US968640A - Refining petroleum. - Google Patents

Description

J. G. BLACK.

REFINING PETROLEUM.

NITED STATES PATENT ormon- ,roHN c. BLACK, or 'aIcHMoNn CALIFORNIA, AssIeNon 'ro s'rnnmmnoir. COMPANY, or nreHMoND, cALIFoaNIAfii ooarom'ronor GALIFORNIA.

REFININ G- PETROLEUM.

` Tofollfwhomt may concern:

, -nin Athe fg This .invention .relates more particularly to the refining of .such petroleum as is ob- --tained from wells in the State of California,

Be it known that I, JOHN C. BLACK, al

citizen of the United States, residing at Richmond, inthe county of `Contra Costa and State of. California, have invented certain new and useful Improvements in Re- Petroleum, of which improvementsv allowing is a specification'.

lresist removal .by treatment with ordinary sulfuric acid of 66 Baume (in however large roportion') although they are removable in large part at least) by means of .appropriately stronger acid, as fuming sulfuric acid or sulfuric anhydrid.

The treatment herein above referred to, which belongs to the prior state of the art, consists in agitating the distillate with sulfuric acid (ordinary or .fuming or anhydrous, as the case may be) allowing the ymixture to settle by standing, drawing oif .the dark colored liquid (called acid sludge) Which settles lout and then washing the oil with water-and afterward with causticv soda lye. When' the vtreatment is performed `vwith .sulfuric acid of suitable' strength to attack said smoky hydrocarbons (say, fum-- ingacid containing fifteen per cent. sulfurie anhydrid) the said sludgevis very acid (according to my experience), its great p acidi-ty being due, as `I believe, to the fact that -tarry bodies (products of the treatment) surround particles of the acidwith a coating which preventsv further action by the inelosed' acid.

v The expression, California oil or Cali- -forniaK petroleum is herein employed as a nvenient designationfof oil of the foregoing description. It is not confined to 4oil actually obtained from wells in California;

vbut it includes ,any petroleum, Wherever found or however obtained, the cracked or .uncrackeii burning oil (kerosene) distillate Specication of Letters Patent.

Patented Aug. 30, 1910..

Application led June 13, 1907. Serial No. 378,724.

vfrom which contains the aforesaid refractory smoky h drocarbons in objectionable proportion an yields a sludge of the character hereinabove set forth, when treated with sulfuric acid suiciently stronger than 66 B. acid to remove said smoky hydrocarbons, s'ay fuming sulfuric acid containing fifteen per cent. of sulfuric anhydrid; A

In treat ing California oil, inthe form ofV vburning oil (kerosene) distillate either with fuming` sulfuric acid or with solid sulfuric. anhydrid 1n order to remove refractory smoky hydrocarbons therefrom, there is a substantial-waste of acid (evidencedby the .great acidity of the sludge), more acid hav- .gas (which latter may or may-not itself'have a beneficial e'ect on the oil) and in-such a state of subdivision and dilution that the mixture remains transparent (or, in other words, nearly or quite free from fog or mist) at twenty degrees Fahrenheit ormore below the boiling point of sulfuric anhydrid (115,0 F The explanation, as I believe, for'this more eicient reaction of the sulfuric anhydrid on the refractory smoky hydrocarbon is not only that the sulfuric acid is in gaseous condition, but alsothat practically each molecule is sufficiently lseparated from every other by intervening-molecules of the diluent gas -to prevent V'its coalescin'g with others and so forming particles of acid A(anhydrid) Vto be enveloped by tarry products. Every molecule ofsulfuric` anhydrid (or nearly so) consequently oombines chemicallygwith one .or morev moleculesI of smokfy hydrocarbon to form a sulfonic or sul one compound.A Such vconi- Epounds are heavierthan the oil; and settling out they forni a sludge which is yof a different color and composition from and of less acidity than that-which results from treaticc fectively without a ixture with diluentv gas; but the use of undiluted gaseous sul-y uric anhydrid would not, according tomy 3Q hydri experien'ce, have the advanta es in avoidin Waste of acid and oil in the s udge ossesse by the use of sulfuric anhydrid su divided and injadmixture with diluent gas; and my experience also leads to the conclusion that the more perfect its state of subdivision in thel diluent gas, in suitably low proportion, the less the waste of acid and oil in the from treating California bons thereof. The sulfuric lanhydrid would 'best (I believe) in any case be of catalytic formation and in its:originalgaseouscondition, as contradistinguished from the gaseous roduct from` va orizing sulfuric an- (Pl from Athe soli state, or from the liquid state, in which .it exists, for example, in fuming sulfuric acid; because (for one `reason) I believe the freshly catalyzed sulfurie anhydrid to be more active and elhcacious than such product; but, irrespective of this -itis (according to my experience) s ecially a ly formed sulfuric anhydrid in its said originally ous condition in order to obtain sulfurlc anhydrid inthe very perfect l state of subdivision in which it is obtainable bycatalytically converting sulfuric dioxid in apreviously constituted mixturev of the same with oxygen and diluent gas in proper proportions.4

