Sept. 25, 1951 C. E. MORRELL. ET AL 2,569,384 RECOVERY OF OXYGENATED COMPOUNDS FROM HYDROCARBON OILS Filed Dec. 19, l947

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Charles22g E. 72 ZZ Sr. Verators es- 2214464- Cluvorres Patented Sept. 25, 1951 2,569,384 UNITED STATES PATENT office 2,569,384 RECOVERY OF OXYGENATED COMPOUNDS FROM HYDROCARBON OLS Charles E. Morrell, Westfield, and James E. McAteer, Cranford, N.J., assignors to Standard Oil Development Company, a corporation of Delaware Application December 19, 1947, Serial No. 792,802 1. 1. Claims, (C. 260-450) 2 This invention relates to the recovery of the Oxygen-containing compounds of One to four lower molecular weight neutral oxygen-contain carbon atoms will enter the aqueous phase while ing organic compounds from mixtures thereof the bulk of the compounds containing five car with hydrocarbon oils by a process involving the bon atoms and more per molecule will be found extraction of Such mixtures with dilute aqueous 5 in the oil layer, although it should be borne in carboxylic acid solutions, such as dilute aqueous mind that the separation of materials into their acetic acid, dilute aqueous propionic acid, etc., respective phases is oftentimes not cleancut and Or mixtures of the same. depends to a large extent upon the conditions Warious processes are known to the art in involved and the over-all composition of the Which a mixture of hydrocarbons and Organic O materials in the condensate from the Synthesis Oxygen-containing compounds are produced. reactor. Some of these processes are the low temperature Processes have been developed for the Sepa carbonization of coal, peat and similar materials, ration and recovery of alcohols, ketones, alde the destructive hydrogenation and distillation of hydes, etc. from the water layer. The starting coals, Wood, shales, etc. Numerous oxidation 15 point in many of such processes is a crude alcohol processes, particularly oxidation of petroleum oil distillation in which the water layer is subjected fractions, such as is described in Ellis' Chemistry to distillation to remove substantially all of the of Petroleum Derivatives, vol. 1, chapter 36, pages oxygenated compounds other than acids there 830 to 845, also yield mixtures of oxygenated from. Generally speaking, it is desired to leave compounds and hydrocarbons of substantially the acids, such as acetic acid, propionic acid, the same boiling range. This invention is par etc., in the bottoms from which they are sub ticularly applicable to the hydrocarbon syntheses, sequently recovered. such as the Fischer synthesis wherein oxides of It is an object of this invention to provide a carbon are reacted with hydrogen in the presence method for the recovery of oxygenated Coms of catalysts to produce synthetic hydrocarbons, 25 pounds, particularly water-soluble oxygenated water and numerous organic oxygenated com compounds from mixtures thereof with hydro pounds, predominantly aliphatic. The oxygen carbon oils. ated compounds produced in the Synthesis oper It is an object of this invention to provide a ation may be a major product or a relatively Small method for the recovery of oxygenated come by-product depending upon the Operating con 30 pounds from the Synthesis oil layer. ditions. These oxygenated materials which are It is also an object of this invention to provide extremely valuable as chemicals, consist of a a method for the separation and recovery of mixture of alcohols, acids, aldehydes, ketones and neutral organic oxygenated compounds and of esters and are difficult to separate from the hy acidic organic oxygenated compounds from mix drocarbon oil because first, they are so numerous, 35 tures of both with hydrocarbon oils. secondly they boil within substantially the same It is also an object of this invention to provide range as the hydrocarbon oils and, thirdly, they a means for allowing the oxygenated compounds often form azeotropes with each other and with normally included in the synthesis oil layer to be the hydrocarbon oils. purified and concentrated along with the oxy Normally when the products of the above-de 40 genated compounds normally obtained in the Scribed synthesis operation are condensed and al water layer. lowed to settle, the condensate separates into a These and other objects of this invention are di-phase System, that is, an upper oil layer con attained by carrying out the extraction of a mix prising substantially hydrocarbons and hydro ture of neutral and acidic oxygenated Organic carbon-Soluble Oxygen-containing materials and 5 compounds in hydrocarbon oils with a dilute a lower water phase comprising substantially aqueous solution of acetic acid which may or water and water-soluble oxygen-containing ma may not contain Small amounts of homologues terials. The oxygen-containing organic con of acetic acid. The acid bottons obtained from . pounds formed in the Synthesis operation range the fractional distillation of the Synthesis Water from very low molecular Weight