US968692A

US968692A - Refining petroleum.

Info

Publication number: US968692A
Application number: US17032703A
Authority: US
Inventors: Clarence I Robinson
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1903-08-21
Filing date: 1903-08-21
Publication date: 1910-08-30
Anticipated expiration: 1927-08-30

Description

`LIPLIIU'I'IOI' FILED AUG. 21, 1903.

Patented Aug. 30,1910.

"SEN uwh..

,t my e Nga I. .ji/enivre' v Ima AUNITED sTATEs :PATENT onrioE.

CLARENCE I. ROBINSON, OF WEST NEW BRIGHTON, NEW YORK, ASSIGNOR TO STAND- ARD OIL COMPANY, 0F BAYONNE, NEW JERSEY, A CORPORATION 0F NEW J ERSEY.

REFTNING PETROLEUM.

'specification of Letters Patent. v Patented Aug. 30, 1910.

Application filed August 21, 1908. Serial No. 170,327.

To all whom it 'may con/ccm:

Be it known that I, CLARENCE I. ROBIN- soN, a citizen of the United States, residing at West New Brighton, in the county of Richmond and State of New ,Yorin Jhave invented new and useful Improvements in Refining Petroleum, of which the following is a specification.

This invention relates more particularly to the rening of such petroleum (as is obtained from the oil fields in the State of Texas, near the town of Beaumont, in Jefe ferson county, the object of the refining being to obtain burning oil (kerosene). Said petroleum is herein referred to as Beaumont oil, or Beaumont petroleum, for convenience of reference. These designations are 4each intended to include oil of the same o-r-substantially similar character wherever found or however obtained. They. include petroleum distillates having such a character, as well as crude and other undistilled petroleum. Y

The ordinary method of refining petroleum has heretofore been to distil the crude petroleum, and to collect 'by itself the fraction which d istils over within the temperature limits of burning oil (kerosene), say, between about 250 F. and 600o F., more or less; the -precise points at 'which the collection ofthe burning oil (kerosene) distillate is begun and ended being varied according .to the grade of oil desired; and when as much distillate proper for burning oil (kerosene) has been collected as can be secured with ordinary distillation, it is a common practice to subject the residue to a species of 'destructive distillation termed cracking, by which is'obtained a further quantity. of hydrocarbons with boiling points w'thin the above mentioned temperature limits and" capable of'being used for burning oil\ (kerosene). The dist-illates from the two distillations (separately or in admixture, according to the grade nfoil to be made) are then treated by agitating the same with ordinary concentrated sulfuric acid (acid of 66o Baum' is commonly used, for the purposeg), allowing to settle and., drawing off the acid sludge (which sinks),

the oil (which remains in the agitator):be ing then washed with water repeatedly and afterward with lan aqueous solution 'of alkali, in order to remove all acid bodies from the oil. The so-treated oil constitutes the ordinary commercial refined petroleum (otherwise burningl oil or kerosene) of the 'United States, provided the petroleum refined is that from the Pennsylvania or the Lima, Ohio, oil fields, only in the case of thei Lima, Ohio, oil a special purification is resorted to, in order to eliminate the Inal- If Beaumont oil isdistilled, with or without cracking, and the burning oil distillate given the sulfuric acid treatment (as stated above), the resulting product, when burned Ain the ordinary petroleum (kerosene) lamps, will smoke badly; and this smokiness cannot be cured by treatment with sulfuric acid (66 13.), howeverlarge a proportion of such acid may be employed. I have discovered that it can be cured by the aid of sulfuric acid containing aboutor above 98' per cent. sulfuric monohydrate (I-I2SO4), hereinafter referred to as 98% sulfuric acid, or more shortly as 98% acid. This acid, as I believeI am the first to discover, is capable of attacking, smoky hydrocarbons of Beaumont oil not acted on by the ordinaryv concentrated acid of 66 B.; .which latter ordi-4 narily,A contains and for the purposes of this specification can be taken to contain from .925% to 93% sulfuric monohydrate. 'When the burning oil fractionv is agitated with such 98% acid, the latter v,unites with the smoky hydrocarbons to form sulfo bodies which settle out in the sludge, after the xagitation is over.

A non-smoking oil can be obtained by simply collecting the burning oil fraction in the customary manner and then subjecting it to sufiicient 98% acid applied in successive portions until a non-smoking oil is obtained after washing and neutralizing..

volume of acid as of oil) and would be' burning oil and 98% acid, respectively.

I have discovered that a large saving in 'the 98% acid canl'be effected by separating burnin subjec'tlng the heavier portion thereof by itself to said 98% acid, the llghter portion the lighter from the-heavier portion of the l o il fraction of Beaumont oil'\and 105.

odorous sulfur compounds peculiar to Lima l But to do this requires an immoderate` amount of acid (namely, about as large a 'practically prohibitive at present prices'of 100 being advantageously treated with ordinary f as to carry over the main vconcentrated sulfuric acid and not withv 98%:

acid. After such treatment, said lighterA portion would best be distilled, a residue of treated oil heilig left in the still. Were said lighter and heavier portions to 'be subjected together to the 98% acid, al material part of the acid used to produce a -nonsmoking product Alltherefrom would be expended on smoky and non-smoking hydrocarbons of a portion of the oil, which can (as just'statcd) advanta ously be refined without it. Burning oiedistillate Yfrom Beaumont petroleum as'it .is received from the condenser is attacked'fhy 98% acidv beforeits content of smoky hydrocarbons becomes so great as to require a treatment with 98% acid. -I have further discovered that an additional saving of 98% acid c an be effected bycollecting the heavier port1on of the distillate with reference toits capaclty for treatment-@Vith a moderateamount of 98% acid (say, about twol less, of such. acid t0 eac treated) and after subjecting the so collected oil to said acid 4in such moderate amount distillng the so treated'oil 'insuch manner ortion thereof while leaving a residue'of t Ie same `in the still. By-A such partial distillation the amount of 98%- acid can be reduced in much greaterratio thai the yield of non-smoking oil is reduced by the residuum left in the ounds, more or still; and by `combining suchafter treatment with the specified collection of the oil to -be treated, 'the major-portion Vofthe burning oil' fraction can be rendered non-smoking lb the aid of s aid moderate amount of aci And itA may notin all cases be necessary or' expedient, in usin this further discovery/to apply the 98%' so ely to the heavier vportion of the distillate; for if the presence-in the treated. oil of all orpatfof thelighter end of the burning oil fraction .would not prevent a satisfactory treatment' of the same with' a moderate amountv Vof acid, the preliminary removal of said lighter portioncould be dispensed Withlff The points at Whichythe different cuts (or v changes of distillatefrecevers) are. to be,

madein any jdistillationcan be ascertained by a preliminary assay, Hereinafter figures obtained in my experience 'will be glven;

but it Will be'understood that they are Given by Way of illustration and example, an not as excluding a Working With other figures.

The burning oil distillate canbe obtained from the crude oil with or without cracking; but most advantageously 4cracking is resorted to, .in order to increase the yield;

and, when cracking is employed, it is. considered an advantage and special improvemeut to collect the burning" oiP li ht endvv (which does not require treatment Ywith 98% acid) in two distillation's,

namely, first, that in which the crude oil.' is distilled; and,

Way toprovoke cracking, after the cracking But, although the burning oil distillate, thus gallon of oil l haveA described and claimed-l inutilizing Beaumont petroleumby which I 'convert the naturally present sulfur therein 105 into 98% acid thesulfur in the aci 'temperature' I (say,

second, that in which the cracked oil distillate is redistilled for burning oil distillate. I, therefore, 'most advantageously (a) distil the crude oil with collection of the burning oil light end so long as it can be utilized without treatment with 98% acid; (b) continue the distillation as long as distillation can safely be carried on and to conduct it in the known or in any suitable temperature is reached, and collecting all the distillatev Without distinction; distil the last mentioned distillate and collect apart the burning oil light end thereof so long as it can be utilized Without treatment With 98% acid, and (d) continue the distillation,-With collection of the heavier ortion ofthe burning oil fraction so ong as' it can be satisfactorily treated for smokikness. with a moderate amount of 98% acid.

obtained without the light end, can be re-L fined with a moderate amount of 98% acid, :such amount is in excess of thel small quan'- tities of 66 B. acid customarily employed in theordinary sulfuric acid treatment; and it, therefore, becomes a matter of so much"A the` greater importance to obtain the'requisite supply of 98% acid economically.

As one means of effecting such economy I- i avail myseLf'of sulfur in the petroleum to i vbe refined as material for the productionof 98% acid. fort-he refining operation.