i By passinga mixture of sulfur dioxid, oxygen and diluent gas, containing about four volumes per cent. of sulfur dioxid over catalytic material, I have obtained sulfuric anh drid in adm-ixture with diluent gas in t e proportion of about three and a half volumes j of the gaseous sulfuric anhydrid to one hundred volumes of the mixture and subdivided therein to such extent that the mixture remained trans arent free from fog or mist) when coole to 32 whereas, the mixtures which I have prepared of air and sulfuric anhydrid vaporized from fuming sulfuric acid, and then cooled,al though containing also three and a half volumes of sulfuric anhydrid per cent. have become full of` mist or fog from the condensed sulfuric anhydrid at less than twenty degrees `Fahrenheit below the boiling point ofsulfuric anhydrid.

advantageous to use the catalytic- It is not inconsistent with good results to havethe sulfuric anhydrid in the mixture proportion than three and a half volumes sults in refining California catalyzed gases containing t is proportion of-sulfuric anhydrid; and the larger its proportion, Vthe more apt the catalyzed gases are to show fog ormlst, when cooled; and in consequence of the less complete state of Vsubdivisionl and dilution thus evidenced, there is more apt to be an unnecessary loss of acid and oil in the sludge through (as I believe) a coalescing of the molecules of sulfuric anhydrid. Moreover, the larger. the proportion of sulfuric anhydrid in the .catalyzed gases, the more energetic is the chemical regeref unduly raising the temperature of the oil undergoing treatment. 'Op the other hand, an undue increase' in the proportion y pense of handling thegases in the treatment and tends to Waste oil by evaporation and oxidation (this last,"of course, in casel the diluent gas should contain oxygen, as it would with air as the diluent).

oxygen and diluent gas suit-able for passing over catalytic material, the most convenient .mode is to burn sulfur (or sulfur bearing material, as pyrites, for example) in air,I as

more air being Asupplied than takes part in plied should furnish just the amount'of oxygen needed to convert the sulfur dioxid into sulfuric anhydrid, the content of sulfur dioxid in thevmixture so obtained of sulfur dioxid, oxygen and diluent gas could not theoretically exceed about fourteen volumes per cent.; and the catalyzed gases in such case could not theoretically contain more sulfuric anhydrid than about fifteen volumes er cent. It is also possible to make suluric anhydrid by catalytic material from sulfur dioxid and ox gen Which are free or substantially free (either or both of them) from diluent gas or are mixed therewith in `tion. In fact, sul uric anhydrid was first successfully manufactured by catalysis by passing sulfur dioxid and oxygen free from diluent gas over the catalytic material. The use of such undiluted or less diluted sulfuric anhydrid isnot wholly excluded in practicing the invention, or in part thereof at least. y

In subjecting the California oil, in the form of burning oil (kerosene distillate, to

sulfuric anhydridras aforesai the reaction is influenced by the temperature. It is pos- Vthereof with diluent gas in a. less or a greater per cent.; but I have obtained excellent re-y etroleum withv actionand consequentlylthe greater the dan- .of diluent gas unnecessarily vadds to the ex" To obtain a mixture of sulfur dioziid,l

customary in making sulfuric anhydrid,

'the actual combustion. If the"air `s0 sup' less propprtions than results from burning sulfur (or sulfur bearing material) in air and `catalyzin'g the roducts'of such conibusn siblef-to-carry on the treatment/at tempeia-r tures not so low as twenty degrees Fahren,

V'heit (if any) below the boiling point of sulfurie anhydrid;"`but it is considered an ad# vantage and special improvement to maindegrees Fahrenheit or more below'said boi And, while this improvement does not necessarily require that the gaseous n mixture `containing the sulfuric. anhydrid should be trans arent at the temperature of the oil during its'treatment with said mixture, it is considereda further special ad'- vantage yand improvement to use a mixture which is transparent atr such temperature.