compounds to 50 layer is especially suitable for this extraction step very high molecular weight compounds and as Will be further explained below. therefore find themselves distributed throughout The material subjected to extraction, accord the oil phase and the water, phase depending on ing to the terms of this invention, is complex their solubilities in these respective phases. In in nature. It is composed of hydrocarbons in general, it can be said that the bulk of the organic 55 cluding paraffins, olefins and in some cases, Small 2,569,884 3 4. amounts of aromatics. In addition, it contains pecially true when it is desired to extract the oxy anywhere up to about 50% or more of oxygen genated compounds from the lower boiling por containing materials, particularly of high molecu tions of the Fischer synthesis oil, say for instance lar weight such as those set out above. In cases the gasoline fraction (up to 400 F.), or some where the material is derived from the hydrocar lower boiling portion of the gasoline fraction. bon synthesis operation, the oil will have dissolved This invention also includes an alternate possi in it alcohols, acids, aldehydes, ketones and es bility in which a lower alcohol such as methyl, ters. Frequently, the esters predominate among ethyl or isopropy or mixtures of these lower alco the high boiling compounds, particularly that hols or mixtures of these with other neutral oxy fraction boiling above 350 F. while carbonyl con genated compounds such as ketones are added to pounds, that is aldehydes and ketones, acids and the aqueous acidic bottoms and this mixture em alcohols, predominate among the oxygen-contain ployed as the extraction agent. For instance, if ing compounds boiling at temperatures up to the entire Fischer synthesis oil is to be extracted about 350° F. Ordinarily the amounts of alcohols or if only the higher boiling portions thereof are and acids found decrease with increasing analyti extracted, it is desirable that considerable cal distillation temperatures due undoubtedly to amounts of the lower boiling oxygenated com the fact that they undergo esterification reactions pounds be added to the aqueous bottoms in order during such distillation treatments. The oxygen to obtain a suitable solvent for the extraction. content of the hydrocarbon oils resulting from the Preferably, however, the amount of alcohols or synthesis operation generally runs from one other low boiling oxygenated compounds com weight percent to ten weight percent. bined with the aqueous bottons is kept at the It has been found that when such a mixture of lowest value consistent with reasonable capacity hydrocarbon oils and oxygenated compounds is and selectivity of the extraction agent for the extracted at low temperatures with a dilute aque oil-soluble oxygenated compounds. Best results ous solution of acetic acid with or without a Small have been obtained by the addition of at least 20 amount of its homologues, the lower molecular volume per cent alcohol, particularly methanol. weight neutral oxygenated compounds present in The aqueous bottoms, either as such or after the mixture are extracted therefrom by the acid reinforcement with lower boiling oxygenated con solvent, leaving the lower molecular weight acids pounds as described above, may be contacted with contained in the mixture in the raffinate phase 30 the oil or suitable fractions thereof under a ya with the hydrocarbon oils. That is to say, the riety of conditions. For instance, the contacting alcohols, esters, ketones, aldehydes, acetals, etc., may be carried out in a batch manner. Prefers through C5 and some Cs, are dissolved by the di ably, however, it is carried out using countercur lute aqueous acetic acid and constitute the extract rent flow of the extractant and the oil, either in phase, while the acids present in the mixture are counter-stage equipment or in a countercurrent undissolved and together with the hydrocarbon packed or plate tower. The optimum solvent to oils in the mixture constitute the raftinate phase. oil ratio will vary over wide ranges depending. The dilute aqueous acetic acid solution en upon the nature of the solvent, i. e. the acid and ployed as the selective solvent according to the lower boiling oxygenated compound-content terms of this invention should contain no more 46) thereof, the oxygenated compound content of the than 5 to 10 weight per cent of acetic acid. The oil, the boiling range of the of being extracted, preferred range is 2 to 5 weight per cent. If other and the temperature of the extraction. As the higher homologues of acetic acid are present they oxygenated compound content of the Solvent is should be restricted to no more than about 35 increased, the optimum solvent/oil ratio, in gen weight per cent based on the weight of acetic acid. eral, decreases. Also the lower the oxygenated The acid water bottoms obtained from the frac compond content of the oil feed, the lower the tional distillation of the synthesis water layer solvent/oil ratio requirements. When extracting contains about 95 weight per cent water and a the higher boiling portions of the oil, either alone typical analysis is as follows: or in combination with the lower boiling portions Weight percent 50 thereof, in general it is desirable to use a rela Water ------95.50 tively high solvent/oil ratio since the solubility of Carboxylic acids------14.47 the higher boiling oxygenated compounds in such Other org. Oxy. Compds.