Process for Obtaining Para-Cresol and Meta-Cresol From a Mixture of Methylated and Ethylated Phenols Characterized by Urea Clathration of Metal-Cresol

This application is related to applications entitled "Process for Separating Para-Cresol from a Mixture of Methylated and Ethylated Phenols," Ser. No. 53,438, "Process for Obtaining Para-Cresol and Meta-Cresol from a Mixture of Methylated and Ethylated Phenols Containing Meta- and Para-Cresol," Ser. No. 53,532, and "Process for Obtaining Para-Cresol and Meta-Cresol from a Mixture of Methylated and Ethylated Phenols Characterized by Selective Complexation with Calcium Bromide and Sodium Acetate," Ser. No. 53,195, all of Gerd Leston, filed on June 29, 1979, which applications are hereby incorporated by reference.

The present invention relates to a process for separating para-cresol and meta-cresol from a mixture of methylated and ethylated phenols. More particularly, the process is directed to obtaining separately high purity para-cresol and meta-cresol isomers from a mixture of methylated and ethylated phenols.

Mixtures of methylated and ethylated phenolic compounds may be derived from coal as products of coal carbonization, as the middle oil from the hydrogenation of coal, from the liquefaction of coal, or from petroleum as alkaline extracts of cracked petroleum distillate. Some of the methylated and ethylated phenols in a mixture derived from these sources have similar physical properties. These similarities in properties make it difficult to separate some of the phenolic compounds from each other. Para-cresol and meta-cresol are compounds that are usually present in mixtures of methylated and ethylated phenols, and they are difficult to separate from the other methylated and ethylated phenols and from each other. For example, para-cresol is difficult to separate from meta-cresol since both compounds have similar boiling points, namely, 201.8.degree. C. and 202.8.degree. C., respectively. The similarity of boiling points of these two compounds precludes their separation by simple distillation and also makes fractional distillation a complicated procedure.

There are several known methods for separating para-cresol and meta-cresol isomers from a mixture containing the isomers, such as a commercial mixture having 40-65 percent of meta-cresol. These methods include treatment of a mixture containing meta- and para-cresol isomers with complexing agents such as urea, sodium acetate, oxalic acid or the like and separation of the meta- or para-cresol isomers in adduct form. Other methods include the formation of a solid complex between a reagent and one cresol isomer. The reagents used include ortho-toluidine, oxalic acid and hexamethylenetetramine. Still other methods for separating meta- and para-cresol isomers involve azeotropic distillation with benzyl alcohol, or selective solvent extraction with methanol-ligroin, or hydrolysis of the sulfonic acid of meta- or para-cresol, or dibutylation followed by distillation and debutylation. Another recently suggested method for separating meta-cresol and para-cresol isomers takes advantage of the different melting points of the compounds and involves subjecting the meta- and para-cresol isomer mixture to crystallization at atmospheric pressure of not less than about 300 atmospheres. Only a few of the foregoing methods of separation have any commercial potentialities, the process usually employed being the butylation method. A more efficient method is thus desired to obtain high purity para-cresol and high purity meta-cresol from mixtures of methylated and ethylated phenols containing compounds such as ortho-ethyl phenol, xylenol and other methylated and ethylated phenols having similar boiling points to para-cresol and meta-cresol.

An article entitled "Rapid Separation of Organic Mixtures by Formation of Metal Complexes", Journal Organic Chemistry, Volume 40, No. 9, 1975, Sharpless, Chong and Scott, describes a convenient and efficient technique for resolving alcohol mixtures. The technique involves preferential complexing of an alcohol by calcium chloride or manganese chloride, examples of useful alcohols being cis- and trans-4-tert-butylcyclohexanol, geraniol, and cyclohexanol. The article further notes that other alcohols, such as large and hindered alcohols, form complexes very slowly, and that the speed of complex formation can be increased by using a small amount of a lower aliphatic alcohol as a catalyst for complexing.

