US2471153A - Process of treating petroleum oils with a copper soap and of producing the copper soap - Google Patents

Description

c. o. HoovER 2,471,153 PROCESS OF TREATING PETROLEUM OILS WITH A COPPER May 24, 1949.

SOAP AND OF PRODUGING THE COPPER SOAP Original Filed Oct. 2, 1946 2 Sheets-,Sheet l C. O. HOOVER May 24, 1949.

PROCESS OF TREATING PETROLEUM OILS WITH A COPPER SOAP AND OF PRODUCING THE COPPER SOAP Original Filed 001;. 2, 1946 2 Sheets-Sheet 2 Patented May 24, 1949 UNITED STATES @ATENT OFFICE PROCESS F TREATING PETROLEUM OILS WITH A COPPER SOAP AND OF PRODUCIN G THE COPPER SOAP Charles O. Hoover, Houston, rex., assignor to Air Reduction Company, Incorporated, New York, N. Y., a corporation of New York Original application October 2, 1946, Serial No. 7 00,823. Divided and this application April 25, 1947, Serial No. 743,886

15 Claims.

fixing certain sulfur compounds, present in the naphthenate in the treatment of crude oil, as described above, or naphthenic acid liberated from crude petroleum oil during the distillation or fractionation thereof is first lconverted into an alkali-metal naphthenate, such as sodium naphthenate, and the alkali-metal naphthenate so produced, or an alkali-metal naphthenate from any other source, is reacted with a copper salt, preferably in the presence of a small amount crude petroleum oil to prevent formation of delof hydrocarbon oil which acts as a solvent for eterious sulfur compounds in the products of the Water-insoluble cupric naphthenate prodistillation of the oil. duced as a result of the double decomposition This application is a division of my applicaof the sodium naphthenate and copper sulfate. tion Ser. No. 700,823 filed October 2, 1946. The process preferably is carried out as a cyclic It is well known that most crude petroleum one in which the cupric naphthenate formed by oils contain sulfur in the form of hydrogen sulreaction oi the alkali-metal naphthenate with de or in more complex forms, the exact natures the Coppel Sulfate S used in 'Gllc treatment 0f of which are not known. When such crudes are hydrocarbon OilS aS described abcVe, and 'the distilled, reaction occurs Which results in the naphthenic acid contained in the distillate from formation of mercaptans and disuldes, which the distillation or fractionation chamber rst is compounds generally are not found in crude reacted with an alkali-metal hydroxide to form petroleum oils. an alkali-metal naphthenate which subsequently In my co-pending application Ser. No. 600,646, is reacted with the lcopper' Salt to form more Patent No. 2,467,429, filed June 20, 1945, I have cupric naphthenate. Thus, the naphthenic acid disclosed a method for the treatment of crude liberated during the treatment 0f the crude pepetroleum oil to stabilize or otherwise modify sulfur compounds, other than hydrogen sulfide, which may be present so that upon subsequent distillation of the crude petroleum oil the sulfur compounds contained therein do not decompose J or react to produce mercaptans, disuldes or other deleterious sulfur compounds in the distillates. In accordance with the method disclosed in that application, cupric naphthenate is added to and intimately mixed in relatively small Thus, not only iS the naphthenc acid liberated amounts With the crude petroleum oi1 prior to during the treatment of the oil recovered and the distillation or fractionation thereof. The adused as one of the materials for forming more dition of cupric naphthenate tothe crude pecupric naphthenate to be used, but the copper troleum oil stabilizes the sulfur compounds, other product of the decomposition is used to form the than hydrogen suinde, contained therein so that Copper Salt used in the reaction with the Sodium upon subsequent distillation or fractionation of naplltllenate- Therefcle, the DIGCSSS iS cyclic the crude petroleum oil they do not react or debOtl'l With TGSDQC t0 0010961 and naphthen acid. compose to form mercaptans and disuldes. F01 a fuller and mcle complete understanding In the process of my aforesaid application, of the invention reference is made to the acthe cupric naphthenate is decomposed during the Compamng drawings in Which heat treatment of the crude oil and yields naph- Fig. 1 is a flow sheet illustrating one method. thenie seid which passes oe with the distilietes. in which the process 0f the present invention Also, any nophthenie acid which is present in may be carried out in a Cyclic manner in conthe crude petroleum oil, as such, will carry nection with the treatment of crude petroleum through the distillation or fractionation chamoil with cupric naphthenate, and ber and pass oil with the distillates, Fig. 2 is a flow sheet of a slightly modied ar- The present invention contemplates a process rangement of producing copper soaps, such as copper Referring first to Fig. 1, a charge of crude. naphthenates, in which naphthenic acid such as petroleum oil passing through a conduit l, to-. that resulting from the decomposition of cupric l troleum is recovered and re-fused.