------2003 aqueous solvents is lower than that of the lower boiling Ones. 100.00 The temperature maintained in the extraction As acetic. acid. 5 5 operation may be varied over a limited range, Alcohol, esters, etc. viz. from the freezing point of the solvent, i. e. The 4.47 weight percent acid content is broken around 0° C. up to about 125° C. Temperatures down into approximately 75 weight percent acetic much above 100° C. are to be avoided when ex acid, 20 weight percent propionic acid, and 5 weight tracting with aqueous acetic acid or aqueous acid percent butyric acid and higher acids. The small (5) bottoms due to the fact that at these higher tem amount of other oxy-compounds present in the peratures acids tend to become extracted from acid bottoms, i. e. the 0.03 weight per cent alco the oil layer as described in our Copending appli hol, ester, etc., is not harmful to the material as a cation Serial Number 7,966, filed February 12, solvent. 1948. In general, we have found that extrac In its simplest form this invention entails taking tion temperatures in the range of 25 C. to 100° C. all or part of the aqueous acidic bottoms from are preferable. the hydrocarbon synthesis water layer from which As previously stated, one advantage of this type substantially all of the alcohols, ketones, alde of operation is that it permits the recovery of hydes, etc., have been removed and contacting the neutral oxygenated compounds from the oil the oil layer resulting from the synthesis product in such a manner (i.e. substantially free of or condensation with the aqueous bottons under ex ganic acids higher than acetic) that they may traction conditions. The total oil layer or appro- . be more advantageously worked up along with priate fractions thereof may be so treated. In a number of cases these bottoms may be used as the oxygenated compounds recovered from the such for the extraction operation. This is es 5 water layer. Another definite advantage is that 2,569,884 6 the carboxylic acids remaining in the raftinate tion, it is to be understood that the invention is may be easily extracted therefrom with water at not limited thereto, as the oil phase could be temperatures between 0° C. and 250 C., prefer processed independently in the manner outlined ably at 165° C. to 250° C., thereby building up a for recovery of the lower molecular weight neu concentration of carboxylic acids to such an ex tral oxygenated compounds and acidic con tent that acid recovery therefrom is made eCos pounds contained therein. Likewise, the inven nomically feasible. tion is not to be restricted by any process by which The fat solvent from the aqueous acid extrac the acids may be recovered from the raftinate tion operation is preferably subjected to distill phase. Such recovery may be accomplished as lation to remove therefrom substantially all the demonstrated by Water-washing or, one may re alcohols, ketones, aldehydes, esters and acetals. sort to other processes as fractional distillation, The aqueous acid bottoms may be further used tralization, extraction with other solvents, in part as an extraction solvent in the oil ex etc. traction step and/or in part sent to an acid The fact that it has been found that dilute recovery operation. aqueous acetic acid at temperatures up to 125 C. The attached drawing represents a flow plan of will not extract carboxylic acids from mixtures one process and accompanying apparatus for thereof with other neutral oxygenated con carrying out this invention in its simplest em pounds in solution, is an extremely important bodiment. feature of the recovery processes here illus Referring to the drawing, numeral f repre 20 trated. It is of particular significance when the sents a reaction zone which produces a reaction neutral oxygenated compounds are being recov product composed chiefly of hydrocarbons and ered from the extract by fractional distillation. oxygenated compounds, which when removed If the oil layer were extracted with water the from the reaction and condensed, form in vessel Water would remove not only the lower molecular 2 an upper hydrocarbon oil phase and a lower 2. weight neutral oxygenated compounds from the water phase, each phase containing dissolved oil layer but the lower molecular weight acids therein varying amounts of organic oxygenated as well. The extract would therefore contain compounds such as alcohols, acids, ketones, alde the C2 through Cs acids. The higher homologues hydes, etc., as explained previously. The water of acetic acid, i. e. propionic