The present invention provides a process which includes a novel combination of cresol isomer separation steps. The process comprises a two-step separation of para-cresol and meta-cresol from a mixture of methylated and ethylated phenols by complexation of each of the isomers with different components. It is an advantage of the present process that the isomer complexation reactions may be accomplished in any order, that is, either of the para-cresol or meta-cresol isomers may be separated from the mixture, followed thereafter by separation of the remaining isomer. The process comprises the steps of (a) for separation of para-cresol isomer: adding to a mixture of methylated and ethylated phenols containing para-cresol and meta-cresol isomers and methylated and ethylated phenols having similar boiling points to para-cresol and meta-cresol, one or more anhydrous or dehydrated inorganic salts selected from the group consisting of calcium bromide, lithium bromide, manganese bromide and magnesium chloride in an amount sufficient to produce a complex between predominantly para-cresol and the salt, whereby the para-cresol-salt complex may be separated from the mixture, and then decomposed to produce predominantly para-cresol; and (b) for separation of the meta-cresol isomer: adding to the mixture of methylated and ethylated phenols an amount of urea sufficient to produce predominantly meta-cresol-urea complex, whereby the meta-cresol-urea complex may be separated from the mixture, and then decomposed to produce predominantly a high purity meta-cresol. The amount of anhydrous or dehydrated inorganic salt added to the mixture of methylated and ethylated phenols to produce a para-cresol salt complex is added in an amount to give a mole ratio of salt to para-cresol in the mixture in the range of about 0.5 to one to 1.5 to one. This addition of the salt is preferably conducted in the presence of a non-aqueous solvent. The addition of the urea to the mixture of methylated and ethylated phenols is preferably performed with an amount of urea to give a mole ratio of urea to meta-cresol in the mixture in the range of about 0.7 to one to about 1.3 to one. This addition is also preferably performed in the presence of a non-aqueous solvent. The order of separation of the isomers may be step (a) followed by step (b) or may be step (b) followed by step (a).

In the process of the present invention, important variables include the salt to para-cresol mole ratio and, to a lesser extent, the variables of para-cresol concentration in the mixture of methylated and ethylated phenols, the solvent used and the temperature of complexing. The salt to para-cresol mole ratio is generally in the range of about 0.5 to one to about 1.5 to one. The para-cresol concentration in the mixture of methylated and ethylated phenols can be any concentration, but generally is at least that concentration that can be purified or separated economically. When the amount of para-cresol in the mixture is low, e.g., on the order of 10 percent, the preferential complexing of the para-cresol can be enhanced by the use of higher temperatures in the order generally of about 70.degree. C. to 130.degree. C. The mixture of methylated and ethylated phenols contains, in addition to para-cresol and meta-cresol, other methylated and ethylated phenols having similar boiling points with the para-cresol and meta-cresol. The solvent used should be a non-aqueous solvent, since water will react with the anhydrous inorganic salt to form one or more hydrates. Generally, the non-aqueous solvent should not, itself, complex with the salt or at least not more readily than the para-cresol. The addition of the salt to the mixture of methylated and ethylated phenols can be initially with or without the use of the solvent, but once the salt is added to the mixture, a solvent should then be employed to facilitate mixing of the salt and the mixture. Generally the temperature at which complexing occurs ranges from ambient temperatures to a temperature of about 130.degree. C., depending upon the concentration of para-cresol in the mixture of methylated and ethylated phenols. If the complex formation is not initiated at higher temperatures, the temperature can be lowered to initiate complex formation, and then raised to a higher temperature. If the para-cresol-salt complex formation is slow, an initiator, such as a lower aliphatic alcohol or a previously formed complex of the para-cresol and salt, can be used to initiate the complexing reaction. Once the para-cresol-salt complex is formed, it may be separated from the mixture by any method known to those skilled in the art for separating solid complexes from liquids. Once separated, the para-cresol-salt complex can be decomposed by thermal decomposition at atmospheric pressure, or by distillation at reduced pressure, or by treatment with water, or by treatment with alcohol. When the complex is decomposed, the high purity para-cresol is recovered and the anhydrous inorganic salt can be recycled for further complex formation with para-cresol, if the decomposition occurs by thermal decomposition or decomposition by distillation.