\The,re` need be no' practical difficulty in this re'ga'df; since a mixture remaining. transparent at 32 F. can be prepared as -herein "above mentioned; and my experience does not tend to -show that 4any benefit (commensurate at least with the, extra cost) would result from treating the oil at temperatures below 32 I have obtained` good results .being then, 'accordin by treating at about 85 F.; but lower,tem peraties would be more advantageous, there to my experience, la saving of acid and oi as compared with an i (therwise precisely similar treatment at 85 F. Temperatures between 40 F. 'and about 60 yFfare considered best. is.,

-`To subject the California oil to the sul- 'furie anhydrid, use can bejmade ofany known or suitable operations and appliances for brin 'ng' gases and liquids into contact v'with eac other. Byiw-ay of example, an"

fag't'ator similar to that commonly used; in treating il with sulfuric acid may be specially mentioned, the agitator being made of iron and without the usual lead lining, and

the freshly catalyzed gases, composed mainly of diluent gas, being drawn (by suction)orv I bein forced (by, pressure) through the distill andserving to agitate the same.; but 'the distillate can be 'showered through the freshly catalyzed ases in' towers; or

l other` known or suitab e arrangements for bringing gases andliquids in contactwith each other can be used. n When reference is herein made to the volume per cent. of sulfuric anhydrid in admix'tur with diluent gas, the sulfuric.

' anhydrid is, of course, to be measured in the gaseous condition; yet non-gaseous sulfuric anhydrd in admixture with diluent gas can be regarded as-constituting a-specified numi ber .of volumes of sulfguric anhydrid per V cent. 'of the mixture, namely, the number of volumes ericent. which the sulfuric anhyydrid vwou d occu y'if the mixture should be heated sufficient y to vaporize yall the nonf gaseous sulfuric anhydrid therein.

l oil (kerosene .The A.California oil in the form of burnin" distillate is treated until it burns 'proper y in a lamp, or/at A least until it 'exhibits .the desired (and feasible.)

amelioration vin respect toits content of l the amelioration thereof is carried; and the rate at which theA sulfuric anhydrid is l,brought into contact with the oil can be varied. Specific 'instances willv vbe given hereinafter by wayA of example.

Reference has so far been made only to California oil,A as herein above defined ;y but there are other oils to Whichthe invention,

` it is believed, can usefully be applied' in whole or in part. There are petroleums so far analogous to California oil that they contain in their burning oil (kerosene) fractions in objectionable proportions, objectionable hydrocarbons which resist removal by ordinary concentrated sulfuric acid of 66 B., although removable in large part at least by ysulfuric acid of suitably greater strength. Such lhydrocarbons may ve objectionable eitherv because composed of so much carbon as to be smoky (as in the case of oils obtained from Wells in Texas near Beaumont, in Jefferson county) or becausecomposed in part `of sulfur (as in the case of oilsobtained from Wells in Chio near Lima, in. Allen county, and Indiana). In 'obtaining burning oil (kerosene) from suoli van analogous oil, the same in the form of burning oil (kerosene) distillate would be ,subjected to sulfuric anhydrid substantially in the form of burningvoil (kerosene) distillate, as well as to )California or analogouspetroleumA as herein above defined in particular, and also to California or analogous petroleum or to petroleum in general in other forms `than that of burning fr oil (kerosene) distillateand evento nonpetroleum oils (mineral, vegetable orl animal) susceptible of refinement. by means of sulfuric -adhydrid The, invention extends to alltreatments embodying new andvr original features herein set forth. The

invention also includes new anduseful ap'- paratus for use in the refining o'f California lor analogous petroleum or other oil; and

each new; useful and original part, improvement or combination (Whether of process or apparatus). is intended to be secured for all the uses to which the same can be applied. Modifications by addition, omisson orothersul wise are permissible indefinitely so'long as the substance is taken of any one or more of the claims at the end of the specification.

Figures l and 2 of the accompanying drawings are each of them a diagram of one form of apparatus in accordance with the inven-` tion; and the following description gives, by way of example, speclic instances of treating California petroleum in' the form of burning oil (kerosene) distillate in accordance with the invention, in eaclf of which instances a batch of lsuch petroleum is so treated by the vaid of apparatus diagrammatically represented.

Referring to Fig. 1, and assuming that one thousand barrels (forty gallons to the barrel) of distillate, suitable for making water white burning oil (kerosene) of 120O F. re test, have been obtained from California petroleum in the known `or in any suitable way, and are to be treated, such distillate is rst given a preliminary treatment by agitation in the ordinary lead lined agitator with ordinary sulfuric acid of 66D B., using,

say, about four pounds to the barrel. Afterv settling, and drawing off the sludge, the distillate is charged into the iron agitator a provided with an interior perforated Huid distributer b at the bottom and an exterior perforated fluid distributer o at the top. Gaseous sulfuric anhydrid, subdivided and in admixture with diluent gas, is then passed through the distributer b into the distillate in theiagitator a until test portions of the distillate (removed from time to time for the purpose) show' that the desired (and. feasible) amelioration of the distillate in re*` spect to smoky hydrocarbons has been eHected. Said portions are best prepared for testing by agitation with ordinary sulfuric acid of 66o B. at the rate of about two and a half pounds to the barrel, followed by settling, drawing of the sludge, and washing rst with water and then with caustic'soda lye;` and they can be tested either-by burning.

them in a lamp or by determining their refractive indexes with a refractorneter. Removal of smoky hydrocarbons is` shown by the refractive index of the distillate being lower after treatment than before the same.