acid, butyric acid, phase is removed via line S to zone 4 which may 3. etc. present in such an extract, form azeotropes be a fractional distillation zone, an extractive with water and, therefore, in a fractional disti distillation zone or a solvent extraction Zone for lation of a synthesis water layer they are divided separation of the water layer oxygenated con between the distillation overhead and residue. pounds into the neutral oxygenated compounds Some of these interfering water azeotropes are taken overhead via line 5, and the acids removed 35 as follows: as bottons via line . The oil phase from vessel 2 is removed via line 7 to extraction zone en Boiling Weight tering at a point below the mid-section thereof. Point, Per Cent In extraction zone the oil phase is counter o C. HO currently extracted with all or part of the acid t) bottoms entering the extraction zone via line 9 at Proponic acid-water------99.98 82.3 Isobutyric acid-water.-- 9.3 79 a point near the top thereof. During the extrac Butyric acid-water------99.4 8.6 tion operation the lower molecular weight neu Isovaleric acid-water------... 99.5 8, 6 tral oxygenated compounds in the oil layer are extracted by the aqueous acid and the resulting extrict is removed for separation of solvent there The crude neutral overhead, therefore, would be from via line . This may be conveniently contaminated by considerable amounts of acids, accomplished by introducing the extract into and the recovery of the acids themselves is there fractionation zone 4 via line 3. Raftinate from by made more costly. Furthermore, the addi extraction zone is removed overhead via line 50 tion of the aqueous extract of the oil layer and consists chiefly of hydrocarbon oils, higher directly to the synthesis water layer which cone molecular weight oxygenated compounds and all tains usually 2 to 5 weight per cent of acetic acid, the carboxylic acids originally contained therein, further reduces the acetic acid concentration and both low molecular weight and high molecular thereby increases its cost of recovery. This is weight. This raftinate is led to water-extraction 5 5 Occasioned by the fact that the amount of acetic tower 2 entering at a point below the mid-section acid present in a typical hydrocarbon synthesis thereof. Water enters the tower at a point near oil layer represents an insignificant fraction of the top via line 3 and the raftinate is counter that present in the water product layer. currently washed at a temperature between 0° C. On the other hand, when the oil layer is ex and 250° C., preferably at about 165° C. to 250° C. 60 tracted with dilute aqueous acetic acid at tem to extract the lower molecular weight acids peratures up to 125 C. only the neutral oxy therefrom. Hydrocarbons substantially free of genated compounds are extracted and when the the lower, molecular weight oxygenated con extract is treated for removal of Solvent there pounds are removed from the extraction zone via is no problem of interference by low boiling acid line 4 and recovered for purification as gasoline Water azeotropes of the higher homologues of and/or further recovery of the higher molecular acetic acid. Thus the neutral oxygenated com weight oxygenated compounds therefrom. Aque pounds may be recovered free of contaminating ous acids are removed from the bottom of the acids. Acetic acid itself forms no azeotrope with ZOne via line 5 and are sent to storage for acid Water and presents no problem in this regard. recovery therefrom such as by distillation, de In order to visualize the amount of C-Cs oxya hydration, conversion to Salts, etc. genated compounds present in the synthesis oil Although the invention has been illustrated as layer, the following data are presented. In a a tie-in with the recovery of the lower molecular certain hydrocarbon synthesis run the oxygen weight neutral oxygenated compounds from the ated compounds extracted by water from the oil water layer of a hydrocarbon synthesis opera layer represented the following approximate per 2,569,884 7 8 centage increases over the amounts obtained by Cato Cs are, of course, also removed but not quan titatively. In addition, incomplete removal of processing the water layer from the same run. Oxygenated compounds containing 6 carbon Per cent increase atoms and above is also effected. The higher Propionic acid------15 molecular weight oxygenated compounds, i. e. Propyl alcohol------20 those containing 6 carbon atoms and above, may , Butyric acid------100 be more completely removed from the hydrocar Butyl and amyl alcohols------600 bon oil by other methods not a subject of this The selective nature of the dilute aqueous acid invention. solvent for the extraction of a Synthesis oil is 10 Although it is a feature of this invention that demonstrated by the data following in which the higher homologues of acetic acid are not ex acid bottoms from a synthesis water layer was tracted from the oil phase, and that the neutral employed as the solvent. The acid