In the meta-cresol separation stage, wherein the meta-cresol isomer is separated from the mixture of methylated and ethylated phenols, the important variables are the concentration of the meta-cresol in the mixture, the temperature of complexing, and the concentration of urea used. Generally, the amount of urea utilized is within a mole ratio of urea to meta-cresol in the range of about 0.5 to one to about 2 to one; prerferably the mole ratio is in the range of about 0.7 to one to about 1.3 to one. The temperature of complexing of the meta-cresol and the urea may be in the range of about 0.degree. C. to about 100.degree. C. at atmospheric pressure. The type of solvent used and the manner of separation of the meta-cresol-urea complex from the mixture of methylated and ethylated phenols are similar to the solvent and procedures used in the formation of the para-cresol-salt complex. It is preferred, however, that the meta-cresol-urea complex be decomposed by hydrolysis rather than thermally.

When the para-cresol-salt complex and meta-cresol-urea complex are separated from the mixture of methylated and ethylated phenols, it is best to dry the complexes and recycle any non-aqueous solvent obtained in the drying process. The non-aqueous solvent can be recycled to the complex-forming step.

In the process of the present invention, para-cresol and meta-cresol can be obtained in high purity form from a mixture of methylated and ethylated phenols having similar boiling points to the para-cresol and meta-cresol isomers. Non-limiting examples of the methylated and ethylated phenolic compounds of the mixture include ortho-cresol, ortho-ethylphenol, thymol, xylenol and trimethylphenols. It is preferred that the mixture contain substantial quantities of para-cresol and meta-cresol; for example, a useful mixture is a commercial mixture of meta- and para-cresol isomers which contains from 40-65 percent of the meta-cresol isomer, the remaining being the para-cresol isomer. Also, the preferred methylated and ethylated phenolic compounds are those methylated phenols that do not form complexes with the anhydrous inorganic salts of calcium bromide, lithium bromide, manganese bromide or magnesium chloride, or that are not thermodynamically favored over the para-cresol-salt complex, or that form complexes at a slower rate than para-cresol and meta-cresol.

The process of the present invention is based on the discovery that certain anhydrous or dehydrated inorganic salts, when used in a certain mole ratio to para-cresol in the mixture of methylated and ethylated phenols, preferentially complex with the para-cresol. The described useful anhydrous salts, especially calcium bromide, also tend to form complexes with the meta-cresol isomer. It is believed, however, that the formation of the para-cresol-salt complex is thermodynamically controlled while the formation of the meta-cresol-calcium bromide complex is kinetically controlled. Thus, while the rate of the meta-cresol-calcium bromide complexation may be higher than that of the para-cresol-calcium bromide complexation at certain high concentrations of the meta isomer, formation of the para-cresol-calcium bromide complex will ultimately prevail because the para-cresol complex is more thermodynamically stable than the meta isomer complex. It is a feature of the present process that when separation of the meta isomer is undertaken firstly, complexation of the meta isomer with urea occurs preferentially and selectively over the para isomer.

The amount of para-cresol in the mixture of methylated and ethylated phenols, and preferably in the mixture of para- and meta-cresol, can be practically any amount of para-cresol since practically any amount of para-cresol can be separated from the mixture as long the proper mole ratio of anhydrous inorganic salt to para-cresol is used. Generally, it is preferred that the para-cresol be present in the mixture of methylated and ethylated phenols in an amount of at least about 15 weight percent.