To supply the gaseous sulfuric anhydridin a suitable state of subdivision anddilution, sulfur (or sulfur bearing material) is burned in a sulfur burner d by means of air; and the products of such combustion, mingled with air in appropriate quantity to supply the oxygen required to convert the sulfur dioxid into sulfuric anhydrid, are catalyzed,

say

convert each hour about two hundred and twenty five and three-quarters poundsA of sulfur (equal to about three and six-tenths ounces of sulfur per hour to each barrel of oil) into sulfur dioxid; and the resulting by platinum. The combustion in thev ur burner d may "be regulated so 'asto1 seven volumes ofsulfur dioxid andninely three volumes (together) of .oxygen and d' appropriate purifier e to the purify -erations customary in mak-ing sulfuric anhydrid by catalytic methods, or to any neces-l passed through the ca talyzing chamber f containing catal tic material (such as platinum, for examp e) lfor converting the sulfur dioxid into sulfuric anhydrid in the known way. From chamber f, the catalyzed ses, -consisting of about seven volumes o sulfuricanhydrid subdivided and inadmixture with about nine three volumes of `diluent converted sulfur dioxid), are passed through thelcooling coil g and trap h (which -receives any products of condensation from coil g) and are then introduced through the Adis- At z' is shown an exhauster, for` drawing the gases through the oil.-` During the treatment the, contents of the agitator are ke t at a point of sulfuric anhydrid, andbest between about 4:05 F. and about 60 F. produced articially by means of water delivered in jets by distributer c onto the outside of the agitator a; but if the water supply available is not cold or not copious enough for giving such low temperature, goed results are at# i tain-able at temperatures aboveabout 60 F. The delivery ofthe catalysed gases may be ing to the amelioration desired; but, with isfactory burning oil (kerosene) should be preliminary treatment; but 'the useful/maximum would be about tenl pounds of the 66 B. acid to the barrel of distillate, according acid has been `found to have little or no, furf' ther effect when used in larger proportion.v After the treatment with the gaseous sulfuric anhydrid is ended, the distillate is althe distillate is transferred. to an ordinary lead lined agitator. In this last it is agiproducts of combustion, consistingof about uent gas, (nitrogen), are; first subjected in an' ing op-y sary or suitablepurication, and are then` gas (composed'o nitrogen, oxygen and unobtained after a treatment 'of about thirty` concentrated sulfuric acid 'of 66 B. in the 120 to my experience; inasmuch as said 669 B.A

tributer b into the distillate in agitator a.

temperature substantially below the oiling continued a longeror shorter time, Aaccordy distillate' of the character mentioned, a satlio lowed to settle; the sludge is drawn off; and

tated with about twenty 'seven hundred pounds of ordinary sulfuric acid of 66 B. (being about two and seven-tenths pounds-to the barrel) in order to improve the color and odor, as well as-to remove sulfur com.

pounds (whether naturally lpresent or absorbed from the gas and not deposited in the Sludge. After drawin oii' the sludge forme by the 66 B. aci the oil'is washed first, with water and then with caustic soda l e and is ready for shipment as burning oil kerosene). p

yReferring to Fig. 2, and lassuming that one has to treat one thousand barrels of distillate similar to that taken byfway of example in the description Withreference to Fig. 1, the combustion of sulfur or sulfur bearing material in .the sul-fur burner d by means of air may be regulated as before so 0 as to convert .each hour about two vhundred and twenty `iive and three-quarters'pounds of sulfur (equal to about three and sixi tenths ounces per hour to each barrel of oil)y into sulfur dioXid. The productsof combustion, containing about seven volumes of sulfur dioXid and ninety .three volumes of oXygen and diluent gas, are passed through catalytic material; in .the form of iron oxid inthe chamber Ze. By this material about half thesulfur dioxid is converted .into sulfactory burning oil (kerosene) .should ,b .efobfA furie anhydrid. The so catalyzed gases are passed through a-,tower Z; and their content \of sulfuric anhydrid is-absorbed in sulfuric acid therein; while at the same time the gases are purified preparatory to the subsequent conversion into sulfuric anhydrid of Vthe sulfur dioXid which escaped conversion by the iron oXid inchamber is. From tower Z the gases are passed through a furtherpuritier m and then .through the catalyzing chamber f containing catalytic material (such as platinum, for example) for converting the sulfur 'dioxid into sulfuric acid in the known way. From chamber f, the

a half volumes of sulfuric anhydrid subdivided -and in admi-Xture with ninety six and a volumes of' diluent gas, are passed through the :cooling c'oil g and ftrap'h, and