The present invention also contemplates a process in which the copper product resulting from the decomposition of the cupric naphthenate, during the treatment of the hydrocarbon oil containing the same, is used as a source material for forming the copper salt, which in turn may be used for reaction with the alkalimetal naphthenate to form the cupric naphthenate.

gether with a small amount of cupric naph thenate introduced through a conduit 2, is pumped by a pump 3 through a charge heater 4 Where the temperature of the crude petroleum oil is raisedto its flashing point, for example, about 750 F. The thus heated crude oil, together with the cupric naphthenate contained therein, is then introduced into the lower portion of a fractionation column 5, whereupon ,the petroleum oil ashes, forming a vapor phase consisting of distillates and naphthenic acid resulting from decomposition of the cupric naphthenate, and a liquid phase consisting of fuel oil'which carries the copper product of the decomposition of the cupric naphthenate. The copper product and the fuel oil settle to the bottom ofthe column and are withdrawn as hereinafter described. Thevapor resulting from the flashing of the hot charge of crude oil may be fractionated into as many fractions as desired. As shown in Fig. l, is divided into a light gas and gasoline fraction which is withdrawn from the top-of the column 5 through a conduit 6, a heavier fractionA of light distillates which is withdrawn ata lower level from the column, through'a conduit l, and a still heavier fraction consisting essentially of gas oii which is Withdrawn from a still lower portion of the columnthrough a conduit ii. The fractions withdrawn-through the conduits e, l and i3 will contain *varying amounts of the naphthenic acid resulting from the decomposition of the cupric naphthenate, and, if the crude oil is of the naphtheme-base type, from the presence of naphthenic acid present, as such in the original crude oil. However, most of the naphthenic acid will be contained in the gas oil fraction withdrawn through conduit 8. The fractions withdrawn through the conduits 6, 'i and S may be passed through condensers 9, Ill and I! in accordance with the usual practice.

In accordance with the present invention any oneor all of-the fractions withdrawn through the-conduits B, 'F 'and 8 Vmay be treated with an alkali-metal hydroxide, preferably molten caustic, to-'form an alkali-metal naphthenate, which subsequently is converted to cupric naphthenate. As shown in Fig. l, the gas oil fraction withdrawn through the conduit 8, which contains a relatively large-percentage of the naphthenic acid resulting from decomposition of the cupric naphthenate used-'in the treatment of the-oiLis passed through a neutralizer I2 where it is caused to react with an alkali-metal hydroxide, preferably sodium hy droxide, supplied in the form of a concentrated solution of about 45 to 50 B. from a container I3-by means of a pump I4 and conduit I5. On introduction of the caustic solution into the neutralizer- I2 lthe water content thereof vaporizes, and leaves the caustic in the molten state. The neutralizer I2 is maintained substantially filled With chains or some inert material which vwill causea large surface contact between the molten caustic and the hot oil vapors containing the naphthenic acid. As thehot gas oil vapors and naphthenic acid-rise in the neutraliser i2 countercurrent to the downward flowing molten caustic the naphthenic acid contained in them comes into. intimate contact with the caustic with the resulting formation of sodium naphthenate and water. The sodium naphthenate which is thus formed has a higher boiling point than the gas oilandsettles to the bottom of the neutralizer as a liquid. The amount of sodium hydroxide introducedinto the neutralizer I2 is equal to or slightly 'more .or less than the stoichiometric equivalent ofthe naphthenic acid contained in the gas oil vapors. The pressure in the neutralizer is not important; it may be that normally prevailing in columns where gas oil vapors are fractionated.

