MXPA00008272A - Improved process for the production of a dihydroxybenzene and dicarbinol from diisopropylbenzene - Google Patents

Abstract

Improved methods for the simultaneous production of dihydroxybenzene and dicarbinol from diisopropylbenzene are provided. These methods provide for continuous and simultaneous production of DHP and HHP using Karr Column extractors operated in series. A very purity DHP-containing solution, the precursor to the dihydroxybenzene, can be produced according to the reported methods. A safe and efficient method for producing dicarbinol from HHP is also disclosed.

Description

IMPROVED PROCESS FOR THE PRODUCTION OF A DIHYDROBENZENE AND DICARBINOL FROM DIISOPROPYLBENZENE FIELD OF THE INVENTION The present invention relates to an improved process for the simultaneous, continuous production of dihydrobenzene (DHB) and diisopropylbenzene dicarbinol (DCL) from diisopropylbenzene. More specifically, this process includes the steps of: oxidizing diisopropylbenzene to obtain an oxidized comprising, inter alia, diisopropyl-ylbenzene dihydroperoxide (DHP) and diisopropylbenzene hydroxyhydroperoxide (HHP); extract DHP and HHP from the oxidized in an aqueous caustic solution using a Karr Column operation, continuously and simultaneously isolating the HHP and DHP in separate fractions of the caustic solution using the Karr Column cooling and extractions with hot methyl isobutyl ketone (MIBK), producing dihydroxybenzene by cleaving the fraction of the DHP extract in the presence of an acid catalyst, and producing dicarbinol by decomposing the HHP fraction under atmospheric conditions using an aqueous alkaline solution.

BACKGROUND OF THE INVENTION It is known in the art that hydroperoxides, such as diisopropylbenzene dihydroperoxide (DHP), diisopropylbenzene monohydroperoxide (HP), and diisopropylbenzene hydroxyhydroperoxide (HHP), can be produced by oxidizing diisopropylbenzenes with molecular oxygen either in the presence or absence of basic catalysts. The oxidation and continuous production of diisopropylbenzene dihydroperoxide from diisopropylbenzenes in the presence of a strong base, such as sodium hydroxide are described, for example, in British Patent No. 727,498 and US Patent No. 3,953,521. describe that the hydroperoxides of m- and p-diisopropylbenzene can be continuously isolated from the oxidation mixture of diisopropylbenzene by caustic extraction, and that the continuous oxidation of diisopropylbenzenes for the production of dihydroperoxides can be achieved by maintaining the pH in the range of between 8 and 11 at the temperature of about 85-95 ° C in the oxidation reactor British Patent No. 727,498, as well as US Patent No. 2,856,432, also disclose that the dihydroperoxides (DHP) present in the oxidation mixture of diisopropylbenzene can to be effectively separated by means of caustic solutions at 4-8% by weight. Hydroperoxide (DHP), part of the hydroxyhydroperoxide (HHP) present in the oxidation material is also extracted into the caustic solution. U.S. Patent No. 4,237,319 also discloses a method for the batch production of m-diisopropylbenzene dihydroperoxide (m-DHP) by oxidizing m-diisopropylbenzene under alkaline conditions. The removal of the DHP in the caustic solution, as described in the prior art, can be followed by the isolation of the DHP for the > production of a dihydric phenol, such as resorcinol or hydroquinone, in various forms. Of those methods, a preferred method in the art is to extract the DHP from the caustic solution in an organic solvent, preferably MIBK. Using this solvent, a temperature of 70-80 ° C and contact times of 5-10 minutes is possible to extract a high portion of the DHP in MIBK with negligible losses due to decomposition. British Patent No. 921,557 discloses that the m-DHP present in the aqueous caustic solution is extracted by the MIBK solvent at 75 ° C. To improve extraction efficiency, US Patent No. 3,932,528 discloses that by adding about 1% ammonia in an 8% caustic soda solution containing 12.3% DHP, the MIBK solvent is more effective at 60 ° C for the DHP extraction through three stages of countercurrent contact.