bottoms sol oxygenated compounds are thus kept free of such vent (synthesis water layer stripped of volatile acid contaminants as propionic acid, butyric acid, neutral oxygenated compounds) contained 4.2 etc., which interfere with the separation of the weight per cent organic acids as acetic acid, neutral compounds, nevertheless, it should be 0.04 weight per cent alcohols as ethyl alcohol and observed that the presence of small amounts of the balance Water. these higher homologues of acetic acid can be Eacample I tolerated. In the first place, they are inherent 2) in the System from which the acid water bottoms Cs-- fraction of synthesis oil was countercur are produced. Secondly, when, as is shown in rently extracted at room temperature with acid the examples cited, some acid is lost from the water bottoms in a glass packed tower employing Solvent to the raftinate phase, these higher homo two volumes of solvent per volume of oil. The logues of acetic acid are the ones lost due to the results obtained compared with extraction with 25 fact that they are more soluble in the oil layer water are as follows: than is acetic acid. Thirdly, although a small Feed composition in milliequivalents/gram; acids 0.76, alcohols 0.72, amount of these acids are present in the original esters 0.14, carbonyls 1.07.) Solvent their concentration is never being in Creased, so that there is little danger of building Solvent Water Apt 30 up a concentration of higher homologues of acetic acid to such an extent that they would Mol Per Cert Extracted: effect extraction of acids from the oil layer or so Acids------33 1 - contaminate the extract as to make their pres Alcohols. - 54 5 ence damaging to the neutral oxygenated com Esters------7 9 Carbonyls.------44 34 pounds. Having fully described the invention in a man 1 Gain in acid content by oil phase, i.e. i mol percent acid (based ner Such that it may be practiced by those skilled on amount in the feed) lost to raftinate phase by acid bottons. " in the art. Eacample II What is claimed is: Similar extraction runs were made at room 4) 1. An improved process for the separation and temperature employing as feed a synthesis gaSo recovery of aliphatic neutral oxygenated com line fraction (boiling range 30-205 C.). pounds comprising alcohols, aldehydes, ketones, Feed composition in milliequivalents/gram: acids 0.70, alcohols 0.57, esters and acetals, from a mixture of neutral and esters 0.25, carbonyls 0.65 solventfeed, volume ratio 0.5:1. acidic oxygenated compounds with hydrocarbons 45 which comprises selectively extracting the neu Acid tral oxygenated compounds from the mixture in Solvent Water Bottoms a liquid-liquid extraction by contact with a sol went comprising dilute aqueous acetic acid con Mo Per Cent Extracted: Alcohols------35 37 taining 2% to 10% acetic acid by weight, at a 2 1 50 temperature between the freezing point of the Acids------Solvent and 125 C., separating an extract phase 1 Gain in acid content by oil phase, i.e. 4 mol% acid (based on comprising the neutral oxygenated compounds amount in the feed) lost to raftinate phase by acid bottoras. and a raftinate phase comprising the hydrocar Solventffeed, volune ratio 1:1.) bons and acidic oxygenated compounds, and re covering the neutral oxygenated compounds from the extract phase. Solvent Water Bishs 2. An improved process for the separation and recovery of aliphatic neutral oxygenated com Mol Per Cent Extracted: pounds comprising alcohols, aldehydes, ketones, Alcohols------47 42 60 esters and acetals, from a mixture of neutral and Acids------21 --1 acidic oxygenated compounds with hydrocarbons The solvent/feed ratios employed may be varied of Substantially the same boiling range which over a wide range and will be determined in any comprises selectively extracting the neutral com particular case by the extraction temperature, pounds from the mixture in a liquid-liquid ex the equipment employed and desired cleanup of 65 traction by contact with a solvent comprising the extractable oxygenated compounds. For dilute aqueous acetic acid containing 2% to 10% most purposes, the optimum range of solvent to acetic acid by weight, at a temperature between feed ratio is 2 or 3 to 1 although operation at the freezing point of the solvent and 125° C., from about 0.25 to 1 to as high as 10 to 1 may be Separating an extract phase comprising the neu Carried out Satisfactorily. 