In order to obtain more complete reaction betweenthe caustic and the naphthenic acid, the sodium naphthenate and any unreacted caustic are withdrawn from the bottom of the neutralizer i2 through a conduit I5 and pumped by a pump Il through a conduit I8 back to the upper portion of the neutraliZer through which it thus circulates. The conduit I8 is provided with a valve I9. A conduit 20 is connected to the conduit I8 between the pump Il and the vaive I9 which normally is so adjusted that a relatively small proportion of the sodium naphthenate constantly is withdrawn through the conduit 2t. The gas oil freed of the naphthenic acid, and steam resulting from vaporization of the water formed during the reaction between the naphthenic acid.

sulfate, or othercopper salt, such as thentrate; chloride, etc., inthe form lof an aqueous solutiony introduced through a conduit 23 from a supply tank 2li. An agitator 25is Aprovided in the reaction chamber 22 `and is operated at a speed suii'icient to impart lav gentle agitation to themixture undergoing reaction therein. If the sodium naphthenate withdrawn through the conduit 20 contains any free caustic, it is neutralized before the sodium naphthenate is reacted with the copper sulfate.

In the reaction chamber 22, the sodium naphthenate reacts with the copper sulfate to form sodium sulfate and cupric naphthenate. The sodium sulfate may be withdrawn from the bottom of the reaction chamber 22 through a conduit 26. The cupric naphthenate which is formed is waterinsoluble but is oil-soluble. Ordinarily enough of the higher boiling constituents of the gas oil will be condensed and withdrawn from the neutralizer I2 along with the sodium naphthenate by entrainment to dissolve the cupric naphthenate as fast as it is formed in the reaction chamber 22. The solution of cupric naphthenate in the gas oil, being lighter than the aqueous solution of sodium sulfate, will form a supernatant layer on top of the aqueous sodium sulfate and will continuously pass over a launder 2 in the tank y22 and be withdrawn through a conduit 28.

If the copper sulfate solution supplied fromthe tank 2d is not suiiiciently dilute to obtain sufficiently rap-idly reaction between and the sodium naphthenate, additional water may beintroduced into the reaction tank 22 through a.

conduit 29.

The cupric naphthenate withdrawn from the` reaction tank 22 through the conduit 28 is cycled back through the conduit 2 and used for the treatment of further amounts of crude petroleum oil in the manner more particularly described inv my aforesaid application.

The bottoms from the fractionation column 5' constitute thefuel oil fraction rand contain all, or at least most, of the copper product resulting from the-decomposition of the cupric Ynaphthe-A nateas described4 above. The copper in such copper product ordinarily will be in the form of cuprous sulde, cuprous oxide, metallic copper, or insoluble copper-sulfur compounds of unknown composition. The bottoms from the fractionation column containing the copperI product referred to above is withdrawn through a conduit and passed by means of a pump 3l to a thickener or lter 32, which may be a hot-oil iilter, a thickener of the Dorr type or a thickener of lter of any other type which will separate the hot fuel oil from the entrained copper product. The separated fuel oil is Withdrawn through a conduit 33 while the recovered copper product is withdrawn from the bottom of the thickener or lter through a conduit 34.

