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Method of separating organic

US 2520715 A
ABSTRACT available in

CLAIMS available in
DESCRIPTION (OCR text may contain errors)
COMPOUNDS BY MEANS OF UREA AND THIOUREA No Drawing. Application March 29, 1947, Serial
No. 738,213
Claims. 1
This invention relates to a process for the extractive fractionation of organic compounds. More
particularly, it relates to improvements in the process of fractionally extracting organic compounds from
mixtures thereof by the use of such complex-forming agents as urea and thiourea.
The fractionation of mixtures of organic compounds presents numerous problems, both technical and
economic. For example, the separation of mixtures of closely allied isomers, such as octane from isooctane, is difficult by any of the more reasonably economic procedures such as alkylation, isomerization
and cyclization is reduced if feed stocks are not of the correct composition, either during the primary feed
state or in recycling operations.
In most of such conversion'reactions an equilibrium mixture is generally obtained comprising fixed ratios
of unconverted feed stockand the desired product, such as from a previous cycle through the converter,
the amount of conversion is correspondingly reduced.

Under these circumstances a mixture of complexes usually was formed. or cyclic compounds such as most aromatics and naphthenes. etc. It has been noted that if only a minor amount of complexes are formed and thereafter separated from the mixture by filtration the thin layer of crystals tends to clog the filter cloth and thus to reduce the efiior a cycloaliphatic structure. toluene. for example. This latter process is usually employed for the purification of aromatics such as benzene. This was due to the characteristics of the complex-forming agents whereby under a given set of operating conditions certain classes of compounds formed complexes with the agents present. as well as non-aromatics. an improvement upon the known process would comprise a revision thereof whereby the final product substantially excluded naphthenes and largely comprises isoparaifins. but appear to be unstable molecular complexes rather than true chemical reaction products. The general procedure known to the prior art comprised treatment of such mixtures with a solution of the complex-forming agent. while it appears to be inert in this respect toward branched compounds such as the isoparafiins. this process were being used for the preparation of high'octane gasoline. If. including straight-chain compounds. In a number of instances a mixture of organic compounds contains a relatively minor fraction of material which will form crystalline complexes with one of the above agents.The two principal means for fractionation of such mixtures on a commercial scale have been by fractional distillation and by solvent extraction. . Many mixtures of organic compounds. Therefore. a new method has been shown to be suitable for large scale separations. ciency of the filtration step. Recently. the treatment of such a mixture with thiourea resulted in the formation of complexes of both of these types of hydrocarbons with thiourea. if both isoparafiins and naphthenes were present in a mixture of hydrocarbons. These processes are particularly applicable to the refinement of petroleum or other hydrocarbon mixtures. namely urea and the unaltered organic compound. This is indicated by their unstable character and the consequent ease of the regeneration of their components. the presence of naphthenes in the product would be undesirable. such as petroleum fractions. For many purposes the presence of one or another type of compound in admixture with other types is undesirable. Under normal operating conditions. The complexes so formed are of indeterminate structure. however. namely extractive crystallization with urea. When thiourea is the complex-forming agent employed the complexes formed thereby are usually. It was found that urea forms crystalline complexes with organic compounds of substantially normal structure. especially those of unbranched structure (which may be suitably fractionated by complex formation with urea) or hydrocarbons of branched chain or saturated cyclic structure (which readily form complexes with thiourea). contain aromatics such as alkylated benzenes. branchedchain compounds. Thus. of a substantially different character in that thiourea forms complexes with organic compounds having either a branched configuration zoo-s74) from mixtures containing other types of compounds usually in excess. thiourea forms only minor amounts of complexes with organic compounds normal parafpounds.

