US2149322A - Oil treating process - Google Patents

Description

March 7, 1939.

M. H'. TUTTLE 2,149,322 on. TREATING PROCESS Original Filed Sept. 6, 1933 A TTORNEYS.

Patented Mor. 7, 2,'149efi'22.l

UNi'rsD STATES PKTENT ol=l=icss amaai omms'mionoclssf mieolmnniev'rntileLNewmehelieNjns-f slmrtoMaxBIille!&Co.,Ine.,NewYol-k. llLY.,amirpiil'atiollIl )ehware sppiieeiionseptenlieransaserismes'sssu e leneweilNovember4. 1937 e l e 4GslmaA-(CL196-13) This invention pertains to an improgvedproces paramnic or lubricating tractionso! a mineral oil of reilnins mineral oil by means of paraiiinio and from the non-parailinio (naplltheliie)l or tarry naphthenic solvents which separate the oil into fractions oi' the oil.' the several non-Aparaillnic relatively paramnic and naphthenic fractions. constituents being removed in a'unitary opera- 5 The present application. embraces matter dition.

vided i'lroin my copendins 'application ser; No. Thecolnbinins of solvents should be'done underl 633.483. lvod July 20. 1932. entitld Prooee Ind conditions such that the tendency or capacity ot www! for septum of mineral-0118"; One. thev solvent for parai'llnics to dissolve non-parmannerofcarrylns outthisprocessisde'scribedin amnics in additionto the paraiiinic values, normy United States Letters Patent 1.912.349. issued a mally dissolved therein, is compensated for or 10 lll! 1933- ,balanced by a like capacity of the solvent for non- Throllsh my invention it i8 poible to @vente paramnicsno dissolve paramnics as' well as the a residual mineral oil into its several components. 'nepnthenms or non peremni, i or constituents. and more particularly into' a m the new ,heee of the rem accompanying is lubritins 011 fraction conta-mins substantially Athe present application endformins e port there 115 all oi the high-boiling paraiilns and into another, of, there i, @om friction 0f the non* In jns. 1 a schematic rprentauon of the d15- wmc r caged fm'phthenic" lues 0f, tribution of the constituents of mineral oil in the om one the types of ,crude ons. w l 20 termodtmpolum A InFlLZthereisshownanidealizedrepx-esenta- 20 A* n0@ n my Punti bm mmv-t tion of e. Mid-continent crude. tosethervwlth e, oleo!! @mmm 0f the Dmc *ndr non' graphical 'representation of the solvent eilect of l c'tractions oa' mixed-baseoilmaybe f obtained hy the, simultaneous .tm ent of the :elmfgngofngfl ma n 198mm 2, originel oil with. notable peremnie solvent enen In M 3 there disclosed 'a mmm .me 251 I meng l enrfgmsglevent ya??? E tation of ilow sheet indicating thecombinasolventfcapaoity of which for pafanics is com- :ieegtfsf th@ augmente: onewn ts ref pensatediororreducedtoaminlmumhythe 'p- 3o mamme went hosenerably, as utilised in the process oi the present invention. l mettesse i .www e ee dem. ne i me conm me and mphthemc www Fig. 1 a reliesentation of illustrativev crude oil A stocks. in w ch the non-parailinic constituents mmlllgdpmgggg il: :gaf: mayvary from as little as 8 per cent. oi thecrude 3, tively nenhthenio, whieh eonpnees eemminaune' n mk s mud s 65 per mt' f the me d oil stock. It is in the treatment of the latter time themineraloiltobeseparatedwithaparamnic., f solvent oi the H0519 consistinsoi' llqueiled. noxof mg present invention is www mallygaseous hydrocarbonsA and petroleum ether, y 40 with e nephthenie solvent mixture continuing; Refem u? F18-- 2 there is shown dlasrm- 40 nemnthenicsolvent having es brood e Ksolvent www hw different wivnwvw in thnir wwe;-r eenitrobeneene for u 'nmwemmc conge capacity to dissolve the several types oi nonstitue'nts oi the oil. and another naphthenic ma nsmuents of crude 0n m' `Fr e leent wmeh he; e, relatively limited servent instance,- sulphur dioxide and furfural are both 4'5 power, controlling the temperature ef the extl'elllely limited solvents which only dissolve a 45 at a point where the broad and vlimited solvents minute Proportion ond limited ranse of cone are miscible to but" e limited extent with-ehe stituents. Solvents .like nitrobenzene, nitroc solvent'and thus cause an effective 'toluene and cre'syllc acid dissolve. substantially separation oi the oil into layers,eand separating B11 the noi-Damme oontituents. includinge 5o thelayers thus produced. The processisparticunephthenes, aromatica .and phltenos, and. 5o larly advantageous in connection with the treiitwhen used .in a'sinsle solvent system, also dis- 'ment of residual oils which contain upwards or' solve a substantial proportion 'of paramnic oil. 40 per cent. of non-parailinic constituents 1n- However; in the double solvent. counterilow syscludins naphthenes, aromatica. and asphaltenes. 'tem employing both paraiilnic `and -naphthenie 'x ss ensblins-thedireot andclean separation of thel solvents. the paraiilnlo solvent producesa clean separation oft'paraiiinic oil fraction.,