The copper product passing through the conduit 34 is delivered to a treater 35 Where it is converted to copper sulfate in any desired manner. This may be done by roasting, treatment with sulfuric acid or a combination of both steps. Ordinarily it is preferred to iirst roast the copper product to convert the metallic copper content thereof to the oxide, in which form it is more readily acted upon by sulfuric acid. The resulting copper sulfate is withdrawn through conduit 35 and passed to the copper sulfate container 24 for reaction with more sodium naphthenate withdrawn from the neutralizer I2.

If the particular crude petroleum which is being treated is of the naphthene-base type and contains a relatively high proportion of naphthenic acid, the amount of sodium naphthenate formed in the neutralizer I2 may be more than would be desirable to convert to cupric naphthenate for re-use in the system. In such a case, any such excess of sodium naphthenate may be withdrawn through a conduit 36 controlled by a valve 31; or the excess naphthenic acid may be permitted to remain in the distillate, reacting only sufcient of the naphthenic acid with the caustic to form the required amount of sodium naphthenate for subsequent conversion to cupric naphthenate. That may be done by restricting the amount of caustic available for reaction with the naphthenic acid in the neutralizer I2, by by-passing a portion of the hot gas oil vapors through a conduit 8a controlled by a valve 8b. On the other hand, should the amount of naphthenic acid contained in the crude petroleum oil be insumcient to compensate for that lost by removal with lighter fractions not treated ,j

for the recovery of the naphthenic acid content thereof, such additional amount of naphthenic acid as may be necessary may be introduced through a conduit 38.

In Fig. 1 only the gas oil fraction withdrawn from the lower portion of the fractionator or distillation column `5 is treated for recovery of the naphthenic acid and its conversion to cupric naphthenate. However, if desired, the fractions withdrawn through the conduits 6 and 'I also could be passed through neutralizers similar to the neutralizer I2 for conversion of the naphthenic acid content thereof to sodimu naphthenate which subsequently would be converted to cupric naphthenate as described above, such neutralizers being indicated in dotted lines at I2a and I2b, respectively.

In Fig. 2 there is disclosed a modied form of the invention in which the heated charge of crude petroleum oil containing the cupric naphthenate is first introduced into a flash drum 40. All of the fuel oil formed as a result of the flashing of the crude petroleum, and the copper product resulting from decomposition of the cupric naphthenate, settle to the bottom of the ash drum, as described in connection with the proci-l ess as carried out with the apparatus of Fig. 1.

All of the vapors from the flash drum are withdrawn from the top through a conduit 4I and passed through a neutralizer I2 where the naphthenic acid content thereof is reacted with caustic to form sodium naphthenate in the manner described above. The hydrocarbon vapors and steam resulting from vaporization of Water produced in the reaction between the caustic and sodium naphthenate is withdrawn from the top of the neutralizer I2 through a conduit 2| and passed into the lower end of a fractionator 42 where they are fractionated into lighter and heavier fractions which are withdrawn through conduits 43, 44 and 45, respectively. Those fractions may be passed through condensers 9', I0 and II', respectively, as is customary. In all other respects, the process represented by the ow sheet of Fig. 2 is identical with that described above in connection with the flow sheet of Fig. 1, and like reference characters, primed, have been used to designate like parts of the apparatus.

From the aforegoing, it will be apparent that the present invention provides a process for producing cupric naphthenate which preferably forms a part oi' a cyclic process for the treatment of crude petroleum with cupric naphthenate in which provision is made for the recovery of the copper content as well as the naphthenic acid content of the cupric naphthenate treating agent, and their reaction to provide additional cupric naphthenate which may be used for the treatment of additional crude petroleum. When used in connection with such a process for fixing sulfur compounds contained in the crude petroleum oil it has the further advantage of improving the quality of the distillates which are recovered due to the fact that the naphthenic acid and any other organic acids which are present in the distillates are removed.