Furthermore. it is possible thereby to remove the aromatic fraction either prior to or subsequent to complex formation or prior to or subsequent to the isolation of the complexes so formed. due to the unreactivity of the aromatics toward either of the complex-forming agents discussed above. particularly those wherein the complex-forming agent is either urea or thiourea.For many purposes it is advantageous to completely separate the aromatic fraction from other types of materials which may be present. By this improvement it is possible to simultaneously separate aromatic constituents from a mixture while other types of separation are being effected with the complex forming agent which is present. . Such selective solvents include especially alcohols. It is another object of this invention to provide for the production of more highly fractionated materials than those theretofore possible by the subject extractive fractionation processes. By raflinate" is meant that portion of the mixture of organic compounds which fails to form crystalline complexes in the presence of urea or thiourea. it has heretofore been difficult to isolate or remove aromati fractions from mixtures to be treated by complexforming agents or from the raflinate obtained in such operations. nitrobenzenes. It is an object of this invention to improve extractive crystallization processes.p'- . 'Due to similarity of melting points such separations are often difiicult when attempted by fractional distillation. Now. in accordance with this invention. modified by the addition thereto of substances such as acetamide. furfural. it has been found that the formation of complexes between urea or thiourea and organic compound mixtures containing both aromatic and nonaromatic fractions may be improved by conducting the complex formation in the presence of a solvent medium for the aromatic fraction.e'.. Other objects will become apparent during the following discussion. It is a further object of this invention to effect the separation of aromatic compounds from other portions of a mixture during a complex forming treatment.plexes which may be formed. the mixture settling into three or more phases. In carrying out the process of the present invention. mixtures 01 organic compounds containing aromatic and non-aromatic fractions may be contacted with a complex-forming agent in the presence of a selective solvent for the aromatic fraction. one of which is a solution of the aromatics. Other suitable selective solvents include dimethyl sulfolane. The selective solvent for aromatic constituents should be substantially a non-solvent for the other components of the reaction mixture and especially for the non-aromatic constituents which may be present as well as for any com.and saturated cyclic com. said medium being a non-solvent for the other components of the reaction mixture. Still in accordance with this invention. said raflinate being substantially free of any aromatic constituents. phenols. After phase separation the three phases may be individually recovered such as by filtration of the crystalline complexes and decanting of the solution of aromatics from the immiscible rafilnate phase. The mixture may then be passed to a settling tank wherein phase separation occurs. Two other phases which will be present are the crystalline complexes formed between the agent employed and at least a part of the non-aromatic constituents of the mixture of organic compounds as well as a raflinate phase immiscible with the solution of the aromatics. aniline or ethanolamines.

especially the paraffins. acids. heptadecane. and olefins.2-pentadiene. 1. undecane.3-butadiene. octane. 8heptadecene. etc.2-butadiene. silicones. according to the process of the present invention are the normal diolefins such as 1. The mixtures of organic compounds which may be treated with urea by the process of the present invention comprise compounds having substantially normal structure and/or compounds having a predominating substituent of substantially normal structure. 5-undecene. etc. hexadecane. 2-decene. the selective solvent may be added to the mixture of organic compounds during or after complex formation. 2-hexene. tridecane. l-hexene. The alcoholic solutions containing modifying agents such as the ethanolamines. l-tridecene. aromatics. pentane. 5-decene. or from other organic compounds such as isoparafiins. 4-octene. tetradecane. mercaptans. carbohydrates. Under these circumstances the alcoholic solutions become substantially non-solvents for nonaromatic constituents of organic compound mixtures. l-dodecene. B-heptene. decane. The hydrocarbons respond especially well to the process of the present invention. octadecane. 2-nonene. esters. 6-tridecene. amides. disulfides. amines. G-dodecene. should contain from about to about 50% of such modifiers. . heptane. naphthenes. Z-heptene. 13-heptacosene. nitrocompounds. It has been found that the presence of substantially inert selective solvents do not appreciably affect the complex formation. ketones.dichloroethyl ether. 3-nonene. Conditions may be employed whereby certain normal organic compounds are separated from other normal organic compounds. l-decene. Olefin hydrocarbons which may be treated by the process of the present invention include 1. 2-pentene. 2-octene. lundecene. the aromatics then never passing through the zone wherein complexes are formed. eicosane. halogenated compounds. sulfides. alcohols. etc. Another class of hydrocarbons which may be formed into complexes with urea. 1. Suitable hydrocarbons which form crystalline complexes with urea include the parafiinic hydrocarbons such as butane. dodecane. nonane. 3decene. and liquid sulfur dioxide. l-pentadecene. 3-hexene.butene. nonadecane. l-octene. In this case the phase separation may be effected prior to complex formation. 3-octene. the phase containing the aromatic constituents may pass through the latter zone and may be separated from the reaction mixture in a subsequent operation. such as hydrocarbons. pentadecane. l-pentene. 2-undecene. The organic compounds of normal structure which may be formed into complexes by the process of the present invention include both saturated and unsaturated compounds. Alternatively. 2butene. ethers. 4-nonene. The normal compounds may be of a number of types. The selective solvent described above may be added to the mixture of organic compounds prior to contacting with either urea or thiourea. Alternatively. l-heptene. hexane. etc. aldehydes.