The anhydrous inorganic salts of calcium bromide, lithium bromide, manganese bromide or magnesium chloride that are used in the process of the present invention are the commercial anhydrous salts or the hydrated forms of the salts that have been dehydrated. Dehydration of the salts can be in any manner known to those skilled in the art. Anhydrous salts are readily prepared from hydrated forms such as aqueous solutions or flaked hydrate forms. It is preferred that either the aqueous or flaked form be heated to around 200.degree. C. in air to give the anhydrous material in a solid chunk, which may be then ball milled or ground for use.

In one embodiment of the present invention wherein complexation of para-cresol is accomplished firstly, a mixture of methylated and ethylated phenols that contains an amount of para-cresol and meta-cresol is treated to complex a substantial portion of the contained para-cresol by the use of one or more anhydrous inorganic salts (hereinafter referred to as salt). These salts are selected from the group consisting of calcium bromide, lithium bromide, manganese bromide and magnesium chloride. One or more of these salts is added to the mixture in an amount to give a mole ratio of the salt to the para-cresol in the mixture in the range of about 0.5 to one to about 1.5 to one. If the mole ratio of the salt to para-cresol is above 1.5 to one, other methylated or ethylated phenolic compounds may complex or may complex to an extent and complicate the separation of para-cresol from the mixture. If the mole ratio of salt to para-cresol is below 0.5 to one, then the maximum amount of para-cresol present in the mixture will not be separated and the yield of the process will be decreased. The preferred mole ratio of salt to para-cresol depends on the particular salt used. The preferred ranges of mole ratio of the salts to para-cresol are as follows: calcium bromide, about 0.8 to one to about 1.2 to one; lithium bromide, about 0.8 to one to about 1.2 to one; manganese bromide, about 0.8 to one to about 1.2 to one; and magnesium chloride, about 0.8 to one to about 1.2 to one. These ranges are all based on the mole ratio of salt to para-cresol contained in the mixture. To obtain the mole ratio of salt to para-cresol in the mixture, it is necessary to determine the amount of para-cresol in the mixture of the methylated and ethylated phenolic compounds. This can be done by any analytical technique known to those skilled in the art for determining the amount of para-cresol in a mixture of organic compounds.

The addition of the proper amount of salt can be performed in the presence or absence of a non-aqueous solvent. If the solvent is not present upon the initial addition of the salt to the mixture of methylated and ethylated phenolic compounds, it must be added at a later time when, upon formation of the complex, mixing of the salt and the components of the mixture becomes difficult. The non-aqueous solvent is added in an amount to facilitate mixing of the components. The non-aqueous solvent should not complex with the salt but, if complexing occurs, then the solvent must complex to a lesser extent than the para-cresol. A few examples of non-aqueous solvents that can be used are toluene, methylene chloride, chlorobenzene, ortho-dichlorobenzene, and lower aliphatic alicyclic compounds such as hexane, as well as oxygenated compounds like ethers, ketones and esters, as long as any complex that is formed is weaker than the complex formed by the para-cresol. The preferred non-aqueous solvent is toluene because of its relatively low cost.

During the addition of the salt to the mixture and complexing of the salt and the para-cresol, the temperature is in the range of about ambient temperature, generally around 20.degree. C., to about 130.degree. C. at atmospheric pressure. If super-atmospheric or sub-atmospheric pressures are employed, the temperature will vary accordingly. Moderate increases in the temperature within this range during complexing will increase the rate of complex formation. If the complex is not initiated at the higher temperatures within the above range, the temperature can be lowered to initiate complexing and then raised to increase the rate of complexing. The higher temperatures are preferred when there is a small amount, e.g., around 15 weight percent, of the para-cresol in the mixture.

If complex formation with a particular salt is not initiated within a reasonable time, an initiator may be used to catalyze complex formation. Such initiators include normal-aliphatic alcohols such as anhydrous ethanol, anhydrous propanol and anhydrous butanol. A catalytically effective amount of alcohol to be used would be about 1 to about 10 weight percent. Another useful initiator is a previously formed para-cresol-salt complex. A complex of para-cresol and calcium bromide, or lithium bromide, or manganese bromide, or magnesium chloride, can be used to initiate complex formation. The catalytically effective amount of the complex used is again in the range of about 1 to about 10 weight percent of the mixture being treated. It is preferred that anhydrous ethanol be used as the complex initiator or, alternatively, a complex be used containing the same salt that is used to complex the para-cresol.