While the invention has been particularly described in connection with the production of cupric naphthenate from naphthenic acid or sodium naphthenate, it is to be understood that the process is equally applicable to the production of other copper soaps of water-insoluble organic acids which are volatile and subsequently stable at the temperatures to which the oil is heated, such as cupric oleate, or cupric tallate. Thus, if cupric oleate, for example, were used for the xation of sulfur compounds in the crude oil, oleic acid would result from the decomposition of the cupric oleate in the fractionation column f `which. could be reacted with the caustic in the neutralizer I2 to form sodium oleate, which subsequently vwould be converted to cupric oleate in the manner described above in connection with conversion of sodium naphthenate to cupric naphthenate.

Also, the process is not necessarily limited to the production of cupric naphthenate or similar cupric salts of water-insoluble organic acids, and would be equally useful for the production of cuprous naphthenate or other cuprous salts of water-insoluble organic acids. In order to produce cuprous naphthenates or other cuprous salts of water-insoluble organic acids it is only necessary that a heater 39, through which the cupric naphthenate may be bypassed and heated to a temperature suicient to cause its reduction to cuprous naphthenate, be inserted in the conduit 28.

While the charging stock introduced through the conduit I has been referred to as crude petro- I aufm st.

ieumicinit visfto :be:understoodzxhatiit mightxbe-r anyntner stookl'vvhich'ritis desiredf-to'treat with;

cupric' naphthenatev for' the iixation .oi.` sulfur compounds contained thereinf- Variouslchan'ges maybe madein the procedure Without 'departing from. theinvention'or Isacriic;

ing-any of lthe advantages thereof.

I claim:

1.1 the-'process of treating petroleumoil With-l acopper-soapofa Water-insoluble organic acid containing `theorganic acidI resulting `from decomposi-ti'onfof the copper soap; the improvement' which comprisesl separately withdrawing th'ecopper-compound and the liberated -vaporsfcontain'- in'gtheprganic acid resulting from'the decomposition of the-copper soap'from the Zone of heat treatment passing withdrawn vapors into intimate lcontact 'with caustic with resultant formation"of'fthefsodium soap of the acid, and reacting ment 'andthe' liberation of vapors containingnaphthenic acid resulting from `decomposition of the copper naphthenate; the improvement which' comprises'separately withdrawing the copper compound and the liberated fvapors containing the naphthenic acid resulting fromthe decomposition of the copper naphthenate from the zone of heat treatment passingwithdrawn vapors into intimate f contact with caustic with resultant formation of sodium naphthenate; reacting the sodium'naphthenate so formed With acopper" sal-tto form cupric naphthenate and using the thusformed cupric naphthenate as the source material ofthe copper naphtlienate used -in the treatmentof further amounts of oil.

3. In'the process of treating petroleum oilwith a' cupric soap ofa water-insolubleorganic acid forthe' fiii'ation of sulfur compounds contained thereininwhich the cupric soap is introduced'v into the oil'and the oil subsequently is suiojectedY to heat treatment and the liberation ofvapors containing' the water-insoluble organic acid re-v sulting from decomposition ofthe cupric soap; the improvement which comprisesv separately withdrawing the copper compound and the liberated vapors containing the Water-insoluble or' ganic acid resulting from the decomposition ofV the cupric 'soap 'from `the Zone of 'heat treatment passing withdrawn vapors into intimate contact with caustic with resultant formation of the sodium soap of the acidj and reacting the sodium soap of the acid" so formed with copper sulfate' to form the corresponding cupric soap, and returning the thus' formed cupric soap for the treatment of further amounts of petroleum oil.