paraldehyde. carnaubyl alcohol. tridecoic. acid.6-octadiene. natural products such as petroleum. 2. Ethers of normal structure forming complexes with urea include acetal.5octadiene.3-pentadiene.2-hexadiene. etc. myristic.4. such as branched parafiins. 4. etc. lauric. These include sorbic and linoleic acids.4. The reason for and use of diluents is discussed hereinafter. pentadecanoic.4-decadiene. etc. etc. Other types of normal-structured compounds which may be treated according to the process of the present invention includes esters. active or inert diluents or solvents may be added to normal organic compounds in order to modify the type and degree of crystallization of the latter with urea. . etc. such as butyric. margaric.heptadiene. 1. especially when treat. caprylidene. stearic.4. diacetylene. lsomerization. crotonyl ether. tiglic acid. and may occur therewith naturally or by reason of some treatment to which the organic material has been subjected. butylacetylene.3.5-hexatriene. 2. 2.3-decadiene. especially those having six or more 'carbon atoms. propylacetylene. such as ethylene glycol. amides. 1. The acetylene acids form urea complexes. nonyl alcohol. diethylene glycol. dioxane. 1. cetyl alcohol. enanthylic.hexadiene. undecylic. etc. caprylic.3-heptadiene. citral adipaldehyde.5-nonadiene. etc. such as stearamide. olefin-acetylenes and the diolefln-acetylenes. caproaldehdye. Acids also may be treated according to the subject process. etc. etc.5-hexadiene. etc.6. 1. capric.6-nonadiene. Typical normal acids forming urea complexes are the normal fatty acids.. ethyl stearate. palmitic.9-decadiene.8-nonadiyne. thioalcohols. cyclization. 1. such as amyl acetate. Aldehydes of normal structure also respond to the process of this invention. 1. 2.6-heptadiene. 2. oleic acid.3-hexadiene. ethylacetylene.5-heptatriene. including 1. 1.. 1. 1.3-pentanedione.3. and the polyhydric alcohols. 2.4-octadiene. or they may contain materials substantially inert toward urea. the inert ingredients are present as isomers of the normal structure compounds. Normal alcohols.17octadecadiene. including halogenated derivatives of the above compounds. amines such as n-decyl amine.6-dodecadiene. Themixturescontainingtheorganiccompounds of normal structure may be composed solely of mixed normal compounds.7 decadiene. pelargonic.1.hexadiene. heptyl alcohol. 1. 2. However. cycloparaffins. isoolefins. 1. etc. amylacetylene. These include the aliphatic monohydric alcohols such as hexyl alcohol.8-decadiene. 1. mercaptans. such as methacrylic acid. 2.3. nitroparaffins. valeraldehyde. dibutyl amine and triethyl amine. 3. palmitone. dodecyl alcohol. 1. amino acids. 1-hepten-3-yne. propylene glycol and hexitol. 2. octyl alcohol.4.octadiene. diacetylenes. Ketones which form urea complexes are exemplified by 3-hexanone. 1.5-hexadien-3-yne. aromatics. caproic. 1.5-octadiene..3hexadiene. Normal hydrocarbons of a greater degree of unsaturation which form crystalline complexes with urea'by the process of the present invention include the triolefines. propyl-diacetylene.8-nonadiene. 1. palmitic aldehyde. thioaldehydes.octyne. 1. Acrylic acids also respond. including butyraldehyde. Usually. alkyl hydrazines.7. valeric. such as alkylation.pentadiene. acetylenes. 1. may be treated by the present process to form complexes with urea. such as heptyl mercaptan: and other organic compounds of normal structure. 1. decyl alcohol. especially those having four or more carbon atoms.octatriene.