`In a divisional application No. 363,712, f filed March 21, 1907,- asacontinuation of 100 this present application and made vconsequenceof'ofiicial requirement of division, I improvements into sulfuric acid; While at the same time I obtain utilizable oils. Qombinations of operations composing these improvements with other operations herein specified form part'of the invention to be protected hereby. 11o i Another means of which I avail myself,

.in order to obtainA the necessary amount of v98% acid at acost which admits of its profitable use, consists in converting again I Sludges .115 from treating Beaumont burning-oil disillate with such acid. Most advantageous'y, the said sludge is heated to an ap"v ropriate fromlabouty 25,0814". to about 60W-"FJ, and thegas thereby evolved 120 is ysubjected to oxidation for the conversion of sulfur dioxidinto sulfuric acid. Before entering the sulfuric-acid-m'aking apparatus (either lead chamber or contact appa; rat-us, for example, gas issubjected to such preparatory operations as may be considered necessaryor desirable.- The roduct of the lead chambers is c oncentrx-itedp to 98% acid in any known or desired Way; that from the contact appa- 130 as may be preferred) the ratus, if not. obtained as98% acid, is converted into the same in any known or desired way.

I have devised certain improvements in utilizing acid sludge from refining petroleum, hereinafter set forth, which I have described and claimed in-my application No. 170,326 of even date herewith, and the .combination of which with other operations for refining Beaumont petroleum is claimed herein.

In the preceding description, whenvreference has been made to the use of sulfuric acid of about .or above 98% monohydrate (HSOQ it will naturally have been understood that the residue, amounting to about 2% or less, is mainly (if not wholly) water. It is possible, however, to have a sulfuric acid of about or above 98% monohydrate (HQSOQ in which the residue of about 2% or less should be mainly (if not wholly) sulfuric anhydrid (S05), instead of water; and such acid would .perform the functions of the water-holding 98% acid; although at the present time it would be dearer. This latter would be strictly a fuming acid; since it would contain sulfuric anhydrid; but the Y proportion of this would be so much less than in ordinary fuming acid (which contains about 10%, if'not more, of sulfuric anhydrid) as materially to affect the cost; and, in view of the fact that I am, as I believe, the first to discover that monohydrated sulfuric acidwill attack the smoky hydrocarbons of Beaumont petroleum and the first to suggest the application thereto of the weak fuming sulfuric acid aforesaid, I believe I am entitled to claim (as I do) the.

application as well of the fuming as of the non-fuming sulfuric acid ofabout or above' 98% 'monohydrate; and bot-h are included in the expression 98% acid. Moreover, the smoky. hydrocarbons of Beaumont oil attacked by 98% acid and not by acid of G60 B. are attacked by fuming sulfuric acid containing less than about 98% monohyldrate (herein referred to as stronger fuming acid and also by sulfuric anhydrid itself (which is also to be understood as covy ered by the expression stronger fuming acid More or less ofthe above described procedure is new and capable of useful application in connection with a treatment of Beaumont burning oil distillate with stronger fuming acid. Such matters are included also in the invention. For example, by the preliminary separation of the burning oil light end from the rest of the burning oil lfraction, I vcan avoid loss of the stronger fuming acid (as well as of good burning oil) which would resultv fromtreating the burning oil distillate as ordinarily collected with such acid, in consequence of the acid combining Withnon-smoking hydrocarbons. Also by separating from the rest.

- be necessary the of the burning oil fraction the portion (consisting as I have discovered of more than half) which can be refined by a moderate amount of 98% sulfuric ac-id, I avoid another loss of the stronger fuming acid which would result from treating burning oil distilllate as ordinarily collected with such acid; for the oil which can be refined by a moderate amount of 98% acid-can be refined by a moderate amount of anhydrid or of fuming acid of less than about 98% monohydrate. In fact, I may use this fuming acid or the anhydrid in place of 98% acid 1n the assay to determine the portion of the burning oil which can be refined with either a moderate amount of 98% acid or a moderate amount of fuming acid of less than about 98% monohydrate or of the anhydrid.

Again, by distilling oil afterit has been treated with fuming acid of less than about 98% monohydrate or with the anhydrid, leaving a proper portion behind in the still, I can effect a material .saving of the acid to be used as compared with that which'would to treat the oil with a single distillation. The said fuming acid, also the anhydrid, `as Well as 98% acid, seems to effect a change in smoky hydrocarbons which, although it does not cause them to settle out with the acid nor to be removed bythe subsequent washing, does cause them to stay in the still in the subsequent incomplete distillation. Still further, I can convert the sulfur in the Beaumont crude oil and in thev acid sludge into 98% acid (Whether fuming `or aqueous) or into fuming acid of less than about 98% monohydrate, or into anhydrid, and can utilize said sulfur in any of these forms in refining Beaumont burning oil distillate. The 0btained acid (or anhydrid) could be used or sold for any purpose to which it might be applicable; and, if desired, said. sulfur could beconverted into 660 B. acid or, in fact, into 'acid of any desired strength for sale or use, as might bepreferred; only the utilization of said sulfur, after conversion 'into proper acid, for removing smoky hydrocarbons from Beaumont petroleum is itselfI an important part of t-he present vinvention, which includes the new improvements herein set forth as well severally as (any two or more) collectively.

There are smoky attacked by fuming or anhydrous sulfuric `acid and not by'98% acid (either aqueous or fuming) the former can be resorted to in place of or in addition to the 98% acid when consideredrnecessary or desirable. It is not essential, although most advantageous, to obtain non-smoking oil directly by the described procedure, as the product could be subjected to further operations or could be mixed with non-smoking oil-in such manner as lto obtain a non-smoking mixture.

hydrocarbons which are` '.gous to Beaumont oil burning oil fraction; amenable to treatmentwith 98%, fuming, or anhydrous sulfuric acid, with or without having sulfur so present in the oil as to be convertible into hydrogen sulfate on exposure to proper temperature (to wit, to about or below 500 The improvements of the present invention'y extend tothe treatment of petroleum analov in connection gous to Beaumont oil; that is to say, it Would be within the invention to subject to the above described operations for refining Beaumont oil or to portion of said operations any petroleum possessing a smoky burning` oil fraction amenable to the specied acid with or without recovery of the sulfur in the acid sludge obtained as by-product, and with or without utilization of sulfur inthe oil.-

In the preceding description, the reference to its use-in the prior state of the art, ordinary concentrated sulfuric acid (herein shortly refered to as 66 4has been mentioned as a refining agent only with the lighter end of the burning oil fraction, it being applied thereto prior to an incomplete distillation thereof. A certain amount of 66 B. acid (say, 6 to 8.1bs. of acid, more or less, to the barrel of oil) can, however,I be applied to said heavier portion preliminary to a further treatment of the same with other acid, and thereby a diminution be effected of the lamount of such other acid necessary to a yield of given quantity and quality. The acid intermediate 66 B. and 98% acids (herein shortly referred to' as intermediate acid can similarly be used, and, when so used, itcan replace a still larger part of 98%l acid, or of the stronger fumin acid, 'if this should be used. Moreover, iit should be desired tainable with avoidance stronger fuming acid, intermediate could be used as a basis to'select a burning oil cut Afor treatment with a'. moderate amount of such intermediate acid, with or without 66 B. acid, and with or without a subsequent incomplete distillation in either case. These apphcations of 66 B. and intermediate acids are included in the invention, 'as .is also the intermediate acid to petroleum.

he invention also consists in a new lor improved l. oil which, in addition to: having a refractive index which is general application of Beaumont or analogous and; 55o@ F.

any new and useful.

apart from the following particulars B. acid or any reason to obtain the best yield ob-f f of both 98% and acid.