The time taken for the complex formation varies for the particular salt used. Lithium bromide is extremely fast in forming a complex with the para-cresol while calcium bromide, magnesium chloride and manganese bromide are somewhat slower. Lithium bromide forms a complex within about three to five minutes compared with several hours for the other salts. The preferred anhydrous salt that is used in the para-cresol complexing stage of the present invention is calcium bromide since it has high selectivity and provides good conversion.

Once the para-cresol-salt complex, preferably the para-cresol-calcium bromide complex, is formed, the complex is separated from the mixture of methylated and ethylated phenols, preferably a mixture of para-cresol and meta-cresol. This separation can be by any method and in any equipment known to those skilled in the art for separation of a solid complex from a liquid solution. Preferably, the complex is separated by filtration to render a supernatant liquid containing the methylated and ethylated phenols including meta-cresol. The filtered complex of the para-cresol and the salt is decomposed to release the para-cresol and recover the salt that can be recycled for additional complexing.

In the second stage of this embodiment of the process of the present invention wherein complexation of the meta-isomer is accomplished subsequent to complexation of the para isomer, the supernatant liquid from the first stage that contains methylated and ethylated phenols and meta-cresol is treated with urea to complex the meta-cresol contained therein. It is an advantage of the process of this invention that a specific mole ratio or minimum amount of meta-cresol for complexation with urea is not required to accomplish efficient separation of the meta isomer. The urea is added to this mixture in a mole ratio typically in an amount in the range of about 0.7 to one to about 1.3 to one of urea to meta-cresol in the mixture. The addition and the complexing usually occur at a temperature in the range of about 0.degree. C. to 100.degree. C. Once the meta-cresol-urea complex is formed, the complex is separated from the mixture of methylated and ethylated phenols. This separation can be by any method and in any equipment known to those skilled in the art for separating a solid complex from a liquid solution. Preferably the complex is separated by filtration to produce a supernatant liquid that contains methylated and ethylated phenols that did not complex and uncomplexed meta-cresol and para-cresol. The meta-cresol obtained upon decomposition of the complex is a high purity meta-cresol that has a purity in the range of about 97-99 percent. When the mixture treated by the process of this invention is a mixture of para-cresol and meta-cresol, the supernatant liquid obtained after the meta-cresol complex is removed in the second stage also contains predominantly meta-cresol in a purity less than that obtained from the meta-cresol-urea complex. The purity of the meta-cresol in the supernatant liquid may typically be in the range of about 90-95 percent.

Before either the para-cresol-salt complex or the meta-cresol-urea complex is decomposed, it is preferred that the complexes be dried to remove the non-aqueous solvent. This drying may be done by any process known to those skilled in the art for drying a solid to remove a solvent. Preferably, the drying is performed by vaporizing the solvent at a temperature above the solvent's boiling point but less than the decomposition temperature for the complex. The recovered solvent obtained from the drying step can be recycled for use in either of the complexing steps.