into the distillate in agitator a. During the treatment -thecontents of the agitator a are kept 4atfa` temperature substantially belowthe boiling point of sulfuric anhydri'd, as before described with reference to Fig. l; and the delivery ,of the catalyzedgasesv may be continuedr alonger or shorter time, as also described. with .reference thereto. With dis- I tillate of the character mentioned, 4a satistained after a treatment of abouts'ixty four hours, fusingaltogether inthe 'tator' Va about eighteen .thousanpoundso sulfuric anhydrid subdivided and.. inadmxtlilfe. with d iluent .gasin the .proportionof about .three catalyzed gases, containing about three andare then introduced through' the distributerv and a half volumes of the former to ninety six' and a' half volumes of the dluent gas- The sulfuric anhydridthus used in agitator ais at the rate Yof about eighteen* pounds ofl sulfuric anhydrid to the I`barrel of distillate. Thev time .of treatment can be shortened somewhat and the amount of sulfuric anhydrid required for a given amelioration of the V oil in respect to smoky hydrocarbons therein can be somewhatgdiminished by using more of the' ordinary concentrated sulfuric acid of 66 B. .in the preliminary treatment, as before described with reference to Fig. l. In using in agitator a catalyzed gases containing about three and a half volumes per cent of sulfuric anhydrid asf described with reference to Fig. 2) the' treatment would best occupy about twice as long as in using therein catalyzed gases containing4 vabout seven volumes per cent .of sulfuric anhydrid (as described with referenceto Fig. l) but the amount of sulfuric anhydrid consumed in agitator awou'ld be about the same. In proceeding. as described with reference to Fig.

furie anhydrid would be abso-rbed in sulfuric acid inthe tower l and would be utilized as might be preferred. l

The preparation 'of thecatalyzed gases as 2, an equal quantity or therea'boutlof sulsgg described with reference to Fig. l may be` inl accordance either with what is known 5as the single conversion system of making. sulfurie anhydrid, of which system the Badische process and the Schroeder process are each an example; while the preparation of such gases as described with referenceto Fig. 2 may be in accordance with. what is known. as the double contersion system of making sul- -ffuric anhydrid, ofwhich system the Mann- The present heim process is an example. invention is not restricted to these processes; but any ayailable processA ofpreparing the catalyzed gases can be used.

The gases from vthe first catalyzing operav vtion of the Mannheim process, namely, the 11o gases from the chamber ,7o ofrFi 2, canbeu'sed as a form ofgaseous sulurlc anhydrid subdivided and in admixture with diluent gas inl the proportion of about three 'and a.

alf volumes percent; only it is considered 1115 uneconomical fto. do so for lone reason on account o thelarge ercentage of unconverted sulfur dioxid Vin tllie diluent gas, which unconvertedfsulfur dioxidmust be .wasted unless utilized subsequently andthe subsequent 120 utilization .of which would no doubt be less l economical, if not open .to diiiiculty other- Wise.I 'The .gases from chamber c could, for

,'example, be/passed into the` oil .in an agitator'through a distributer therein, the same 125 asdescribed with reference to Fig. 2 for the gases from chamber f of said. Fig'. 2.

apply. :the gas treatment in making hurnlng oil lflero'senel from petroleum analogous to California oil, as yherein above 13 0 set forth, the procedure can be substantially as described, such analogous oil being subjected in theform of burning oil (kerosene) distillate in agitator a to the subdivided and diluted sulfuric anhydrid Jfrom the catalyz,

ing chamber funtil the'desired (and .fea-

and also for treating non-petroleum oils with Ordinar treatment, if preferred. For example.,v1n

' treatment.

(whether of mineral, yvegetable or animal origin) to which the as treatment may be applicable, the proce ure .need not-."(I" believe) .be substantially varied. I do ynot profess to have actually applied the gas case the gas' treatment to all oils. In an treatment would be continue until the desired (and feasible) 'amelioration in the oil under treatment should be efectedyand it may well be found expedient to adjust the rate atwhich the catalyzed gases are delivered into the agitator, according to the case. While sulfuric anhydrid is able to re'- move ,hydro-carbons which resist sulfuric acid of 66o B., it is also able to remove some at least of the bodieswhich are removable by 66 B. acid; and hence a gas treatment with sulfuric anhydrid can be used .in general wherever a treatment with sulfuric acid is appropriate.