4; In'th'eprocess of treating petroleum'oil witha cupric soap of a Water-insoluble organic acid for the xation'of sulfur compounds' contained therein' in which the cupric soap is introduced into the oil and the oil subsequently is subjected toheat treatment and the liberation of vapors containing'a water-insoluble organic acid result- `l0 forithex'ation of sulfur compounds contained: therein vinwhicn the copper soap is introduced? into the-foil and the oil subsequently is subjected` to' -heat y treatment and theliberation 'i of vapors' in'gL-from :decomposition` of r thezfcuprio soap :the c improvement l which f comprises"separately'vy Jvvitha: drawing-the .copperfcompound and the liberated.; vapors containing@ the Water-insoluble'v organico acidi'esulting from" the decomposition" of other cupric soapfrom the zoneof heat treatment pass ing. withdrawn vapors `into' intimate contact'witlr. molten f caustic with'y resultant formationt oix'they sodium; soapofthe acid,v and reacting the sodium;` soap-cf:theacid'fsolformed. with a coppersalt tow` form the corresponding cupric soap, and returning/the .thus formedfcupric soap; for vthe treatment of ffu'rther amounts f of petroleum` oil,A

5. In the process of treatingrpetroleum Voil-Wiltli; a cupric soap of a Water-insoluble organic'acid for the iixation oi'sulfur compounds..contained; therein iin-which. the. copper soapzis introducedfl into the oil andthe oil subsequentlyfis subjected; tolieattreatment and the liberation ofvapols'-'- containing rthefwater-inso1ubleorganic acid reesultingiroml decomposition' or" the cupric'fsoapil tpe improvement' which comprises separatelyl withdrawing tlie cop-per compound-.andv-theliber i ated vapors contcin-ing` the water-insolublefoimganic acidi-resulting from the:decomposition/of#4 the cupric soap from the zoneof heat treatment v passingV the Withdrawn vapors'into intimatefcon` tact with caustic with resultant for-mation'oi the sodiumsoap ofthe'acidireactingthe sodium soapl offthe acid .so formedr withaicopper salt-infant' aqueous mediumV in the presence of an oil in Which-f the: cupric soapLof-the acid *is soluble, Wherelo'yr` the cupric soap-'formed -is taken up by'and dis-f= solves in the oil-and the resulting solutiorriorms av-supernatant layer on the aqueous mediumg'andf' separatingthe'oil solution of thefcupric soap from"l the aqueous lmedium, and returning the f sepa-J- rated oilsolution of the cuprioy soap for treatment* of further amounts of petroleum oil."-

6i vIn the process of treatiirgpetroleum 'o-ilvvitli' a copper soap ot'a Water-insoluble organic acid* for-the xationof sulfur compounds contained'l tlierein-invfhich the copper soap is introduced* into theoilfand the oil subsequentlyis' subjected" toy heat treatment with the liberation -of vap'ors` contain-ing the Water-insoluble 'organic acid"'re''- suitin'g from' decomposition of the copper soapi' and apoppercompoun'd; the improvement which" comprises'converting the copper compound'to a" copper salt, passing"liberatedvapors containing? the -Water-insolub1e organic acid into intimate f contact With caustic with resultant formationof the sodium soap of theacid, reacting the sodium" soap so formed with the copper salt'iormed from the separated `copper compound to form the'corresponding cupric soap, and using the thus formed" cup-ric soap asthe source material 'othecopp'er soap used in' the treatment of further amounts" of petroleum'oil.

Y. in the process of treating' petroleum oil with" a copper soap ofia Water-insolublerorganic acid. for the xaton o'sulfur compounds contained. therein in which the copper soap is introduced'into the oil and the oil subsequently is subjected' to'h heat 'treatment with the liberation tof vapors coni taining the 'waterlinsoluble organic acidresult-r ing from decomposition of the copper soap and av-copper compound; theimprovement which comprises converting thecopper compound toV acop- 'per salt, passing liberated vapors containing the 'y Water-insoluble organic" acid' into intimate con;` tact With molten' caustic' with resultant 'formationof'the sodium soap ofthe acid, reacting the" sodium' soap4- so formed with the copper"sali."v

' formed lfr'omthe separated copper compound to" form` the corresponding cupric soap, and using the thus formed cupric soap as the source material of the copper soap used in the treatment of further amounts of petroleum oil.