' the portions distilling over in 25 ten,'.'

twenty, thirty, forty or more ten-thousandths less than that of oil of like boiling point obtained from Beaumont petroleum by the, ordinary procedure of fractionally distilling with or without cracking and then treatin the burning late wlth 66 index may be, suliciently below .1.4600 for the oil to be non-smoking. whenburned in ordinary kerosene lam s; (b) possessing-mobility` proper for clim ing a" lamp wick; (c) distilling, mainly if not wholly, within the temperature limits ofburning'oil (kerosene), to wit, between about 250 F. and 600 F. more or less; (d) yielding between 400 F. on a test distillation within temperature intervals of 25 F. portions of distillate, of which most, if not all, are, re-

spectively, of greater gravity by two, three,-

four, five or more degrees Baume than the portions similarly yielded in the same teni.- perature intervals by Pennsylvania petrooil (kerosene) distilv B. sulfuric acid, and which` and most advantageously is, y

leum and of which the, portionsdistilling i over between 400 F. and 500 F.'may, and most advantageously do, average notl lighter t-han 40 B., say, about 35 B., more or`less,

for a straight'Beaumont product, is further' distinguished in some one/or more or all of as hereinafter set forth, namely: (e) the oil exhibits in the portions distilling over in 25 F. intervals between 400 F. and 500 lF. or 550 F. bromin-absvorbing capacities which are on the average lless by one, two,l three, four vor I more per cent. than those of the. ortions distilling over in 25 F. intervals etween 300 F. and 400 F.; (f) the'bromin-absorbing capacities of the portions' distilling over in 25 F.- intervals betweenv 400 Ffand 500 vFf-or 550 F. "iverage less than six per cent., say, about one per ce1:1t.,'n1orev or less, for a 'straight Beaumont' product; (g) the refractive indexes of the portions distilling.

over in 25- F. intervals between 400F. and 500 -F. average not more than 1.4620 (say, 1.4600) when the densities ofthe same portions average 35 B. with an allowance at the rateof plus 20. ten-thousandths for each degree below or minus l'ten-thousandths for each degree above 35 B.; lso that if the 400 F.-500 F. portion's should average 345 age above 1.4630;.or if the densities should average 36 B..the refractive indexes should not average above 1.4605; (lz.) the oil has in the portions distilling over in 25 F. intervals between 300 F. and 400 F.' hydrocarbons that quickly reduce fuming` to nonfuming sulfuric acid in amounts which on the averageare larger-,than the amounts in F intervals between 400 F. and 500 F. or 550 F.; the oil exhibits in all or part of the portions distilling over in 25 F. intervals between ',B. 4the refractive indexes should not aver- E tion.

300 F. and 400 F. characteristics of an oil which has been incompletely distilled after subjection to sulfuric acid; (lo) the oil eX-- the portions distilling over in 25 F. inter-v vals between 400 F. and 500 F. or V550 F.

characteristics of one "givenl an incomplete distillationv after subjectionto 98%v acid as abovevv defined or to othersuch sulfuric acid 'as attacks smoky hydrocarbons of Beaumont oilnot attacked'by acid yof 66B. Oil thus distinguished which isl in whole or in -part'vai product of Beaumont or analogouspet-roleumfv is more, especially but not exclusively claimed; for it is intended to 'include petroleum or hydrocarbon oil in general of the specified properties, as well as products of Beaumont or analogous petroleum in particular.' In some of thelclaims the average refractive ,index of the 400 F. to 500 F. portions is statedfor oil where said portions `average between about 34- B. 'and 36 B., as not above 1.4610 for oil y of B. with allowance at the rate of plus forty or minus twenty ten-thousandths lfor each degree B. respectively, beloweork above 35'v B. I haveobtained such new or improved oil from-Beanmont :petroleum by the refining above described.

Any suitable apparatus can be used'to carry on the processes of the present inven- A relinin plant is vhereinafter described@- which` it 1s considered best to use.

VThe""following isn a description of what is considered the best Inode of carrying the invention into eect,referencebein`g had to the accompanying drawing which 'is a diagram of the rbefore mentioned plant. "In Athis description details are given with fullness, and particularity by Way of example and illustration, in order the better to en-l ableA those skilled vin theart to make and use. my ,'invention, and the several portions thereof as setl forth'in the preceding more general descrlptlon and in the hereinafter Written claims; but'it will, of course, be understood that modiiieations can be made, so long as lthe substance of any one or more of the hereinafter written claims is taken.

The crude Beaumont petroleum is su plied after the usual manner to .the cru e oil vstill a by a charging line b; and when the still has been filledlto the desired level itis heated so as gradually to raise the temperature ofv the vstills contents, -The gas and vapo-rs as they are formed by the heat4 vare cooled to condense the oil vapors'.y

pass over to the condenser c wherein they n The liquid of condensation flowsl into the distillate receiver d. The gas, includinga'ny uncondensed vapor, `passes either by the line e to be burned as fuel or otherwise disposed 'of, or by the gas line f to be utilized in sulfuric acid making. While the temperature 'of the vapors as they leave the still ais below about 500 F., more or less, the gas fr'ornA the condenser cfconsists of about. or labove 85% hydrogen sulfid (ordi.- narily, if not always) and is then delivered vto gas'line f; The temperature is raised to this degree more gradually than 4in ordinary distillation,v being regulated with special reference to the production 'of yhydrogen sulfid' to the best advantage, and the distillate being allowedto take care of itself.

Should the hydrogen suld given olf at any time below about 500 F. be found'v to be unsatisfactory in quantityv o-r'quality, it can be sent into line eas long as it may b e so; but in my experience this change o f lgas line has not. been found expedient" until about 500 F. is reached. At about or above thisdegree the gas should be turned into the line e, so soo-n as the evolution of hydrogenv sulfid fails in quantity or quality,

the line 'f remainingiclosed during the rest of the run. Y

VvWhile the temperature is rising toward 500 F., theA distillate collects in' the receiver d until it becomes too smoky for utilization without'removal 'of smoky hydrocarbons therefrom beyond what can be aca4 complished by treatment with 66 B. acid and redistillation. This has been found in my experience to be when the gravity of the distillate at the worm end (that is, beforeA it enters the receiver d) is about 42 B., more `or less, the temperature of the vapors escaping from the l F., more or less. The distillate then in the receiver is'hereinafter referred vto as the first `burning oil cut. It belongs to the .lighter vend of the burning oil fraction. It

amounts, in my experience, to from five to still a being Vabout 400 ten per cent. of the crude oil supplied to still a. The inlet of receiver d is then closed and that of receiver gv is opened, so that the distillate from condenser will flow into this latter receiver. A This change of ceiver vhas been effected, in my experience, before thel yield of hydrogen sulfid becomes unsatisfactory; so that for a time after the change of receivers the heating of the still a is regulated with speciall reference tothe evolution vof hydrogen suliid. Afterward the heat viifgfstill a is regulated (as customary) Withf'special reference to thedistillate to be obtained.

The distillation is vcarried on with cracking which commences (in my eX' erience) When the temperature offthe liquid oil in the still a is about 600o F.,- more or less, the

, three receivers couldbe used for this ftillate, respectively.

distillate inthe two receivers 0E and g then amounting to about 40%, more or less, of

the crude oil supplied tqthe said still au The distillation is continued as long as it is safe to do so, say, till the dstillate in .said two receivers' amounts to about 85% of said crude oil. The oil in receiver g is herein termed the cracked oil distillate; although a large percentage is composed of uncracked products. f

It' is customaryvto have a receiver into which the distillate can be vturned whenever it becomes undesirable in quality, the result of something accidental; vthe receiver k is provided' for such purpose. .When necessary, its inlet can be opened, those of the re-A ceivers d and g being closed. Any one of the:

ose, the other two serving to collectpthe'l rst burning oil cut and the After the completion of arun, the crude oil still a can be emptied through the .targ line j or in any suitable way,lprepa`ratory-f to relling with crude oil for anew run.

Y The cracked oil distillate from receiver gj .is delivered by pum 1', through line a, into distillate still la, w erein it is distilled -toV separate the burning oil from'the heavierv .f raction. The vapors'pass over to the con- -denser l, where the are reduced to the liquid, stata-.any uncon ensed products escaping by the line m, to be used as` fuel oras may j' -be desired. The distillate is collected in the receiver n until it becomes too smokyv to be used: -in burning oil -without ,removal of the .smoky lvhydrocarbons beyond what lcan be effected by treatment with 66 B. acid\and redistillation. In my experiencethis occurs when the oil from the worm end is about 42 B., the temperature ofthe vapors from the still lo being about 420 F., more or 4less, and the distillate in'receiver n being .in oil cut.

- about 31 about.' eight per cent. of the crude oil s upplied to still a. This portion of distillate is erei'nafter referred to as thesecond burn- -Like the first burning oil cut, `it elongs to the lighter end of the burning voil fract1on. y

After i-t has been collected, the oil from condenser'l is run into ,receiver p, so long as Y I the distillate from the worm end can be made' non-smoking by treatment with a.

Vmoderateamount of 98% acid and distillation of the so-treated oil. In myex erience, -the distillate (hereinafter termed t e third 'burning oil cut) can be thus collected in the `receiver p until it amounts to about 30%" ofthe'crude oil supplied to the still a, the gravity ofthe oil at the worm end being. B., more or less, .andtheltemperalture-'ofI the vapors escaping from the dis' }til1at e stillk being about -5507-1-F-fmorejor less. Thel residuum inthe distillate still .7c

cracked oil disr Vsludge tank w, the oil is washe the one stilllc'serves for both; distillations.