2-dimethyl.5. 3ethyldecane. 4-methylheptane.5-diethyloctane.3.3.5-dimethyldecane. isohexane.6. 2. 1.Isoparafllns which form complexes with thiourea include isobutane. 5 methylnonane. 6 propyldodecane. 4-methyl-G-propylundecane. 2.6-pentamethylheptane. 2.6-dimethyl-3isopropylheptane. 2.5 dimethyloctane. 2.7-dimethyl-4-isobutyloctane.11.4. 2.3dimethylnonane.4 tetramethylpentane. 1.2. 4. 4-ethylundecane. 2 methyl 4 ethylhexane. 2.6. 2.4. 2.5 tetramethylhexane. 2. 2.3-dimethyldecane.4 dimethylpentane. 1.3.5-tetramethylhexane.4.2. 3.4 trimethylheptane.4trimethyloctane. 3.3.4. 4 methylnonane.4-trimethy1heptane.5 dimethylheptane. 5 propyldodecane.3 dimethylhexane.4. 4. 2-n-propylbutane. 2-methylheptane.4. 3-ethylhexane. 2-ethylpentane.3. 3 ethylheptane.dimethyl 3 ethylpentane.4.3 trimethylheptane.5-diisopropyloctane. 2. 3. 2.2 dimethylpentane. 2.l0-trimethyldodecane.5-trimethylheptane.6 tetramethylheptane. 2.9-dimethyldecane.2.2.6 dimethylnonane.dimethyldodecane.4. 2.ethyldodecane. 2 methyloctane. 2.1 dimethylpentane.3. 2. 4-methyldecane. 2.7 dimethyloctane. 4-propyldecane.2. 5.2. 2.3. 2. 2.2. 3. 2.2. 2. 2.3 dimethylpentane.diethylhexane. 1.4-dimethylnonane. such as alkaryl hydrocarbons wherein at least one alkyl group.7.3 trimethylhexane.3-tetramethylhexane.5-tetramethylheptane. 2. 2.5. 3-methylhexane.5-. 2. 2-methylhexane. 2.7. 2.6trimethy1heptane.4.4 dimethylhexane.7 trimethyloctane.7 trimethyloctane. 2. 2.4 dimethyloctane. 2.4 trimethylhexane. 2.6-trimethylheptane.3.5 trimethylhexane.2. 2. 3. 4 propylundecane.dimethylpentane. 3. 2. 5-ethylnonane. 2.Hydrocarbons which form complexes with thiourea are those having a predominating member which is a substantially branched radical or a naphthene radical.4 dimethylheptane.9- .2. 3-ethyloctane. 2. 3.7tetramethyloctane. 2.7 tetramethyloctane.dimethylundecane.3-dimethylnonane. 2 methyl 3 ethylpentane. 2.4 trimethylhexane.3.4 trimethylhexane. is an isoparaifin radical of about six or more carbon atoms.4-tetramethylhexane.4. 2. 2.3 dimethylheptane. 2. 2.3. 2. 3. 2.2-dimethylpropane.2dimethylpentane.2.3 din'iethyl 3. 2.6-dimethyldecane. 2-ethylbutane.5 dimethylnonane. 2.9-trimethyldecane.3. 5butylnonane.5-dimethyloctane.6. 3.4-dim'ethylhexane. 6methyl-7. 4ethylnonane.6 dimethylheptane. 3. 2.3. 4 isopropylheptane. 5 propylnonane. 3. 2.3. 3.3-trimethylpentane.2.3. 4methylundecane. 2.2. 2.3-trimethylpentane.methyl 5 ethylheptane. 2.3dimethylhexane.2. 2. 2 ethylpropane.2. 3 methylundecane.3-tetramethylheptane.3-dimethylbutane. 3.7.2 dimethyloctane.4 trimethylpentane. 2-isopropylbutane.3. 2. . 3-methylheptane. 2-methyl 5 propyloctane.2. 2 methylnonane. 3-methy1 3 ethylheptane.3-dimethyloctane.4ethylhexane. 2.4. 2.6. 3-methylpentane.2-dimethylheptane. 2.4 dimethyl 3 ethylpentane.3.3.2-dimethylhexane.3.6 trim'ethylheptane.3-trimethylbutane.6-dimethyloctane. 2 methyl 3 ethylhexane.tetramethylbutane.4dimethyloctane. 2. 3ethylpentane. 3.6-diethyloctane.methyldecane.2. 2.3. 4 ethylheptane. 2. 2. 2.3 trimethylhexane. 3-methyloctane.2. 2.dimethyl-4. 3 methyl-3-ethylpentane. 2.3-dimethylpentane.methylpentane.4-dimethylpentane.6.3 diethylpentane.6 dimethyloctane.4 tetramethylhexane. 2.4 7 dimethylheptane. 2.2.5 trimethylhexane. 2. 3 methylnonane.tetramethylpentane. 2.4.6-tetramethyloctane.3-trimethylheptane.2.2. 2. 2. isopentane. 5methyldodecane. 3.3 dimethyloctane. 4methyloctane. 2.3 dimethylheptane. 2.2.tetramethyloctane.4 diethylhexane.5.dimethylhexane. 2. 3. 2. 4 propylheptane.3.3.2. 3. 6.