8. In the process of treating petroleum oil with cupricnaphthenatefor the fixation of sulfur compounds contained therein in which cupric naphthenate is introduced into the oil and the oil subsequently is subjected to heat treatment with the liberation of vapors containing naphthenic acid resulting from decomposition of the cupric naphthenate and a copper compound; the improvement which comprises converting the copper compound to a copper salt, passing liberated vapors containing naphthenic acid into intimate contact with caustic with resultant formation of sodium naphthenate. reacting the sodium naphthenate so formed with the copper salt formed from the separated copper compour' to form cupric naphthenateand. returning the cupric naphthenate for the treatment of further amounts of petroleum oil.

9. In the process of treating petroleum oil with a copper soap of a Water-insoluble organic acid for the nxation of sulfur compounds contained therein in which a copper soap is introduced into the oil and the oil subsequently is subjected to heat treatment with the liberation of vapors containing the water-soluble organic acid resulting from decomposition of the copper soap and a copper compound; the improvement which comprises passing liberated vapors containing the water-insoluble organic acid into intimate contact with caustic with resultant formation of the sodium soap of the acid, converting the copper compound. to a copper salt, reacting the sodium soap with the copper salt formed from the separated copper compound in an aqueous medium in the presence of an oil in which the cupric soap of the Awater-insoluble organic acid is soluble, whereby the cupric soap formed is taken up by and dissolves in the oil and the resulting solution forms a supernatant layer on the aqueous medium, separating the oil solution of the cupric soap from the aqueous medium, and using the thus separated oil solution of the cupric naphthenate as the source material of the copper soap used in the treatment of further amounts of petroleum oil.

l0. In the process of treating petroleum oil with a copper soap of a water-insoluble organic acid for the fixation of sulfur compounds contained therein in which the copper soap is introduced into the oil and the oil subsequently is subjected to heat treatment with the libera-A tion of vapors containing the Water-insoluble organic acid resulting from decomposition of the copper soap and a copper compound; the improvement which comprises passing liberated vapors containing the water-insoluble organic acid into intimate contact with caustic with resultant formation of the sodium soap of the acid, converting the copper compound to copper sulfate, reacting the sodium soap, at an elevated temperature and with agitation, with the copper sulfate formed from the separated copper compound in an aqueous medium in the presence of an oil in which the cupric soap of the acid is soluble, whereby the cupric soap formed is taken up by and dissolves in the oil and the resulting solution forms a supernatant layer on the aqueous medium, and using the thus separated oil solution of the cupric naphthenate as the source material of the copper lo' soap used in the treatment of further amounts of petroleum oil.

ll. In the process of treating petroleum oil with a copper soap of a water-insoluble organic acid for the fixation of sulfur compounds contained therein in which the copper soap is in.- troduced into the oil and the oil subsequently is subjected to heat treatment and the liberaation of vapors containing the water-insoluble organic acid resulting from the decomposition of the copper soap, the improvement whichy comprises withdrawing the copper compound resulting from theA decomposition of the copper soap, separately withdrawing all of the oil vapors containing the water-insoluble organic acid, passing the separated vapors into intimate contact with caustic with resultant conversion of the water-insoluble organic acid to the sodium soap thereof, separating the oil vapors freed from the water-insoluble organic acid. fractionating the separated' oil vapors, reacting the sodium soap with a copper salt to form the corresponding cupric soapy and using` the thus formed cupric soap as the source materialA of. the copper soap used in the treatments of further amounts of oil.