It is to be understood, however, without further statement, that where? one still, agitator or other vessel is shown, in practice u as many ofsuch vessels as desired can be used, and that it is not 'material todistil or oils with acid in the same vessels. .1

The rst'and second burning oilcuts are treated .with vordinary concentrated acid either separatelyor mixed together, 4as may .to'collect different oils, or to treat-diiferent be preferred. AThey aredelivered from their respective receivers 'd and n bythe pump 1' through a branch ofthe oil line s to the agitatorjt. Here' the oil is agitated as custom- 'ary inthe sulfuric acid treatment with acid of G60-B.; and, after settlin and drawing off the acidsludge throug pipe u,4 into repeatedly with water and then with asolution' of caustic alkali. The' water and alkaline solution can lbe removed .'(after proper settling in each-case) through the draw-olfv my experience, about ten pounds of 66J B.= acid to a barrelof the distillate treated is suiicient. The treated oil is delivered by pump ythrough part -of oil-line .Sinto distillate I' still k and 1s subjected to an incomplete distillation therein, that is to say, it is distilled so long as' the oil from the worm'end is satisfactory( According `to my experience, the distillation may well be stopped when the oil from the worm end is between 39 "B. and 40 B. The effect of the incompletel distillation, after the acid treatment, 1s to reduce the oils content yof ulfur, as well as its content ofsmoky'hydro arbons. The oil from condenser Z during rthis distillation collects in the receiver n. The residuum in still k, amounting, .in my experience, kto between ten and twenty per cent. of the charge of said 'stille c, is then run -oif throuv h the tar line g, leaving the still k ready or the next run.- The third burning oil cut is' pumped fromreceiver p into agitator tand 1s there vagitated'with 98% acid in moderate amount for 'about'an'houn In this time, according to my experience, the effect of the .acid` w1l1 be exhausted. .The acid shouldbe applied in 'two portions and may be in all' a out two pounds, more or less,- of acid to each gallon of the oil treated, namely, ofthe third burning oil cut. The oil should have a temperature lof about. 90 F., more or less, at the beginning of the treatment. The acid sludgerv is drawn off intol the tank. fw, and the treated oilis washed repeatedly with water and afterward 'with a solution of custic 60, still a, together with a small proportion of alkali as in the ordinary sulfuric acid treatment.v

rlhe treatment4 with 98% acid greatlyimproves the oilfbut it will still containan excess of smoky hydrocarbons, aswell as acidy compounds which would cause the lamp wick to be charred were the oil without further refining burned in a lamp. The treated oil is, therefore, delivered by pump y, through oil line s, into distillate still/c and subjected to an incomplete distillation, that is, a distillation so long as the collected distillate constituting'the third burning oil cut, after mixture with the light ends (first and; second burning oil'cuts) furnishes a product which as 'a whole shows either by burning in a lamp orby the refractometer the proper freedom from' smoky hydrocarbons. According to my experience\tledis tillatio-n would best not be continued after the oil from the worm end reaches 29%o B. or somewhat lighter (sa-y, between 30o B.

rand 31O B.) if .the still should be running` slowly.' The third burning oil cut\is cols lected in the receiver 79, or in the receiver n, if desired. The residuum, amounting, in my experience, to about ten per cent., more or less, of the treated oil charged into the still Z6, will contain the worst (smokiest) por-tions of the oil. It is`run olf by the tar line Q.

By the precedingoperations there will.

have been "obtained one, twoor three lots of oil, according to the collection in one, two or three receivers of the distillates from the incomplete distillation of the three burning oilcuts. The refining of said distillates is finished by subjecting them,A separately or two or more of them in admixture, to treatment in the usual way with a small quantity of 66 B. acid Ain the agitator ,and the finished oil is thence run by line a introthe tank 2,'wherein the oil from different cuts can be mixed, if not already in admixt-ure.

'In my experience, Beaumont crude' oil contains such a small percentage of light products that steam stillingl is not necessary for low 'test burning oil (kerosene) but if itshould be desired to'increase the fire test, the finished oil, or one or both the lighter burning oil cuts, may be steam stilled to bring the product to the desired test. Ac-

/cording to my experience, it should suilice finished heavier portion and the whole steam stilled. n 4 v The hydrogen sulfid from the crude oil present are burned, the .hydrogen suld V.being converted thereby into sulfur dioxid and water. These may both be delivered through gas line 5into the lead chamber 6 for -making sulfuric acid. They could be delivered into a tower7 5 but this is'not conn sidered desirable, in view of the large pron portion of ,water vapor inadmixture with the sulfur dioxid. The water could, how'- ever, be separated by condensationy and the sulfur dioxid, being heated, could be sent either into tower 7 or lead chamber 6. It could be sent into other lsulfuric acid making apparatus. v

The acid sludge froml tank w is delivered through acid sludge line 8 by pump- 9 into the acid sludge still 10 until the. latter is illed to the desired level (say, 200 barrels of acid sludge in a still of 500 barrels capacity). The still is provided with a rotary stirrer 11, in order to check foaming. After chargingV the stillis heated so as lto keep up a good delivery of sulfur dioxid, say, about 2,500 cubic feet,v more or less, per, hour.

The evolution of gas begins at about 2200 F. (temperature of the liquid), and at about 600C? F. should be practicallycomplete, only coke remaining in the still. y

The gas and vapors from still 10 (which may be of iron) are passed jthrough the condenser 12 (which should have a lead worm), in order to separate the small amount of oil vapors carried over with the sulfur dioxid. The sulfur. dioxid then passes by gas line 13 -to a storage gasometer 14, from which (after being heated) it is sent either into tower 7 or chamber 6, 1n order to be converted into, sulfuric acid.

Toward the end of the operation, in removing the last portion of sulfur from the sludge, 'some hydrogen sulfid comes over. 105 To convert this into sulfur dioxid (and wa-J ter) the gas may be passed through the y burner 4-on its way to the lead chamber 6. As the' gas from condenser 12 isl cold thro hout the operation, it should be heatiavd`r before itwris admitted into tower 7 or chamber 6. This can be done by passing all the sthrough a burner (as 4, for example) 1n which vcombustion yielding sulfur dioxid is going on. *Such passage insures 'also the combustlon of any small quantities of vhydrocarbons, which may be present in the gas. All the sulfur dioxid from such burner would passinto the sulfuric-acidmaking apparatus. v 1

The oil from condenser '13 runs into the receiver 15. It andthe coke (removed from the still 10 preparatory to the next run) can be used as fuel or otherwise disposed of.

The dilute sulfuric acid from the lead 125 chamber 6 is rcarried by line 16 to an apparatus 17, where vit isy concentrated to 98% acid byheating or by adding sulfuric anhydrid or by the vaid of both operations. It is delivered by acid line 18 toa storage tank 130 l (d) yield between '400 400G/F. and 500O less; (c) exhibit 19 from which it'passes by line 20 to the tank 21 from which it is delivered .by pump 22 into the agitator t as above described. The acid of 66 B. can be obtained from another portion of thesame dilute acid and be delivered in the The finished oil in tank 2 will: (a) have a refractive index which is less as herein above specified than that of oil of like boiling point obtained from Beaumont petroleum by t-he ordinary fractional distillation and treatment of distillate with 66 B. sulfuric acid,and which, according to my experience, should be ab0ut.1.4540, and, therefore, sufficiently below 1.4600 for the oil to Lbe nonsmoking without admixture of other oil with the Beaumont product; possess mobility proper for climbing a lamp wick.; (c) distil mainly, if not wholly, within `the temperature limits of burning oil (kerosene); F. and 550 F. on a test distillation within temperature ntervals of 25 F. portions which are, respectively, of greater gravity as herein above specified than ythe portions similarly yielded in the same temperature intervals by Pennsylvania petroleum and which may, according to my experience, be such thatthe average of t-he portions distillilg over between F."is about 35 B., more or in the portions distilling over in 25 F.`intervals between 400 F. and

' or more) than those 500",F. or 550 F.v bromin-absorbing Capacities which on the average are less as herein above specified (say, by about four per cent.

of the portions distil- F. intervals between 300 F. and 400 F.; (f) exhibit in the portions distillingover in 25- F. intervals between 400 F. and 500 F. anaverage bromin-absorbing capacity of about one per cent., more or less; (g) exhibit in the same 400 F.--l