As a general proposition it will (I believe) be found best to a ply treatments sulfuric aci of 66 B.- acid before and a er the gas treatment with-sulfuric a-nhydrid; but 1t may not in all cases bagmfo'und desirable to do so; and I do not w'sh torestrict myself to the use of such preliminary and subsequent treatments or of either of them. The proportions of 66o B. acid to be employed in such preliminary and subsequent treatments (if used) would be jadjusted according to the case. The oil 'can be subjected to any other treatment before or after or concomitantly with the 'gas refining California oil, the same in the form of burning oil (kerosene) distillate couldl be given (if preferred) a treatment with fuming vsu furic acid before or after or con- 'comitantly with the gas treatment; and the oil could be rerun before or after the gas The expression those of the hereinafter Written claims in which it occurs means primarily other petroleum, but by extension it vincludes nonpetroleum hydrocarbon oil which is capable of yielding (or consists in whole or in part of) burning oil distillate, other appropriate other oil as specified in" hydrocarbon oil, and falso other oil in general, as vegetable fatty oil, forexample, to which a treatment With sulfuric acid would be appropriate.

i The expressions means as specified connected with said conveyer for subjecting oil to the thereby conveyed sulfuric anhydrid and means as specified connected with said conveyer for subjecting oil to the thereby conveyed-gases are eachA of themused in contradistinction to means for subjecting a liquid in general to 'aeriform fluid in general or for subjecting liquid sulfuric a'cid in par'- ticular to aeriform fluid composed of or containing sulfuric anhydrid. Said expressions each of them primarily refer to means composed of (l) an upright vessel for holding a body of the oil during treatment and (2) a distributer near the bottom of said vessel for introducing aeriform fluid composed of or containing sulfuric anhydrid into the body l of oil in said vessel, appropriate appliances (not shown) ybeing used to su ply the said vessel with California or ana ogous petroleum or other soil as specified in contradistinction to other' liquid, and a distributer for applying cooling liquid to -the outside of said vessel being advantageously, but not j necessarily, provided. lSaid' expressions, each of them, by extension also include in- 'strumentalities in general of known (or of any suitable) description for bringing aeriform'iiuid and liquid intocontact With each other when, and only Whernqsaid instumentalities are designedly arranged With reference to the subjection of California or analogous petroleum or other oil as specified to aeriform fluid composed of or containing sulfuric anhydrid.

The expression means as s ecified for separating the resulting sludge rom the sotreated oil refers primarily to a funnelshaped bottom on the aforesaid upright vessel in which the oil is held While subjected to ythe aeriform fluid composed of or contain# ing sulfuric anhydrid, said bottom having a draw off at the small end of the funnel, so that the sludge after settlingout in -said vessel can readily be drawn oil'l before drawing off the treated oil. By extension said ex pression includes instrumentalities in general'of known or any suitable description for separating liquids of different grivities from each other when, and only when, said instrumentalities are designedly arranged With reference to the separation from California or ucing temperature and in the form of burn-- ing oil (kerosene) vdistillate containing smoky or sulfurous hydrocarbons which 'resist removal by sulfuric acid of. 66 B. to'

such mixture, continuing the treatment with such mixture until an amelioration of the oil is elfected in respect to its content of said I smoky or sulfurous hydrocarbons, and separating the resulting. sludge and4 the. so refined oil from each other, substantially -as described.

2. 'The improvement-in refining Californialor 'analogous petroleum', consisting in subjectig such petroleum at sludge producing temperature and in the form of'burning oil (kerosene) distillate containing smokyy 4or sulfurous hydrocarbons which resist removal by'sulfuric acid of 66 B to gaseous sulfuric anhydrid,' continuing the treatment with, such-reagent until an'amelioration of the oil'v "subdivided sulfuric anhydrid and diluent is effected yin respect to its content of said smoky or sulfurous hydrocarbons, and sepa. rating 'the resulting sludge and the s rei-ined oil from -each other, substantiall as described. a

f3. The improvement -in. refining oil, to' wit, California or analogous petroleum or.

other roil as specified, consisting in forming outside the` oil to betreateda mixture of subdivided sulfuric anhydrid and diluent gas, subjecting .said oil at .an artificially produced temperature of not.' less than twenty degrees Fahrenheit below 'theboiling point of sulfuric anhydrid .to such i'nix' ture, continuing the' treatment'` With-such mixture until an ameliorationis 'effected in tlie oil, and separating the resulting sludge from the so refined oil, substantially 'as 4described. v

4. The improvement in refining oil, to

` Wit, California or analogous, petroleum o r other-oil as specified, consisting informing Outside of the` oil to be treated a mixture of subdivided sulfuric anhydrid and diluen't gas containing not more than'about fteeny per cent. by volume ofsaid sulfuric anhythe, resulting sludge from drid, subjecting said oil at sludge-producing continuing the treatment with such mixture until an amel- -ioration is effected inthe oil,'and separating the so refinedI oil, substantially as described.-

5. 'The improvementin refining oil, to wit, California oranalog'ous petroleum or other' oil as specified, consisting informing outside-of the oil to' be treated a mixture-'of subdivided sulfuric anhydrid and diluent gas containing not less cent.- and not more than about fifteen percent.- by volume o f said sulfuric anhydrid, subjecting said oilat sludge producingtemperature to such mixture, continuing the treatment with such mixture-.until an amel-f iol-ation is eifecte'dinthe oi-l, and separatingthan about one per substantially `as desoribed.-