In the decomposition of the para-cresol-salt complex and the meta-cresol-urea complex, decomposition of the two complexes is performed separately but in a similar fashion and thus will be discussed together. The decomposition is preferably performed by heating the complexes to a decomposition temperature of about 200.degree. C. at atmospheric pressure. Alternatively, the complexes can be decomposed by distilling the complex at a reduced pressure, or by hydrolysis, or by cleavage with other agents, such as an alcohol, that form stronger complexes than the para-cresol or meta-cresol complex. Thermal decomposition is preferred for releasing the para-cresol and meta-cresol isomers and recovering the salt and urea since it is the most economic method of decomposition and since the complexing agents recovered can be recycled for use in further complexing. The thermal decomposition can be performed in any equipment known to those skilled in the art useful in conducting decomposition reactions. Preferably the thermal decomposition is performed in a Rinco evaporator at temperatures up to about 200.degree. C. and under reduced pressure. Alternatively, the complexes can be decomposed at a temperature of around 125.degree. C. under vacuum conditions. In another alternative embodiment, the complex can be hydrolyzed with a sufficient amount of water to decompose all of the complex. Also, since alcohols form stronger complexes than phenols, the alcohols can be used to cleave the complex such that the alcohol will be substituted in the complex for the para-cresol or the meta-cresol. The disadvantage of this decomposition method is that the solid complexing agent is not directly recoverable for recycling. When hydrolysis is used for decomposition, the halide salt or urea recovered would have to be dehydrated again before it could be recycled.

The para-cresol recovered from the decomposition reaction may contain a minor amount of meta-cresol and other methylated and ethylated phenols such as ortho-ethylphenol. If improved purity is desired, the para-cresol can be complexed repeatedly as is done in methods of fractional distillation. The meta-cresol recovered from the decomposition reaction is a high purity meta-cresol in the range of about 98+ percent purity, but may contain minor amounts of para-cresol and other methylated and ethylated phenols.

The complex formation of the para-cresol and the anhydrous inorganic salt and the complex formation of the meta-cresol-urea can be performed in conventional reaction equipment. Also, the complexing can be performed in a batch manner or a continuous manner where the reactants are cascaded from one reaction vessel to another.

FIG. 1 is a flow diagram of a preferred embodiment of the present invention .

The mixture of methylated and ethylated phenols from which para-cresol and meta-cresol are separated in the preferred embodiment contains a two-to-one mole ratio of meta-cresol isomer to para-cresol isomer. This mixture enters a complexing zone 12 through a conduit 10 together with calcium bromide which enters the complexing zone through a conduit 14. The amount of calcium bromide added to complexing zone 12 is preferably an amount which will give a mole ratio of calcium bromide to para-cresol in the range of 0.7 to one to about 1.0 to one. A non-aqueous solvent, preferably toluene, is also added initially to complexing zone 12 through a conduit 16. In complexing zone 12, the mixture of meta- and para-cresol isomers, the toluene and the calcium bromide are mixed at a temperature of around 100.degree. C. for about eight hours, there being sufficient toluene present to ensure thorough mixing of the components during the complexation stage. At the end of this time a substantial portion of the para-cresol is complexed with calcium bromide and this complex, along with the supernatant liquid containing meta-cresol, is removed through a conduit 18 from complexing zone 12. The supernatant liquid may contain small quantities of ortho-cresol, xylenol, ortho-ethylphenol, or other methylated or ethylated phenols.

The supernatant liquid which includes the para-cresol complex leaves complexing zone 12 through conduit 18 and is conveyed into a filtration zone 20, where the complex is separated from the supernatant mixture. The wet para-cresol-calcium bromide complex is conveyed from filtration zone 20 through a conduit 22 to a drying zone 24, where the complex is dried and the toluene is separated from the complex. The toluene is then recycled through a conduit 26 to a conduit 28 where it is mixed with additional toluene and conveyed to filtration zone 20 to wash the wet complex. The supernatant liquid from which the para-cresol-calcium bromide complex has been removed is conveyed from filtration zone 20 via conduit 30 to complexing zone 32.

After the para-cresol-calcium bromide complex has been dried in zone 24, the complex is conveyed through a conduit 34 to decomposition zone 36. In zone 36 the complex is heated to a temperature of around 200.degree. C. at atmospheric pressure to decompose the complex to produce para-cresol and to regenerate the calcium bromide salt. The product para-cresol product leaves decomposition zone 36 through conduit 38 and is of a purity of about 98 percent. The regenerated calcium bromide leaves decomposition zone 36 through conduit 14 and is conveyed to complexing zone 12 to further complex with the para-cresol isomer. In an alternative embodiment, additional calcium bromide can be added to conduit 14 through conduit 40 from an outside source (not shown).