.portions an average refractive'index'of about 1.4600, more or less; in the portions distilling over in 25O F. 1ntervals between 300 F. and'400 F. amounts of hydrocarbons that quickly reduce fuming to non-fuming sulfuric acid, the average of which amounts is greater than those in the respective portions distilling over in 25 F. intervals between 400 F. and 500 F. or 550 F.; (i) exhibit in the portions which distil over in 25F. intervals between 300 F. `and 400 F. 'characteristics of an oil ling over. in 25" which has been incompletely distilled after same way to the said agi- (It) have F. and 500 F. or 550 FQ for the decoloration limits of the mvention; and possiblyl some one or more of the characteristics mentioned might be absent from some of the resulting products. By mixing-a product of the prec1se character stated with other oils, products can be obtained which donot have or exhibit all these. properties or phenomena, but which yet are within the invention. The possession by the oil of the characteristics mentioned under (i) (le) and (l) would be obvious from the processes used in 0b-y taining the same. v

To show `the characteristic (It) the 011 may be distilledin a liter flask, such as ordinarilyused in the laboratory for fractional distillations, and the distillate be collected in separate portions for each interval of 25F. as -indicated by a thermometer whose bulb is placed in the upright neck of the flask just below where the side tube is joined thereto. A sample of each distillate portion is -then treated by agitation with fuming' sulfuric acid and repetition of the operation (if necessary) until the acid, when drawn ofi',- is found to fume. The percentage by 'which the volume of a given distillate portion has then been diminished is to be taken as the f percentage therein before testing of hydrocarbons that quickly reduce fuming to nonfuming sulfuric acid. The 'fuming acid used should be 90 per cent. sulfuric monohydrate and 10 percent. sulfuric anhydrid.

To vshow characteristic (g) a test/distillation may be made and the portions coming over in'25 F. between 400 F. and 500 F. separately collected and tested for refractive index with the refractometer. The four numbers so obtained are then added tpgether yand* divided by four to get the average refractive index of said portions. j

p To show' characteristics (e) and a test distillation may be made and the` distillate portions coming over 25. Faintervals collected" separately.. A` measured amount of each distillate portion is dissolved in enough carbon disulfid to give a solution of five times the volume of dissolved distillate. AA. s/mall quantity, say, 5 cc. (containing 1 cc; of distillate) of the said solution is placed in a dry stoppered '.bottle, which is wrapped in a` piece of cloth to keep out the light. Five times the volume (25 .cc.), of/a decinormal solution of bromin'. in

dry redistilled carbon'disuld is added; and the bottle, with its contents, after having been shaken, is set away ina dark vplace 4for fifteen minutes. Then a'few cubic centi- -meters of potassium iodid solution and a littleKV starch solution for indicator are added; the solution/lof brominand oil is` decolorizedwith a decin'ormal solution of sodium thiosulfate.; and the volume required is noted. The subtracburned in an Ordinar tion of thisfvo'lume from the volume of thiovsulfate solution required to decolorize the same Volume 25 cc. as above) of the bromin solution without the -oil gives a measure from which the percentage' of 'broinin absorbed by the oil can lbeY calculated. For simplicity of calculation, each cubic centimeter of said.'

measure can betaken. asr indicating in every. caseone per, cent. of bromin absorbed;and

'no regard need be given` to the `difference in specific gravity of the portions.: ofdistillate coming over in different 25F. intervals. y

To show characteristic (d) a test distillation can be made and the distillate pi'tions coming over in 25 F. intervals aboveJ L100 F. 'collected separately. The distillatepor-` tions obtained can be tested with anhyd'rometer and-the results averaged or compared Aseverally with those obtainedby similarly testing distillate portions'simil'arly obtained in the A.same temperature vintervals from Pennsylvania petroleum, either directly from the crude Pennsylvania oil, or from either the burning oil distillate, or the `finished burning oil derived in the usual way from such crude. i l

To show characteristic (c) the oilcan be distilled in a laboratory flask provided with a thermometer in thenpright neck as aforesaid. .A

To show characteristic (b) the oil may be petroleum (kerosene) lamp. A good vame will show that the oil has the proper mobility; were it too viscous, not enough oil would climb the wick tosupport the flame.

' In my experience an oil with a refractive index of 1.4540 or 1.4545 will beV non-smoking, while onewith an index of 1.4600 will o \be smoky, although substantially less so.

than oil of like boiling point obtained in the .Ordinar` way from Beaumont petroleum.

Probab y one with an index of 1.4560 would pass as non-smoking; and one with even a hi her index might do so.

o show characteristic (a) the refractive index of the oil canbe obtained by the refractometer in the lniown way and the result compared when necessary with that obtained similarly from` oil of like boiling point obtained from Beaumont petroleum' the lordinary fractional distillation and treatment of distillate with 66 B'. sulfuric acid.

Where two or more of the characteristics (lac), (f). (arend e) met@ ige-determined, one distillation would, of course, suice, .the amount distilled being sufficient to yield portions of distillate in. the respective 25 \F. intervals large enough for the teststo be made upon the same.

In carrying out the refining of Beaumont etroleum in accordance withthe invention, instead ofcollecting 'as part of the cracked oil distillate the oil which comesrover after the first burningl oil Vcut .and before cracking begins, said oil'could be collected intwo portions,l thefirst of which need `not be distilled again before subjection to the 98% acid.. According to this modification of the described procedure, afterfthe rst burning oil cut had been collected -in the receiver cl asl above described, the distillate would next be collected in the receiver h so long as the oil from the worm end should be sufficiently deprived of smokyhydrocarbons by treat- Iment with a moderate amount of 98% acid followed'by an incomplete distillation, and then the rest'of the distillate from the crude oil would be 'collected 4in receiver g (a fourth 'receiver being provided for emergencies). -The oil in receiver g would be distilledin still Ic andthe distillate collected partly in the receiver l'11, and partly in the receiver p as'above` described. The oils from receivers d andi?J (separately or in admixture) `would be treated with acid .of 66 B., .followed by incomplete .distillation of the treated oil as before described for thefirst and second burning oil cuts. 4'The oils froml receivers 71J and p (separately or in admiX- ture) would be subjectedv to 98% acid, followed by incomplete-distillation of the sotreated oil, as before `described for the third l burning oil cut. Moreover, instead of treating the said third burning oil cut with'98% v acid in. the first instance, `it could first be treated in whole or in part `with 66 B.

acid and then with 98%- acid. Or before subiecting thel said cutl to the 98% acid, it

could in whole or in partfbe treated with acid intermediate 66 B. acid and 98%, with or without a preliminary treatment with 66 B. acid. In this Way there might be a saving of acid.

4In my experience 66 B. sulfuric acid can be used with beneficial eect on the oil to the extent of six to eight pounds there- `of to the barrel of oil (40 gallons to the barrel). Also in my experience nonfuming acid of about one per cent. below 98% acid has doneA effective work when employed to the extent'of about two-thirds of a pound thereof to the gallon of. oil.

Vlfhen employing (either or both) 66 B. acid and intermediate acid in connection with 98% acid, it is considered best to select lthe third burning oilv cut with reference to replaced' therebylr and, according to myexperience, the yield in quality and quantity of vfinished oil would be practically the same, as .if vneither 66 B. acid nor intermediate ido n i,

acid, but only 98% acid, two pounds to the gallon of oil, should be used.

' 98% acid with either or both the 66 B .and-

2dol

y by sulfuric anh drid. yThis woul be done intermediate acids) which is made the basis for selecting thethird burning oil cut may be less5 than two pounds to the gallon of oil,

or it may be more than said two pounds, so

long asit is moderate in amount.

The .finished oil in 'any of the foregoing cases should possess all of the before mentioned characteristics (w-Z, both inclusive, as above). Nor would the possession Vof themby the finished oil in any casenecessarily be .affected 'by a partial replacement of98% acid with fuming sulfuric acid containing less than about 98% monoh drate or by using of sai fuming acid or anhydrid a 4'weight about equal to the amount of 98% acid replaced .thereby,a`nd otherwise pro-` ceeding as above set forth. If an entire re- 'placement should be made, the oil obtained would have all the specied characteristics except those duetosu'bjection to 98%. acid.

it should be preferred to e'ect theremoval of smokyjhydrocarbons without the incomplete distillation after treatment witli 98% acid or with the stron er fu'ming acid, this could `be done, the acid -being applied, say, in lots oftwo pounds to the gallon pf oil until sufiicient freedom from smoky hydrocarbons results and the procedure otherwise being as above set forth; and in such case the oil obtained would have all the specified characteristics except those due to said incomplete distillation. In case 98% acid should be also entirelyrep'laced by the aforesaid stronger fuming acid, the finished oil would also lack thejcharacteristics due to subjection to 98% acid.