'6. The improvement in refining oil', to wit, California zor analogous petroleum or other oil is fspecified, consisting in forming outside ofthe oil to be treated a mixture Fahrenheit 'below the boiling point of suldrid and` diluent, gas, subjecting said oil at sludge producing temperature to such 1111xture, continuing the treatment with such mixture until an amelioration is effected in the oil, and separating tlie'resulting sludge from the so refmedoil, substantially as de' scribed. i

Y 7. The improvement -in refining oil,. to. wit, Californial or analogous petroleum or outside of 4the q il to be treated a 'mixture transparentat the 'treating temperature of pera-ture to the so obtained catalyzedgases, continuing the treatment with said gases until an amelioration' is eected in the oil, and separating the resulting sludge and the so reined oil from each other, substantially as described.' l

4ot-her'oil as specified, consisting in-obtaining a'mixture of sulfur. dioxid, oxy en anddilu-l or sulfur bearing material in air, passing rial for' convertingsulfu'r ,dioxid 'intfsulproducing temperature` to the so obtained with said gasesuntilan amelioration lis efin sludge'and the so ref ined 011. fromot er, substantiallyas described."

wir,

j ing the oil at sludge producing temperature to catalytically formed sulfuric anhydrid'in furie anhydrid of subdivided sulfuric an'hy- 9. .The improveme'lt rening oil, to' wit, California or analogous petroleum. or

`tl1e so obtained mixture over catalytic :natecatalyzed 'gases,.; continuing tl1'e treatin/ent 10. 'll} ie improvement in refining-oil, t o` Ca ifornia or analogous petroleumforother oil asv specified,- consistingin'subject- .its Voriginal gaseous state of format1on,' con' f tinuing the treatmentwith'such reagent un- -tlie resulting sludge-from" thesorefined bil,

transparent at not less than twenty degrees.

Y other oil as specified, consisting .in forming.'

roo

ing-'sulfur dioxidI into sulfuric anhydrid,4 subjecting said oil, at sludge producing temvent gas bythe aid of a combustlon of sulfur' f furie anhydrid, subjecting said oil atsl-udge fected in' the oil, and separating the result# f eacl'iV 'fined oil from-eacli other, substantially as wit, California or analogous peti-o eum or wit, California or analogous petroleum or California or analogous petro elim or 'other veyingtheiice the therein formed sulfuric an y ri i at sludge producing temperature whilesaid til'anamelioration is effected in the-oil; and separatin the resulti'n slud 'and the so refined oi ifrom'each ot er, sistantially as described.

11'. The improvement inrefinin -oil,`tot

other oil as specified, consisting in subjecting the oil at a temperature notless than twenty degrees Fahrenheit below the boiling point of sulfuric anhydrid to catalytically formed sulfuric anhydrid in its orig'- inai gaseous state of formation, continuing theV treatment with such reagent until an amelioration vis effected inthe oil, and separating the resulting sludge andthe so re.-

described. y y

12. The improvement in refining oil, to

oil :is specified, consisting of means forcatalytically forming sulfuric anhydrid, -a 'gas conveyer leading from said means and cond in its original gaseous state of catalytic formation, means as specified connected with said conveyer for subjecting the oil to thereby conveyed sulfuric anhydrid sulfuric 'anhydrid is: yet in its said original gaseous' state of catalytic formation, and

' the resulting sludge rom the so re means as specified' for separating ,the result- A esac-m in A slud'geffrom these refined oil, substantia y as described.

14. Apparatus for refining oil as Specified, consisting ofmeans for producin a mixture of sulfur dioxid, oxygen and iluent gas and. for passing said mixture over catalytic material for converti-ng sulfur dioxid into sulfuric anhydrid, a. gas conveyer leading from said means and conveying thence the gases obtained by passin said mixture over said catalytic materia, means as specified connected with said corrveyer for subjecting oil to the thereby conveyed gases at sludge atu're, and means as s epied for se aratin ned ci?, substantially as described.

1 5. Apparatus for-refining oil, Vto wit, California or analogous petroleum-or other oil ase specified, consisting of means for burning sulfur or 'sulfur bearing material .in air and for passing the products of such combustion in the form of a mixture which contains free oxygen over catalytic material for converting sulfur dioxid into sulfuric anhydrid, a gas conveyer leading from said means and conveying thencethe gases ob` tained by passin said mixture over said catalytic materia means as specified connected with said conveyer for subjecting oil to the thereby conveyed gases at sludge producing temperature, and means as specified for se arating the resulting sludge fromthe so re ned oil, substantially as described.:

In testimony whereof I axmy signature, in presence of two witnesses.