After separation of the para-cresol isomer, the supernatant liquid typically has a concentration of the meta-cresol isomer of about 95 percent by weight of samples taken from the mixture. The supernatant liquid is delivered to complexing zone 32 through conduit 30 together with urea supplied through conduit 33. The supernatant liquid and the urea are mixed at a temperature of about 20.degree. C. for several hours to allow complexation of the meta-cresol isomer with the urea. The complex of meta-cresol-urea and the uncomplexed mixture is conveyed from complexing zone 32 through conduit 44 to filtration zone 46.

In filtration zone 46 the meta-cresol-urea complex is separated from the uncomplexed mixture. The complex is withdrawn from the filtration zone 46 through conduit 48 and delivered to drying zone 50. In drying zone 50 the complex is dried and toluene is removed through conduit 16. A portion of the toluene is introduced back into filtration zone 46 through conduit 52 to wash the wet meta-cresol-urea complex, with the remainder of the toluene returning through conduit 16 to complexing zone 12 for reuse in the complexing of para-cresol.

The dried complex is conveyed from drying zone 50 through conduit 54 to decomposition zone 56 wherein the meta-cresol-urea complex is decomposed by hydrolysis. The meta-cresol withdrawn from decomposition zone 56 through conduit 58 has a purity of around 98 percent. The regenerated urea is then dried and withdrawn from decomposition zone 56 through conduit 42 and is conveyed to complexing zone 32 for further complexing with the meta-cresol. Additional urea can be added to complexing zone 32 through conduit 33 from an outside source (not shown).

The uncomplexed mixture leaving filtration zone 46 by conduit 60 consists of 85-95 percent pure meta-cresol. This mixture can be used as a less pure meta-cresol product or can be treated in other ways to obtain pure meta-cresol.

The following examples set forth specific embodiments of the invention. However, the invention is not to be construed as being limited to these embodiments for there are, of course, numerous possible variations and modifications. All parts and percentages recited in the examples and throughout the specification are by weight, unless otherwise specified.

In each of the following examples, meta-cresol isomer is separated from mixtures having a greater proportion of meta-cresol isomer than para-cresol isomer. Mixtures having greater concentrations of the para isomer over the meta isomer may be treated in accordance with the procedures described in the aforementioned related applications for removing substantial amounts of para isomer from the isomer mixtures.

To a reaction vessel equipped with heating apparatus, stirring means and a thermometer, there is charged a mixture of 342 parts meta-cresol and 18 parts para-cresol together with 800 parts powdered urea, approximately 3,300 hexane and about 80 parts ethanol. The mixture is stirred continuously over-night with the temperature of the mixture being held at about 20.degree. C. The solid reaction product, amounting to about 1,058 parts, is then filtered, washed with additional amounts of hexane and dried. The hexane solvent is removed from the filtrate by heating, there being a residue of 98 parts. Gas chromatographic analysis of hydrolyzed solid reaction product and filtrate residue rendered results reported to Table 1.

To a reaction vessel equipped as in Example I, there is introduced 675 parts of a mixture of meta-cresol and para-cresol isomers in a two-to-one molar ratio, together with 1,000 parts of urea, 80 parts ethanol and 3,300 parts hexane. The mixture is stirred for about 24 hours, with the temperature being maintained at about 20.degree. C. The solid reaction product, amounting to 1,261 parts, is filtered, washed with hexane solvent and dried in vacuo. The hexane solvent is removed from the filtrate by heating, there being left 420 parts residue. Gas chromatographic analysis of the hydrolyzed solid reaction product and filtrate residue rendered results reported in Table 1.

Although specific examples of the instant invention have been set forth hereinabove, it is not intended that the invention be limited solely thereto, but is to include all the variations and modifications falling within the scope of the appended claims.