I2. In. the process. of treating petroleum, oils, with cupric` naphthenate for the iixation of sulfur compounds contained therein in which cupric naphthenate is introduced into thev oil and the oil subsequently is subjected to heatv treatment with the liberation of vapors containing naphthenic acid resulting from-the decomposiftion of the cupric naphthenate. the improve-1 ment which comprises withdrawing the Acopper. compound resulting from the-decoI-npositionl of the, cupric naphthenate, separately withdrawing all of the oil vapors containing the naphthenic acid, passing the separated vapors into intimate conta'ct with caustic with resultant conversion of the naphthenic acid to Sodium naphthenate, separating the oil vapors freed of the naphthenic acid, fractionating the separated oil vapors, reacting the sodium naphthenate with a copper salt to form cupric naphthenate and returning the cupric naphthenate for the treatment of further amounts of petroleum oil,

13. In the process of treating petroleum oils with a cupric soap of a water-insoluble organic acid for'the xation of sulfur compounds contained therein in which the cupric soap is introduced into the oil and the oil subsequently is subjected to heat treatment with the liber` ation of vapors containing the water-insoluble organic acid resulting from the decomposition of cupric soap; the improvement which comprises withdrawing the copper compound resulting from the decomposition of the cupric soap, separately withdrawing all of the oil vapors containing the water-insoluble organic acid, passing the separated vapors into intimate contact with caustic with resultant conversion of the water-insoluble organic acid to the sodium soap thereof, separating the oil vapors freed of the naphthenic acid, fractionating the separated oil vapors, reacting the sodium soap with a copper salt in an aqueous medium in the presence of an oil in which cupric soap of the acid is soluble, whereby the cupric soap formed is taken up by and dissolves in the oil and the resulting solution forms a supernatant layer on the aqueous medium, separating the oil solution of the cupric soap from the aqueous medium, and returning the separated oil solution of the cupric 1l soap for the treatment of further amounts of petroleum oil.

14. In the process of treating petroleum oils with a copper soap of a water-insoluble organic acid for the xation of sulfur compounds contained therein in which the copper soap is introduced into the oil and the oil subsequently is subjected to heat treatment with the liberation of vapors containing the water-insoluble organic acid resulting from the decomposition of the copper soap; the improvement which comprises withdrawing the copper compound resulting from the decomposition of the copper soap, separately withdrawing all of the oil vapors containing the water-insoluble organic acid, passing the separated vapors into intimate contact with molten caustic with resultant conversion of the water-insoluble organic acid to the sodium soap thereof, separating the oil vapors freed of the naphthenic acid, fractionating,r the separated oil vapors, reacting the sodium soap at an elevated temperature and with agitation, with a copper salt in an aqueous medium in the presence of an oil in which the cupric soap of the acid is soluble, whereby the cupric naphthenate formed is taken up by and dissolves in the oil and the resultant solution forms a supernatant layer on the aqueous rnedium, separating the oil solution of the cupric soap from the aqueous medium, and using the oil solution of the cupric soap as the source material for the copper soap used in the treatment of further amounts of oil.

15. In the process of treating petroleum oils With cupric naphthenate for the ixation of sulfur compounds contained therein in which cupric naphthenate is introduced into the oil and the oil subsequently is subjected to heat treatment with the liberation of vapors containing naphthenic acid resulting from the decomposition of the cupric naphthenate and the formation of a copper compound; the improvement which comprises separating the copper compound and converting it to copper sulfate, passing al1 of the oil vapors containing the naphthenic acid into intimate contact with caustic with resultant conversion of the naphthenic acid to sodium naphthenate, separating the oil vapors freed of the naphthenic acid, fractionating the separated oil vapors, reacting the sodium naphthenate, at an elevated temperature and with agitation, with copper sulfate formed from the separated copper product, in an aqueous medium in the presence of an oil in which cupric naphthenate is Soluble, whereby the cupric naphthenate formed is taken up by and dissolves in the oil and the resultant solution forms a supernatant layer on the aqueous medium, separating the oil solution of the cupric naphthenate from the aqueous medium, and returning the oil solution of cupric naphthenate for the treatment of further amounts of petroleum oil.

CHARLES O. HOOVER.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,068,979 Fischer Jan. 26, 1937 2,091,239 Hall Aug. 24, 1937 2,113,496 Roon et a1 Apr. 5, 1938 2,273,263 Happel et a1. Feb. 17, 1942

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