If an loil which has 4the characteristic (71,)

' should be mixed with Pennsylvania or Lima i' oil, themixture might or might not show in the portions distilling over between 300 F.

and 400 F. a larger percentage of hydrocarbons that quickly reduce fuming tov nonfuming sulfuric acid 'than in the portions' distillin over between 400 F. and 500 F. or 550. .f y l If an oil vhaving the characteristicv (e) should be mixed'with Pennsylvania or Lima oil, the mixture would (unless the latter oil should be in too large proportion) show al greater percentage of bromin absorbing ydrocarbons in the portions dlstillingover preceded by l ceases between 300 F. and 400 F. than in the portions distilling over between'400 F. and

500 F.- or 550 F.; but the difference in percentage would be less than in the straight Beaumont product. In my product claims,

therefore, which mention characteristic (e), l

I do not restrict myself to a difference of four or more per cent., but include a; difference of one, two or three er cent. as well. Similarly, I do not restrict my product claimswhich mention characteristic (d) in such sense that the respective distillate portions should be denser thanv those yielded by Pennsylvania petroleum in the same temperature intervals `by'five or more degrees Baume, but I intend it to include cases where the difference may or four degrees Baume. v

Should it lbe desired for any reason to select a burning oil third cut-or other burnf 'ing oil distillate with reference to its treatbe only two, three ment with la moderate amount ofintermediate acid with `or without 98% acidand with or without 66 B. acid, an assay could be. made with the predetermined amount v of such acid or acids and the collection of distillate-stopped when oil from the worm end `shouldattain the proper 'gravity for stopping as shown by the assay.

According to .my experience, a greater amount of 66 B. acid than about 6 or 8 pounds tothe barrelof oil accomplishes but little work iii-proportion to the quantity of acid used. Such acid, I believe, `would not give a practical yield of oill with refractive index as low as 1.4600,:however large an amount ofl it might be employed.` Also, according to my experience, intermediate acid, if used for more than about two-thirds of a pound of acid to the gallon of oil, would be moreexpensive than the amount of V98% acid which would be rreplaced thereby.

Non-fuming acid `containing fullv 98% to 98%% monohydrate is considered the best. acid to use,whether supplemented or not vby (-eith'eror both) 66 B. acid and intermediate acid.- The expression 98% acid as herein employed is not restricted, however, to that containing full 98% or more of sulfuric monohydrate; but it includes acid .containing about (although under) 98%.

monohydrate, and vin particular it includes non-fuming sulfuric acid containing such an approximation to 98% ofv sulfuric monohydrate as to give a fair yield of oil with a refractive index as low as or lower than about 1.4540 or 1.4545, or even between'this figure and 1.4600.

should it be Sd desired, the acid from (either or both) the hydrogen suld from the Beaumontl or analogous crude oil and -the sulfur dioxid from the acid sludge can be used for treating Beaumont or analogous oil in theform vof 66 B. acid, intermedia te acid, or stronger fuming acid as well as in ,the formr of 98% acid; or it can be sold any desired kind or degree of concentration, the acid for treating the Beaumont or analogous burning oil distillate being secured by purchase or in any properway.

In the hereinafter written claims where Athe following expressions occur they have the following respective' meanings, namely: (as). The expression such sulfuric acid as Will attack smoky hydrocarbons of Beau- Amont petroleum not attacked by 66 B. sulfuric acid means primari/ly sulfuric acid of about or above 98% monohydrate- (fumingas well as non-fumin'g'), and secondarily other propel' sulfuric acid, as fuming sulfuric acid containing less than about 98% monohydrate, o r sulfuric anhydrid, or acid of suitable strength intermediate 60 B. and 98% acids. The use of any one'of the acids or using two or more in` succession would be the `use of acid rvithin the expression.

(b). 4The expression l, burning oil fracv tion of such petroleum means primarily the hydrocarbons suitable for 'burning oil (kerosene) which can' be obtained from Beaumont or 'analogous etroleum by distillation with the aid of) cracking to increase the yield of the burning oil, and secondarily the hydrocarbons suitable for burning oil (kerosene) which can be otherwise obtained from Beaumont or analogousv petroleum, as, for example, by distillation without such cracking. v

(c). The expression separating the lighter from the heavier portion of the smoky burning oil fraction vof suchy petroleum means primarily a separation in two distillations in one of which lightluncracked hydrocarbons are obtained (as in the distillation of the crude oil, for example) and in the other of which light cracked hydrocarbpns are obtained (asin the distillation of the cracked oil distillate, for example), the said burning oil fraction being obtained from the Beaumont or analogousl oil by distillation with thev aid of cracking to increase the yield of burning oil. The expression also means a separation of .the light hydrocarbons in other ways,'as, for example, a separation of themin one or more 'distillaltions from the cracked oil distillate. (if

cracking to increase the yield of burning oil is resorted to) or from the crude or other uncracked oil (if resort ,to such cracking be not had).

(d). The expression the procedure being carried on inthe specified manner 'for reducing the amount of Aacidemployed means that the procedure consists in partl of some one, two or three or of all' four 'of the following' operations which. are severallyand collectively calculated to diminish the ratio of acid consumed toyield Aof nonsmoking or less smokyburning oil, namely,

(1) separation of the lighter from the jectingthe l.smoky burning oil fraction Vof and incompletely distilling` the. 'so-treated fraction, substantially as described.

heavier portion of the burning oil fraction for admixture after subjection of the said heavier portion by itself to such sulfuric acid as will attack smoky hydrocarbons of Beaumont petroleum not attacked by 66 B. sulfuric acid, so that such acid is not consumed -on the said lighter portion without corresponding increase in the said yield; (2) incomplete distillation of thelighter portion, after it has been subjected to ordinary concentrated sulfuric acid, whereby smoky hydrocarbons are left in the still whose removal otherwise might require more expensive acid; (3) collection of the burning oil 'fraction with reference to a satisfactory treatmentthereof with a moderate amount of acid, since a larger volume of so collected distillate than of distillate as ordinarily heretofore collected can be made nonsmoking or less smoky with a given amount of acid; (4) incomplete distillation of the oil Asubjected to such sulfuric acid as will attack smoky hydrocarbons of `Beaumont petroleum notl attacked by 66o B. sulfuric acid; for smokyhydrocarbons are thereby left in the still whose removal otherwise might require more acid. i

In my divisional application No. 363,713, filed March'21, 1907, asa continuation of this present a vplication and '"iade in consequenceof v cial requirement of division, I have described` and claimed the apparatus herein disclosed, intending thereby to protect `all and singular the new and useful parts, improvements and. c ombinations embodied in said apparatus.

I claim as my mvention or discovery; 1. In refining Beaumont or analogous p etroleum, the) improvement consisting in subjecting the smoky burningioil fraction (of such petroleum to the specified 98% sul-J furic acid, substantially as described.

2. lInrefining 'Beaumont or analogous petroleum, the improvement consisting in sub- 110 such .petroleum tosuch sulfuric acid as will. attack smokyL hydrocarbons-of Beaumont pea troleum nota'ttack'ed by '66 B. sulfuric acid,

1.15 `3. In refiningfeaumont'or analogous petroleum,the improvement consisting in collecting the `burning oil fraction Awithfrefer- I ence toits cap'acityffor satisfactory treatment Vwith a moderate amountA of` appropriateacid, and subjecting the so-collected oil to va moderate'amount of such sulfuric acid as will attack smoky hydrocarbons of Beaufurie acid, substantiallyas. described.;A

4. In refining Beaumont or analogous pe troleum, the improvement consisting '1n collectillgl the burning oil fraction With .refer-v ence to. its capacity for satisfactory treatment with a moderate amount of appropri- `ate acid, subjecting the so-collected oil to a moderate amount of such sulfuric acid as will attack smokyhydrocarbons of Beaumont petroleum not attacked by 66 B. sulfuric acid, and incompletely distilling the so-treated oil, substantially as described.

5. In refining Beaumont or analogous petroleum, the improvement consisting in separating the lighter from the heavier portion of the smoky burning oil fraction of such petroleum, subjecting 'said heavierport-ion by itself -to such sulfuric acid as will attack smoky hydrocarbons kof Beaumont petro-- leum not attacked by 66 B. sulfuric acid', and mixing the said lighter `portion with the so-tieated heavie portion, substantially as described.

6. In refining Beaumont or analogous petroleum, the improvement consisting in separating the li hter from the heavier portion of the'smo burning oil fraction of such petroleum, subjectin said heavier por.Y

tion .by itself to such su furic acid as will attackv smoky hydrocarbons of Beaumont petroleum not attacked by 66 B. sulfuric acid, incompletely distilling the so-treated portion, and mlxin the said lighter portion with the distillate rom suchincomplete distillation, substantially as described.