1. l-methyl-i-isopropyl 2 dodecyclohexane. 1. 7.8-dimethyl-5-ethy1. Steam distillation. 1-methyl-2.1diethylcyclopentane. Complexes may be formed having varying amounts of the complex-forming agent combined with the active organic compound. 5.5-trimethylcyclohexane.1. it is preferred practice to contact the mixture with urea employed in an amount in excess of that necessary for complete complex formation.4-diethylcyclobu. butylcyclopentane. isopropylcyclopentane. 3.3-dimethyl-5-ethylcyclohexane. 1-methyl-3ethylcyclopentane.8-dimethyltetradecane. 1..2dimethylcyclohexane.trimethylcyclopentane. pentamethylcyclohexane.3. there remains the step of decomposing the complexes in order to recover the active organic compounds present therein.While a number of methods have been found for effecting "such a decomposition or regeneration. 1.2.2-dimethyl-3. 1. etc. isoamylcyclopentane. triisopropylcyclohexane.3-dimethyl-5-ethylcyclopentane.6. 1. The formation. 1.5 -cyclohexylnonane.propylcyclopentane. 3-cyclohexyl. 1. Simple distillation.3.'the extractive fractionation may be carried out with the intention of removing from the mixture the maximum amount possible of the compounds of normal structures present.11tetrapylcyclobutane. 1-methyl-3-propylcyclohexane. amylcyclopentane.1-dimethylcyclohexane. 1.2dimethylcyclopentane. 0.3-trimethylcyclohexane. propylcycloheptane.3. 1. 1.3 -ethylpentane. 1. l-methyl 2 ethylcyclopentane. methylcyclohexane. propylcyclopentane. .trimethyl-4-isopropylcyclopentane. 1. isobutylcyclopentane. separation and purification of the complexes having been accomplished as described hereinbefore.4diisopropylcyclobutane. l-methyl-3-isopropylcyclohexane. 2-cyclopentylpentane. amyloyclohexane. The ratio of the complex-forming agent to active organic compounds will vary with the type of mixture to be treated and with the conditions of complex formation.3 dimethylcyclohexane. 2.dimethyltetradecane.2. Application of a solvent for the complexforming agent. 1.2-tetramethyl-3.5-diethylcyclopentane. 1-methyl-3butylcyclopentane. 1. 3-ethyltetradecane. 1. In this particular case. 1-methyl-2.1-dimethylcyclopentane. 1. butylcyclohexane.cyclohexane.3-diethylcyclohexane.3 dimethylcyclopentane.7-diethyldodecane. When the temperature or other conditions during complex formation are such that about 3 mols of the agent combined with about every 4 carbon atoms of the active organic compound-it is preferred practice to contact the active organic compound with an amount of the agent somewhat in excess of this ratio. cyclopentane. octadecylcyclohexane. ethyl-.G-diethylcyclohexane.2. 4-cyclohexylheptane.1 tane. ethylcyclopentane. methylcyclopentane. 2. For example. cyclohexane. l-methyli-ethylcyclohexane. 1.2-dimethyl-3. the following methods have been found to be the most satisfactory for use when carrying out the process of the present invention: A. 1.7.3-dimethyl-2 ethylcyclopentane. 1-methyl-3propylcyclopen tane. heptylcyclopentane.

