oxidation-can successfully be enrployed'in treating Canadian and. similaroils for the removalof the sulphur compounds contained therein. the still, it may be separated from the solid portion of the residuum by settling and decantation, or by straining, or partly by both;

or the liquid portion (all or partly) may be If any heavy oil remains in 8c distilled oft, in which last-mentioned-pase any 8 dissolved oxide is added to the deposit, whereas in other cases it is drawn off with the liquidand can be added in solution to a new Some of the liquid may adhere to the deposit; but its presence is not objectionable,

but rather advantageous, as assisting inmain tainingthe-temperature of the furnace. The

furnace such as employed in the most analogous metallurgical operations.

Crude petroleum maybe treated in the nanner described; but for local and industrial roasting and oxidation can be performed in a v reasons it is preferred to treat the burning oil 7 obtained by distilling the crude oil'in theYo'r-l dinary way. One reason .for the preference that the residuum is large in treating crude oil and the distillation of the said residuum is necessary, in order to recover the metallic oxide (or its compound) dissolved therein.

'In practically applying the treatment to the burning oilj distillate about teh td fifteen per centum (10% to of heavy oil is added thereto, with the oxide or its compound,'and

after the burning oil has been distilled off theheavy oil holding the metallic oxide or its co m pound in solution is added, together with the proper amount of additional oxide, to the next charge to be distilled,and so on. ,This 'procedure is of course not essential to the invention.

In order the better to enable those skilled in the art to practice the invention, the following detailed descrlptionris given, it being understood that the inventicn isnot restricted to thenumbers stated, nor toother details, but that these are given only by wayof example.

Anordinary three-hundred-barrel still is".

supplied with three 'hund red'barrels (300 bbls.) of oil, composed of, say,fifteen per centum I (15%) of heavy oil of from thirty-six to thirtynine degrees Baum' (36 to 39 B.,) and the remainder of burning oi ldistillate boiling at two hundred and twelve "degrees Fahrenheit (212 F.) or over. To this oil is addeda mix ture of sixteen hundredpounds (1,600 lbs.) of plnmbic oxide, three'thousand pounds (3,000 lbs.) of c'upric oxide, and three thousand pounds (3,0001bs.) of plaster'of-pariaall finely ground, mixed, and bolted. Plumbic and cu- 25 duced into the still .with another charge-of the burning oil distillate sufficient in energetically and reduce quickly and act very 7 without One of them could be used alone, or one pric oxides are used because they loss.

. or bothcould. be replaced by or used in connection with another agent or agents, as hereinbefore indicated, and the plastermight be omitted. As soon as the still is charged it is fired, and when the temperature reaches two hundred and twelve degree Fahrenheit (212 F.) or over, according tothe boiling-point of the'oil, steam is injected at the bottom,so as to agitate and mix together the contents of the still; or if a mechanical agitator is employed, it is set in operation as soon as the firing is commenced. The-agitation is continued during the whole run. When the burning oil has been distilled'off and only the heavy oilr'ei the liqui 20 eledintoa maintained, say,

furnace a portion at a time mains,the stillis shut down, and when cool all on and the remainder or solid portion is shovstrai'ner or bed" having a canvasl'inedfalse bottom, under which a vacuum is by a steam-jet,in order to ex- Theliquid filtered or strained drawn from the still,-is intr0- pedite draining. 'ofl,and also that quantity to make up three hundred barrels, (300 bbls.,) the quantities of oxide and plaster before mentioned are then added, and the burning oil is distilled on", as before. The same round of operation is then repeated. The'powder remaining on the straineror canvas, when freed as much as practicable from oil,is thrown into the front part of a roastingand 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 efl'ect the'revivification at one operation. As" each fresh portion is added the portions previously introduced are'pushed' back until thewhole charge has been transportion of the residuum is drawn compounds whose ,The mass becomes red roasted.

ferred to the furnace. hot and is thoroughly sure a perfect and quick roasting. It is stirred until below red heat, and is then discharged, from the furnace, r'eground,and bolted, and is ready to be added to a fresh charge of oil to be distilled. It is evident that parts .of the inventionmay be used separately, as well as that modifications can be made in details'without departing from the spirit of the same.

The fine division.of the powder audits composition in- '55 The proportion of oxides should correspond to the sulphur in the oil, which variesin 'oils even from the same locality. Those given are f. ample to treat oil containing one per centum the property of dissolving leadoxide by distil- I ling the same withthe oxidating oxides, especially the roasted and oxidated residues of pre- -vious operations, mixed with or dissolvedinth'e oil under treatmen't,and washing the distillate from such operation with sulphuric acid, substantially as described.

. r 80 In testimony whereof I have signed this specification in the presence of two witnesses.

. v HERMAN FRASCH. Witnesses:

WM; -FLocK,-. J. H. FLocK.