,A JoHN o. BLACK. A' Witnesses WILLIAM C. HARRIS,

F. S. BAiicooK.

u conform to the record of. the cage in the Patent Oce.

I Signed and sealed this' 10thday of January, A. 11,1911.l

"ofc siLLinGs,

Acting (lbf/missioner QfPaeiits.

- oil, to wit," California or analo ous petroleum or otherA reducing temperisjhercbyr certifiedthatin Letters .atellt bla/968,644), granted Auigiist', 1916, upon the application of J oliii C. 4l'llack, of Richmond, California, for an irnprovement in "C'Renin Petroleum, errors appear in the specification requiring correction as follows:` Page 2, line 2.,.the` sulfo'nicu should read sulfuric, and same page,l line 125, the worli fin part should read a pas-i5; and that A the said Letters Pateln't'shold beiread With these corrections therein that the same may 'fined oil from-eacli other, substantially as wit, California or analogous peti-o eum or wit, California or analogous petroleum or California or analogous petro elim or 'other veyingtheiice the therein formed sulfuric an y ri i at sludge producing temperature whilesaid til'anamelioration is effected in the-oil; and separatin the resulti'n slud 'and the so refined oi ifrom'each ot er, sistantially as described.

11'. The improvement inrefinin -oil,`tot

other oil as specified, consisting in subjecting the oil at a temperature notless than twenty degrees Fahrenheit below the boiling point of sulfuric anhydrid to catalytically formed sulfuric anhydrid in its orig'- inai gaseous state of formation, continuing theV treatment with such reagent until an amelioration vis effected inthe oil, and separating the resulting sludge andthe so re.-

described. y y

12. The improvement in refining oil, to

oil :is specified, consisting of means forcatalytically forming sulfuric anhydrid, -a 'gas conveyer leading from said means and cond in its original gaseous state of catalytic formation, means as specified connected with said conveyer for subjecting the oil to thereby conveyed sulfuric anhydrid sulfuric 'anhydrid is: yet in its said original gaseous' state of catalytic formation, and

' the resulting sludge rom the so re means as specified' for separating ,the result- A esac-m in A slud'geffrom these refined oil, substantia y as described.

14. Apparatus for refining oil as Specified, consisting ofmeans for producin a mixture of sulfur dioxid, oxygen and iluent gas and. for passing said mixture over catalytic material for converti-ng sulfur dioxid into sulfuric anhydrid, a. gas conveyer leading from said means and conveying thence the gases obtained by passin said mixture over said catalytic materia, means as specified connected with said corrveyer for subjecting oil to the thereby conveyed gases at sludge atu're, and means as s epied for se aratin ned ci?, substantially as described.

1 5. Apparatus for-refining oil, Vto wit, California or analogous petroleum-or other oil ase specified, consisting of means for burning sulfur or 'sulfur bearing material .in air and for passing the products of such combustion in the form of a mixture which contains free oxygen over catalytic material for converting sulfur dioxid into sulfuric anhydrid, a gas conveyer leading from said means and conveying thencethe gases ob` tained by passin said mixture over said catalytic materia means as specified connected with said conveyer for subjecting oil to the thereby conveyed gases at sludge producing temperature, and means as specified for se arating the resulting sludge fromthe so re ned oil, substantially as described.:

In testimony whereof I axmy signature, in presence of two witnesses.

,A JoHN o. BLACK. A' Witnesses WILLIAM C. HARRIS,

F. S. BAiicooK.

u conform to the record of. the cage in the Patent Oce.

I Signed and sealed this' 10thday of January, A. 11,1911.l

"ofc siLLinGs,

Acting (lbf/missioner QfPaeiits.

- oil, to wit," California or analo ous petroleum or otherA reducing temperisjhercbyr certifiedthatin Letters .atellt bla/968,644), granted Auigiist', 1916, upon the application of J oliii C. 4l'llack, of Richmond, California, for an irnprovement in "C'Renin Petroleum, errors appear in the specification requiring correction as follows:` Page 2, line 2.,.the` sulfo'nicu should read sulfuric, and same page,l line 125, the worli fin part should read a pas-i5; and that A the said Letters Pateln't'shold beiread With these corrections therein that the same may Corrections in Letters Patent No. 968,640;

It isihereby certified that in Letters Patent No. 968,640, granted August30,

19K), upon the application of John C. Black, of Richmond, California, for an improvementin Refining Petroleum, errors appear in the printed specification requiringr correction Aas follows: Page 2, line 2, the:l word Sulfonic should read salftm'c,

and same page, line 125, the worlls in part should read a part; and that the said Letters Patent should be read with these corrections therein that the .same may i. conform to the record of. the ease in the Patent Ofce.

il Signed and sealed this 10th day of January, A. D., i911. i r [SEAL] C. U. BILLINGS,

Acting Urn/1m axz'oner (gf Patents.

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