The crystalline complexes so formed were removed by filtration and the two liquid phases were separated by decantation. fractionation according to solubility may be readily accomplished. thus regenerating the organic compounds and complexforming agents and. a solution of part of the regenerated organic compounds which form and may be readily separated from the insoluble fractions which are present. simultaneous destruction of the complex and fractionation or the organic compounds regenerated therefrom may be accomplished. It has been found that due to their unstable character. When such a mixture is heated the complex decomposes. the complex-forming agent and the organic compounds in complex combination therewith separately recovered in their original state. splitting into the component parts of the complex may be readily accomplished. For example. Following the regeneration by such means it is usually necessary to purify or fractionate the regenerated compounds and the regenerated complex-forming agent for further use. A further type of regeneration comprises addition of a solvent for the complex-forming agent such as water or alcohol to the complex and the application of heat to facilitate the regeneration. One of the liquid phases . Fractionation by simple heating is satisfactory for some purposes. Application of a solvent for aparticular fraction of the regenerated organic compounds.D. By this means the regenerated organic compounds separate from the solution of the complex-forming agent and subsequently may be fractionated by normal purification or fractionation procedures. The complexes. E. Steam distillation is preferable where the organic compounds to be regenerated are of such high boiling point that their distillation would be accomplished by substantial decomposition. if it is desired to enrich the feed with low boiling normal hydrocarbons. The process of the present invention is useful for the preparation of high octane gasoline for minutes the reaction mixture was allowedto settle into three phases. as has been pointed out hereinbefore. complexes of urea and a mixture of normal hydrocarbons may be decomposed by distillation and the distillant may be recycled to the mixer. in presence of such a solvent. the exact nature of which has not been deduced. are relatively unstable formations which appear to be loose combinations involving hydrogen bonding or some form of molecular attraction. Hence. The distillation may take place under normal or reduced pressures and the temperature and pressure are so adjusted that the complexes-are readily destroyed and the compounds regenerated therefrom are distilled into fractions which can be utilized for the purposes considered herein. Heating. A more preferred type of regeneration comprises the addition of a solvent for one or more fractions of the organic compounds to be regenerated from the complexes. Steam distillation is a refinement of the above process and the principle of regeneration and fractionation applies here as well. By subjecting the complexes to distillation.