7. In refining Beaumont or analogous petroleum, the improvement consisting in separating the lighter from the heavier portion of t e smoky burning oil fraction of Such petroleum, collecting the said heavier portion with reference to its satisfactory treat-ment with a moderate amount of appropriate acid, subjecting' the so-collected heavier portion by itself to a moderate amount of such sulfuric acid as will attack smoky hydrocarbons of Beaumont petroleum not attacked by 66v B. sulfuric acid, and mixing the said lighter 'portion` with the 'so-treated vheavier l portion, substantially as described.

8. In refining Beaumont or analogous petroleum, the improvement consisting in separating the li hter from the heavier portonof the smo y burning oil fraction of such petroleum, collectingithe said heavierf portion With reference to its satisfactory treatment with a moderate amount of appropriate acid, r`subjecting the so-collected heavier portion by itself ,to a moderate amount of such sulfuric acid as will attack smoky hydrocarbons. of Beaumont petro leum not attacked by 66 B. sulfuric acid, incompletely distilling the so-treated heavier portion, an mixin the said lighter portion With the distillate rom Jsuch incomplete distillation, substantially as described.

9. In refining Beaumont or analogous' petroleum, the improvement 'consisting jin separating the lighter from the heavler portion of the smoky burning oil -fraction .o-f such petroleum, subjecting said lighter por-l tion-to ordinary concentrated sulfuric acid, incompletely distilling the so-treated lighten portion, and mixing the distillate from such incomplete distillation with a heavier portion of said fraction from which smoky hydrocarbons have lbeen separated, substantially as described.

l0.`IA In refininggBea'umont or analogous petroleum, the improvement consisting Ain separating the lighter fromthe heavierv portion of the smoky burning -oil fraction of such petroleum, subjecting said lighter portion to ordinary concentrated sulfuric, acid, incompletely distilling the so-treated lighter portion, subjecting said heavier portion by `itself to such sulfuric acid as Will attack' smoky hydrocarbons of Beaumont petroleum not attacked by" 66 B.- sulfuric acid, and mixing the distillate from the income plete distillation of said lighter portion with the so-treated heavier portion, substantially as described.

11. In'reflning Beaumont or analogous pe-A troleum, the improvement consisting in separating the lighter from the heavier portion of the smoky burning oil fraction ofsuch petroleum, subjectingsaid lighter portion to ordinary concentrated sulfuric acid, incompletely distilling the spo-treated lighter portion,- subject-ingJ vsaid heavier portion by itself to such sulfuric acid -as will attack smoky hydrocarbons of Beaumont petroleum not attacked by 66 B. sulfuric acid, incompletely distilling the so-treated heavier portion, andl 'mixing the distillates from the two incomplete distillations, substantially as described.' I a i 12. In refining Beaumont or analogous petroleum, the im rovement consisting in separating the liglif'er from the heavier portion of the smoky burning oil`fraction of tion to ordinary concentrated sulfuric acid, incompletely .distilling the so-treated lighter portion, collecting with reference to its satisfactory treatment with a moderate amount of appropriate acid, subjecting the so-collected heavier portion by itself to a moderate amount of such sulfuric acid as Will` attack lsmoky hydrocarbons .of Beaumont petroleum not attacked by 66 B. sulfuric acid, and mixing the distillate from' the 'incomplete distillation of said .lighter portion With the s otreated heavier portion, substantially as `described. 1

13. In refining 'Beaumont or analogous separatingthe lighter from the heavier portion ofthe smoky burning oil frac-tion of tion to ordinary concentrated sulfuric acid, incompletely distilling vthe so-treated lighter -portion, collecting Athe vSaid heavler portion'v 'with reference to its satisfactory treatment such petroleum, subjecting4 said lighter por` the said heavier portion petroleum, the improvement consisting in such petroleum, subjecting said lighter por- A' with a moderate amounty of appropriate acid, subjecting the so-collected heavier .portion by itself to a moderate amount of such sulfuric acid as lWill attackv smokyhydrocarbons `of Beaumont petroleum `not attacked by 66 B. sulfuric acid, incompletely -,distilling the so-treated .heavier portion, and mixing the distillates from the tWo incomplete distillations,.substantially as described.

14. In reining Beaumont or analogous.

petroleum, the improvement consisting in obtaining burning oil distillate from such petroleum With the aid of cracking to increase. the yield ofburning oil, separating the lighter from the heavier portion of said distillate in tWo distillations in one of Which light uncracked hydrocarbons and in the other of Which light cracked hydrocarbons are obtained, 'and mixing both such sets of hydrocarbons with a heavier portion of the burning oil fraction of such petroleum from which smoky hydrocarbons have been separated, substantially as described.

15. In refining Beaumont or analogous petroleum, the improvementJ` consisting yin separating the 1i hter from the heavier portion of the smo burning oil fraction `of such petroleum, and in. subjecting said heavier portion by itself to suchnsulfuric acid as Will attack smoky hydrocarbonsof Beaumont petroleumnot attacked by 66 B. sulfuric acid, substantially as described.

16. AIn refining Beaumont or analogous petroleum, the improvement consisting in separating the lighter from the heavier portion of the smoky burning oil fraction' of such petroleum, and in subjecting said heavier portion by itself to such, sulfuric acid as Will attack smoky hydrocarbons of Beaumont petroleum not attacked b 66 B. sulfuric acid, and in 'incompletely istilling the so treated oil, substantially as described.

17 In refining Beaumont or analogous petroleum, the im rovement consisting ,in heating such petro cum toL evolve hydrogen' sulfid, converting it into such sulfuric acid as will attack smoky hydrocarbons of Beaumont petroleum not attacked by 66 B. sulfurie acid, and subjecting the smoky burning oil fraction of such petroleum tothe soobtained acid, the procedure being vcarried on in the specified manner for reducing the amount of acid employed, substantially as described. n

18. In refining Beaumont or analogous petroleum, the improvement consisting inv subjecting the smoky burning oil fraction of'^sucl1 petroleum to such sulfuric acid as will attack smoky hydrocarbons of Beaumont petroleum not attacked by 66 B. vsulfuric acid, converting the sulfur content of the resulting acid sludge into such acid as aforesaid, and subjecting oil of said fraction to the so-obtained acid, the procedure "being carried on in the4 specified manner for dias will attack smoky hydrocarbons of Beaumont petroleum not attackedby 66 B..v sulfurie acid-subjecting the so obtained burning oil distillate tov such sulfuric acid as aforesaid obtained inv part from said gas,

converting the sulfur content of the resultant acidv sludgeinto 'such sulfuric acid as aforesaid, andA subjecting so obtained burning oil distillate to the so obtained acid, the procedure being carried onv in the specified manner for diminishing the amount of acid employed, substantially as described.

20. A new or improved petroleum or hydrocarbon oil which has a refractive index less as specified than is possessed by oil of Alike boilingpointvobtained from Beaumont petroleum by the ordinary fractional distillation and treatment of distillate lWith 66o B. sulfuric acid; Which has mobility proper for climbing a lampl Wick; Which distils Within the temperature limits of burning oil (kerosene); Which yields bey tween 400 F. and 550 F. on a test distil- 'refractive index, mobility, volatility and gravity which has not been so treated; substantially as described.

21. A new or improved petroleum `or hydrocarbon oil which has a refractive in-l dex less as specied than spossessed by oil of like boiling point obtained from Beau mont'petroleum by the ordinary fractional distillation andftreatlnent of distillate with 66 B. sulfuric acid; which has mobility proper for climbing a lamp wick; which dist-ils Within the temperature limits of burning oil (kerosene); which yields between 400 Ffand 550 F. on a test disti1 lation Within temperature intervals of 25 F, portions of distillate which' are, respectively, of greater gravity as specified than the portions similarly yielded in the same temperature intervals by Pennsylvania petroleum; and which isfurther distinguished by 'exhibiting the characteristics of an' oil which has been incompletely distilled after subjection to such sulfuric acid as attacks smoky hydrocarbons of Beaumont petrol amv `leurnnot .attacked by 66 B. acid, in contradistinction to oil of the same refractive in-y dex, mobility, volatility and gravity which hasr not been so. treated and distilled; substantially as described.'