70 tral oxygenated compounds and a raftinate phase By the solvent extraction process as described Comprising the hydrocarbons and acidic oxygen in this invention all the oxygenated compounds ated compounds, and recovering the neutral oxy containing up to and including five carbon atoms genated compounds from the extract phase. are quantitatively removed from the oil layer 3. A process according to claim 1 in which the with the exception of the esters. The esters of s neutral oxygenated compounds comprising alco 2,569,884 O hols, aldehydes, ketones, esters and acetals, con of carbon are hydrogenated in the presence of tain from 1 to 6 carbon atoms per molecule. a catalyst to yield a product which when Con 4. A process according to claim 1 in which the densed, separates into a hydrocarbon oil phase solvent is aqueous acid bottoms containing not and an aqueous phase, which comprises Sep more than 35 weight percent of higher homo s arating the hydrocarbon oil phase from the logues of acetic acid based on the weight of aqueous phase, fractionally distilling the aque acetic acid recovered from the water layer of a ous phase to produce an overhead product com hydrocarbon synthesis reaction product. prising essentially neutral oxygenated organic 5. An improved process for the recovery of compounds, and an aqueous bottoms comprising neutral aliphatic oxygenated compounds Cons O 2% to 10% by weight of acetic acid and not more taining 1 to 6 carbon atoms per molecule from than 35 weight percent of higher homologues of a mixture of such neutral oxygenated compounds acetic acid based on the weight of acetic acid, with hydrocarbons and acidic oxygenated com extracting the hydrocarbon oil phase in a liquid pounds of substantially the same boiling range, liquid extraction at a temperature between about said mixture resulting from the catalytic hydro 5 0 C, and 125 C. with Said aqueous bottoms Con genation of oxides of carbon which comprises taining the acidic oxygenated compounds, Sep selectively extracting the neutral oxygenated arating an extract phase comprising neutral compounds from the mixture in a liquid-liquid oxygenated compounds contained in the oil extraction by contact with a dilute aqueous Solu phase and a raffinate comprising the hydrocar tion of acetic acid containing approximately 2 20 bons and acidic compounds contained in the oil to 5 weight percent of acetic acid, at a temper phase, combining the extract phase with the ature between the freezing point of the solvent original aqueous phase for recovery of neutral and 125 C., separating an extract phase Com compounds therefrom by distillation, and ex prising the neutral oxygenated compounds and tracting the raftinate with water to recover acidic a rafflinate phase comprising the hydrocarbons 25 compounds therefrom. and acidic oxygenated compounds, and recover 11. An improved process for the Separation of ing the neutral oxygenated compounds from the neutral and acidic oxygenated aliphatic com extract phase. pounds from reaction products produced in a 6. A process according to claim 5 in which hydrocarbon Synthesis reaction whereby Oxides the extraction is carried out at a temperature SO of carbon are hydrogenated in the presence of between 0° C. and 125 C. a Catalyst to yield a product which when con 7. A process according to claim 5 in which the densed, separates into a hydrocarbon oil phase ratio of solvent to feed extracted is between and an aqueous phase, which comprises Sep 0.25 to 1 and 10 to 1. arating the hydrocarbon oil phase from the 8. An improved process for the separation and aqueous phase, extracting the hydrocarbon oil recovery of aliphatic neutral oxygenated come phase in a liquid-liquid extraction at a temper pounds comprising alcohols, aldehydes, ketones, ature between about 0° C. and 125 C. with a esters and acetals, and of organic acidic oxygen dilute aqueous solution of acetic acid containing ated compounds from mixtures thereof with hy 2% to 10% of acid by Weight, and separating drocarbons which comprises selectively extract an extract phase comprising neutral oxygenated ing the neutral compounds from the mixture Compounds phase and a raftinate comprising the in a liquid-liquid extraction by contact with a hydrocarbons and acidic compounds phase. Solvent comprising dilute aqueous acetic acid CHARES E MORRELL. containing 2% to 10 weight percent acetic acid, JAMES H. MCATEER. at a temperature between the freezing point of 45 the solvent and 125 C., separating an extract REFERENCES CTED phase comprising the neutral oxygenated come The following references are of record in the pounds and a raftinate phase comprising the acidic oxygenated compounds and the hydron file of this patent: carbons, recovering the neutral oxygenated con UNITED STATES PATENTS pounds from the extract phase, and recovering Number Name Date the acidic oxygenated compounds from the raft 1838,547 Haslam ------Dec. 29, 1931 nate phase by extraction with water. 2,348,191 Canelford ------May 9, 1944 9. A process according to claim 8 in which the 2,457,257 Michael et al. ------Dec. 28, 1948 acidic oxygenated compounds are recovered from SS 2,472,219 Lyons ------June 7, 1949 the raftinate by extraction of the raftinate with 2,476,788 White ------July 19, 1949 water at a temperature between 0° C. and 250° C. 2,505,752 Burton ------May 2, 1950 10. An improved process for the separation of neutral and acidic oxygenated aliphatic come OBER REFERENCES pounds from reaction products produced in a to U. S. Naval Technical Mission in Europe, hydrocarbon synthesis reaction whereby oxides page 90,