In the process for the fractionation of a liquid mixture of hydrocarbons. and sepa. the inert nonaromatic fraction and the alcoholic acetamide solution of urea. The crystalline complexes were heated in the presence of water to about 75 C. In the process for the fractionation of a liquid mixture of petroleum hydrocarbons wherein crystalline complexes are formed between a fraction thereo fand thiourea. thereby forming three phases. the improvement which comprises conducting said complex formation in the presence of a solvent. acetamide and alkylated benzenes. the improvement which comprises conducting the complex formation in the presence of an alcoholic solution of acetamide. whereby complexes are formed between urea and at leastpart of said straight-chain hydrocarbons. 4. said mixture also containing an aromatic . said mixture also containing an aromatic fraction and a non-aromatic inert fraction not forming complexes with urea under the fractionating conditions.10 rately recovering the complexes. wherein crystalline complexes are formed between a fraction thereof and an agent of the group consisting of urea and thiourea. thereby forming three phases. The process which comprises treating a mixture of petroleum hydrocarbons containing aromatic and substantially straight-chain hydrocarbons with urea. 2.. wherein crystalline complexes are formed between a fraction thereof and urea. said solvent being a solvent for the aromatic fraction of the mixture and a non-solvent for the nonaromatic inert fraction and the crystalline complexes. a liquid non-aromatic inert phase. 3. a liquid solvent phase containing the dissolved aromatic fraction and the solid crystalline complex phase. forming complexes with the agent under the i'ractionating conditions. whereby crystalline molecular complexes of urea and normal octane formed. acetamide and aromatic fraction. at which temperature the complexes decomposed to yield the normal octane originally present in the gasoline and an aqueous solution of urea and two phases were separately recovered by decantation. and separately recovering the complexes prior to separating the solution of aromatics from the remaining portion of the non-aromatic hydrocarbons. and separately recovering said complexes. a liquid non-aromatic inert fraction phase. The other liquid'phase comprised the raifinate and contained substantially no aromatics but the entire quantity of iso-octane present in the original gasoline. in the presence of an alcoholic solution of acetamide which is a solvent for the aromatic fraction but a non-solvent for the remainder of the reaction mixture. 5. isooctane and alcoholic solution of urea. a liquid solvent phase containing the aromatic fraction dissolved in the alcoholic acetamide solution and the solid crystalline complex phase. whereby a solution of said aromatic fraction is formed. The process which comprises treating a mixture of alkylated benzenes. and separating said phases.comprised the alcoholic solution of acetamide containing dissolved therein substantially all of the alkylated benzenes in the original gasoline. iso-octane and normal octane with a saturated alcoholic solution of urea having 20% by weight of acetamide dissolved therein. I claim as my invention: 1. In the process for the fractionation of a mixture of petroleum hydrocarbons. said mixture also containing an aromatic fraction and a non-aromatic inert fraction not.

1952 Process for decomposing adducts US2634261 * Jan 9. 1937 466. 1949 .396.081. the improvement which comprises conducting said complex formation in the presence of an alcoholic solution of an ethanolamine which is a solvent for the aromatic fraction but a non-solvent for the remainder of the reaction mixture. 1950 Nov 25.189 Great Britain Jan. PATENT CITATIONS Cited Patent Filing date Publication date US2081524 * Oct 27. 011 Mission. FET'IERLY.303 Cummings et al. 1937 US2396303 * Dec 7. REFERENCES CITED The following references are of record in th file of this patent: UNITED STATES PATENTS Number Name Date 2. Tech. ' LLOYD C. 5 pages. 1946 Applicant Title Process for solvent extraction of Rohm & Haas Refining hydrocarbon oils GB459189A * Title not available GB466980A * Title not available * Cited by examiner REFERENCED BY Citing Patent Filing date Publication date Applicant Title US2588602 * Dec 27. 1937 2. 1946 FOREIGN PATENTS Number Country Date 459. 1940 Mar 12. thereby forming three phases. and separating said phases. 1937 OTHER REFERENCES Beng'en.980 Great Britain July 9. Reel 143. 1934 May 25. 1948 Apr 7. 1952 Fractionation of organic compounds US2619501 * Apr 10. 1947 Mar 11. 12. 4. a liquid solvent phase containing the aromatic fraction dissolved in the alcoholic ethanolamine solution and the solid crystalline complex phase. 1953 Socony Vacuum Oil Co Inc Separation of wax from residual lubricating oil US2642378 * Sep 13.fraction and a non-aromatic-inert fraction not forming complexes with thiourea under the fractionating conditions. 1953 Shell Dev Urea complexes Jun 16. Mar. a liquid non-aromatic inert fraction phase.524 Barnes May 25.

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Classifica tion .