22. `A newl or improved petroleum or hydrocarbon oil which has a refractive index less yas specified than is possessed by oil of likelboiling point obtained from Beaumont petroleum by the ordinary fractional distillation and treatment of'distillate with' 66 B. sulfuric acid; which has mobility proper for climbing. a lamp wick; which distils within the temperature limits of burning oil (kerosene); which yields between 400 F. and 550 F. on a test distillation'within temperature intervals of 25 F. portions of distillate which are, respectively, of greater gravity as specified than the portions simi larly yielded in the same temperature intel'- vals by Pennsylvania petroleum; and which is further distinguished by having in the portions distilling over in 25 F. intervals between 300 F. and 400 F. amounts of hydrocarbons that quickly reduce fuming to non-'fuming sulfuric acid, which amounts are larger than those in the portions distilling over in 25 F. intervals between 400 F. and 550 F.; and also by exhibiting in these latter portions an average bromin-absorbing capacity which is less than six per cent. and also less as specified than that of theportions distilling over. in 25 F. intervals be# tween 300 F. and 400 F.; substantially as described.

23. A new or improved petroleum or hydrocarbon oil which has a refractive index.

less than 1.4600; which has mobility proper (kerosene) which yields between-400 F. and 500 F. on a test distillation withintemperature intervals of 25 F. portions of dis- 4F{tillateuwhose densities average not heavierA than about 344 B.' nor lighter thanabout 40 B.; and which is--furtheri distinguished by having in the portions distilling overA inr2v5 F. intervals between `300 F. and 400 F. amounts of hydrocarbons that (iluiekly reduce fuming to non-fuming suluric acid, which amounts are larger than those in the portions distilling over in 25 F. intervals between 400 F.`and 550 F.;

tions an average bromin-absorbirng capacity which is less than six per cent. and also less asspecied than that of the portions distilling y,over in 25 F. intervals between 300 F. and; 400 F.; substantially as described.

.65' within the temperature limits of burning oil (kerosene); which yields between 400 24. .A new or improvedv petroleumor hy F. and 500 F, on a test distillation within temperature intervals of 25 F. portions of distillate whose densities average not heavierthan about 345 B. nor lighter than about 40O B.; and which is urtherdistinguished by exhibiting characteristics of an oil which has been subjected to` 98% sulfuric acid, in

contradistinction to oil of the same refrac- 40 B.; and which is further distinguishedv by exhibiting the characteristics of an oil which has been incomple-tely distilled aftenl subjection to such sulfuric acid as attacks smoky hydrocarbons of` Beaumont petroleum not attacked by 66 B. acid, in con- ,tradistinction to oil of .the same refractive stantially as described.

2G. A new or improved petroleum or h vdrocarbon oil having mobility proper for climbing a lamp wick; distilling Within the temperature limits -of burning oil (kerosene); and yielding between 400 F. and 500 F. Y perature intervals of 25 F. portions of distillatewhose vdensities average" not heavier than' about 344 B. nor lighter than about 40 B., whose rei'ractive indexes average not more than 1.4620 plus twenty or minus lif- .teen ten-thousandths for each degree B. the

average density is heavier or lighter than 35 `B.,and whose characteristics in general arev those due to a subjection to 98% sulfurie` acid, in contradistinction to oil of the same vrefractive index, mobility, volatility and gravity which has not been so treated ;l substantially as described.

27. vA new or improved petroleum or hy-` drocarbon oil having mobility proper for climbing a lamp wick; distilling within the on a test distillation within temtemperature limits of burning oil (kerosene); and yielding between 400 F. and` 500 F. ona test distillation within temperature intervals of 25 F. portions of distillate whose densities average not heavier than about .34%,LO B. nor lighter than about 40 B., whose refractive indexes average not more than 1.4620 plustwenty or minus fifteen ten-thousandthsfor each degree B. the

average density is heavier or' lighter than 35 B., and whose characteristics in eneral are those due to an incomplete distillation Y viaess after subjection to such sulfuric acid as attacks smoky hydrocarbons of Beaumont petroleum not attacked by 66 B. acid, in contradistinction to oil of-the samerefractive index, mobility, volatility and gravity which has not been so treated and distilled; substantially as described. Y

28. A new or improved petroleum or hydrocarbon oil having mobility proper for climbing a lamp wick; distilling within the temperature limits of burning oil (kerosene) g and yielding between 400 F. and 500o F. on a test distillation Within temperature intervals of 25 F. portions of distillate whose vdensities average notheavier than about 344B. nor lighter than about 40 B., whose refractive indexes average not more than 1.4620 plus twenty or min'us iifteen tenthousandths for each degree B. the average density is heavier or lighter than B., whose contents of hydrocarbons that readily reduce fuming to nonfuming sulfuric acid average less than the contents of the portions distilling over in 25 F. intervals between 300 F. and 400 F., and whose'bromin-absorbing capacities average less than six per cent. and also less as specified than those of the portions distilling over in 25 F. intervals between 300 F. and 400-F.; substan-' ftially as described.

29. A newV or improvedpetrol'eum or hy;

` drocarbonrv oil having-mobility proper for climbing a lamp wick; distilling within the temperature limits of burning oil (kerosene) and yielding between 400 F. and 500 F. on al test distillation within temperature intervals of 25 F. portions of distillate whose densities average between about 34 B. and 36 B., and whose refractive indexes degree B. it is lighter than 35 B.; substantially as described.

30. A new or improved petroleum or hydrocarbon oil having mobility proper for climbing a lamp wick; distilling within the temperature limits of burning oil (kerosene and'yielding between 400 F. and 500-, F.

on a test distillation within temperature intervals of 25 F. portions of distillate 'whose densities average between about 345 B'..and v 36 B., whose bromin-'absorbing capacities average less -than'six per cent., and whose refractive indexes average not more than 1.4610 with an allowance at the rate of plus forty ten-thousandths for each degree B. the

average density is heavier or minus vtwenty for each degree B. it is lighter than 35 B.; substantially as described. I

31. In refining Beaumont or analogous petroleum, the improvement consisting in subjecting the smoky burning oil fraction of such petroleum to such non-fuming sulfuric acid as will attack smoky hydrocarbons of Beaumont` petroleum not 4.attacked by 66 B. sulfuric acid; substantially as described.

32. In rening Beaumont yor analogous petroleum, the improvement consisting in subjecting the smoky burninor oil fraction of such petroleum first to sulfuric acid in- Itermediate 66 B. sulfuric acid and the specified 98% sulfuric acid and afterward to such sulfuric acid as will attack smoky hydrocarbons of Beaumont petroleum not attacked by rthe said intermediate acid; substantially as described.

In testimonywhereof I. have signed my name to this specification inthe presence of two subscribing witnesses.

40. average not more than 1.4610 with an allow-V CLARENCE I ROBINSON' ance at the rate of plus forty ten-thou- Witnesses: sandths for each degree B. the average J. E. EGGLEsTo'N, density is -heavier or minus twenty for each A. P. ARNOLD.

It is hereby certified that in Letters Patent No. 968,692, granted August 30, 1910, 'uponl the application of Clarence I. Robinson, of West New Brighton, New York,4 y for an improvement .Refining,Petroleuin, errors appear in the printed specification requiring corrections asi follows: Page 4, line14, the Word sulfate should read sud; page 13, lines 7 3l74,the word convertings should read converting; and that the said Letters Patent should be read with these corrections therein that the` same 'mayl conform to the record 'of the case in the Patent Oiiice. I

' Signed-.and sealed this'10th dayv of January, A. 11,1911.

[Sala] A -o. c.l BiLLiNGs,

I l i .Acting Coniim'ssz'oner 0f Patents.

Corrections in Letters Patent No. 968,692.

Y viaess after subjection to such sulfuric acid as attacks smoky hydrocarbons of Beaumont petroleum not attacked by 66 B. acid, in contradistinction to oil of-the samerefractive index, mobility, volatility and gravity which has not been so treated and distilled; substantially as described. Y

29. A newV or improvedpetrol'eum or hy;

' Signed-.and sealed this'10th dayv of January, A. 11,1911.

[Sala] A -o. c.l BiLLiNGs,

I l i .Acting Coniim'ssz'oner 0f Patents.

Corrections in Letters Patent No. 968,692.

Corrections in Letters Petent No. 968,692.

^ It is hereby certified that in Letters Patent No. 968,692, granted August 30, 1910,

Vupon the application of Clarence I. Robinson, of West New Brighton, New York,

for an improvement in RefiningPetroleuin,n errors appear in the printed speciiication requiring correetion n follows: Page 4, line 14, the wor sulfate should read sujd; page 13, lines I3-'74, Athe word convertings should read cmwertz'ng; and that the said Letters Patent should be read with these corrections therein thnt the same may qonform to the record 'of the case in the Patent Ofiice. Signed and sealed this 10th day of January, A. D.,191l. l

[me] C. C. BILL'INGS,

Acting Commissioner of Patents.