This is best )illustrated in Fig. 3, where it is shown that the oil in the preferred form of the invention, at the middle of the system so that the fresh parafiinic solvent rises, after washing the naphthenic exoil from non-parailinic tract, andi the mixtureof non-parafnic solvents settlesthrough the crude oil, after washing the parail'inic fraction at the upper end of the system. In the drawing, there are shown various ex amples of suitable solvents which may be com /bined according to the present invention. For instance, when a small proportion of a limited,

16 non-paramnic solvent is combined with a large i "proportion of` a broad, non-paraiiinic solvent,

`such as cresylic acid, a non-parailnic solvent is obtained which may be used with a paraiilnic solvent, such as propane, to produce a good separation of the lubricating constituents of a residual oil from the non-paraiiinic constituents,l of theoil. l,

The broad solvents which dissolve all the `nonparalnic constituents including naphthenes,

g5 aromatics and asphaltenes may. thus be made particularly effective .by incorporating therewith suitable amounts of limited solvents which dissolvel only certain small proportions ofsome of the non-paralnic constituents.

so While propane has been described as a pre- 40 ,'ployed .of the class ferred parainic solvent it is to be noted that it is most eflicient when used with any of nitrobenzene, nitrotoluene or the organic tar acids and their derivatives. Further, its use may be ex- 1 tended byifproper proportionin'g of the non-parailinic or naphthenic" solvent members.

The higher boiling paramnic solvents -tend to lower the critical solution temperature of. the duo-solvent .system and when solvents are emoi pyridine, anilinel and l high critical solution temperature with propane. the higher 'boiling parainic solventsv maybe substituted to lower the. CnS., T. (critical solution temperature) and' so increase the solubility of oil in the naphthenic solvent.

It will be appreciated that the present invention comprehends as an integral part of the process thereof, that solvents of medium or average t solvent capacity -for either parainsor non-parafllns or s'o-called naphthenicsi of mineral oils may be used together in. suitable proportions to iurfural' resulting in provide mutually immiscible two-solvent-layer l systems., It will be appreciated further, from the data herein, that the solvent eiIect of the several solvents of medial solvent capacity may be duplicated or approximated by the proper combination of broad solvents,- as presentedabove, with limited solvents. i 4 j It is to .be noted that the capacity ofthe solvent materials, either for parafli'ns or nonparaiiins, may-be compensated for by the use of appropriate solvents for non-paramos -andparaflns, respectively, sothat a clean, clear separa tion of the parailinic or lubricating constituents oi a mineral oil may be separated from the nonparaiiinicor tar-forming naphthenic constituents. The various combinations of individual solvents .to effect or give rise to composite solvents?` approximating the preferred paraflinic and nonparamnic solvents, is shown in Fig. 3 and has@ been dicussed in more detail hereinabove. t Fromthe foregoing it will be'seen that an imto be treated is introduced,

escasas portant feature of the present discovery resides in the, sfact that non-paramnic solvents of progressively greater general solvent power for all vof the constituents of mineral oils as well as the non-parainic constituents thereof, may be combined with other solvents for non-paramnics, or certain constituents thereof, to form restricted solvents which may baus'ed with paraiinio solvents of restricted solvent capacity for non-paramnics whereby to complement the same and 'permit the securing oi eective and clean separation of the-paraiilnic values of an oil from the non-paraiiinic values thereof. As an important feature ot this method it is to be noted that the' composite solvents'for the non-paraiiinics must be substantially immisible or insoluble in the sol-s vents used for dissolvingy the paraillnics in a mineral oil. Further, the said solvent for parafnics and the solvent for non-paramnics, or naphthenics, must be characterized by such dierences in their specic gravities that the formation of two-layer systems is furthered and made possible so as to permit the ready and emcient separation of the Asolvent systems and their respectively dissolved mineral oil fractions from each other.

Thus by employing a parailinic solvent in comrbination with a mixture of non-paraiiinic solvents, one of which has a broad solvent capacity for all non-paraipic oils, as well assome solvent capacity' for paraiinic oils, and one having a relatively limited solvent capacity, not only may an emcient separation of the oil be obtained, but also the critical solution temperature may be controlled at a suitable temperature for satisfactorily rapid separation of the oil into layers. i

It is to be understood that this invention is not to be limited by any theory of operation expressed or by any example given, and that it in-s cludes modications and variations falling within the appended claims.

What I claim is: -1. Process yof separating a mineral oil containing parainic and naphthenic type constituents into two liquid phases, one of which is rela,- tively paraiiinic and the other of which is relatively naphthenic, which comprises commingling the mineral oil to be separated with a paraiiinic solvent of the group consisting vof liquefied, norvent power, controlling the temperature of the mixture at a point where. the broad and limited solvents are miscible to but a limited extentwith the paraiiinic solvent and cause an eiectiv separation of the oil into layer and separating the layers thus produced.

2.-Process acclaimed in claim 1 wherein the limited solvent has a markedly higher miscibility temperature with the parainic solvent and oil than has thebroad solvent.

3. Process as claimed in claim 1 wherein sais paralnic solvent is liqueed propane.l

4. Process as claimed in claim 1 wherein the oil treated is a residual oil, and wherein the residual oil is introduced to thepresence of both paramnic and naphthenic solvents between the points where thevsolvents are introduced. A

MALCOLM HARLEY TUT'ILE.

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