U.S. Patent No. 4,059,637 discloses a method whereby the DHP present in the caustic solution is extracted using IBK solvent in a four stage countercurrent mixer-settler type extraction. The caustic solution containing the DHP used in the extraction of the mixer-settler type was previously treated with MIBK at a temperature below 30 ° C to remove the oxidation by-products having the 2-hydroxy-2-propyl group such as hydroxyhydroperoxide diisopropylbenzene (HHP) and diisopropylbenzene dicarbinol (DCL). It is reported that the HHP content of the caustic solution containing "-DHP" before being fed to the mixer-settler for extraction is approximately 4.2% After the extraction, the purity of the DHP in the MIBK solution reported is 93% Several patents describe different acid type catalysts and temperatures to obtain a dihydric phenol such as resorcinol or hydroquinone from DHP by cleavage For example, British Patent No. 743,736 describes sulfuric acid as the catalyst for the cleavage of m-DHP in the presence of a MIBK solvent under reflux conditions With a residence time of between about 7.5-10 minutes and 0.2% by weight of H2S04 catalyst, 99.6% of the DHP is decomposed British Patent No. 819,450 describes a sulfur trioxide catalyst for the cleavage of m-DHP, it is reported that sulfur trioxide produces a cleavage reaction much faster than corresponding amount of acid ^^ sulfuric. The decomposition of m-DHP is carried out continuously in two reactors connected in series, using MIBK and acetone as the solvents used in the cleavage operation. Canadian Patent No. 586,534 also discloses the use of a sulfur trioxide catalyst to cleave m-DHP, in the presence of 0.3% by weight of water in the cleavage reaction. The American Patent No. 3,923,908 discloses a process for cleaving di-hydroperoxides from di-propylbenzene in the presence of impurities such as isopropylphenyldimethylcarbinol (MCL), diisopropylbenzene hydroxyhydroperoxide (HHP) and diisopropylbenzene dicarbinol (DCL) using a sulfur trioxide catalyst and a solvent. In order to effectively use the dihydropyrrobenzene hydrobromide peroxide (HHP), the Application Japanese Patent 95-304027 and the Patent Application Japanese No. 95-301055 describe a method by which a solution of MIBK containing HHP is reduced by hydrogen in the presence of a palladium-alumina catalyst (a material containing 1% by weight of palladium metal) in an autoclave equipped with a stirrer, at a pressure of hydrogen of 6 atmospheres and a reaction temperature of 90 ° C, to obtain diisopropylbenzene dicarbinol (DCL). Although this method produces DCL from HHP, the safety of this process is questionable, since it involves the manipulation of hydrogen at high pressure in the presence of a highly volatile solvent (MIBK) at high temperatures. An important aspect recognized in the art for producing high purity dihydric phenol by the hydroperoxidation technology is to prepare a high purity cleavage feed (DHP) from the oxidation mixture of diisopropylbenzene. Although DHP is produced in the oxidation of DIPB, it may not be easy to completely remove the DHP from the oxidation mixture for use in the cleavage step of the hydroperoxidation process. In a first standard step of separating the DHP from the oxidized, a caustic extraction is typically carried out using a 4% or 8% NaOH solution. During this extraction, DHP is extracted as well as other impurities present in the oxidized, - such as HHP, acetyl-isopropylbenzene hydroperoxide (KHP), MHP, etc. When an 8% NaOH solution is used, it is known that 90-95% of the HHP and KHP present in the oxidation mixture in the caustic solution are extracted, along with approximately 1-2% of MHP. The MHP present in the caustic solution is extracted again with a DIPB solvent. The solution comprising the DIPB, the extracted MHP and other extracted oxidation impurities can then be recycled to the oxidation reaction and subjected to oxidation. This extraction of DIPB does not have much effect on the removal of other impurities such as HHP and KHP from the caustic extract solution, however. To remove the HHP from the caustic solution, typically, extraction of the MIBK solvent is carried out at low temperature. Despite this operation, the concentration of HHP in the caustic solution before the final MIBK extraction may still be relatively high and, therefore, it has been found that this method is a difficult route to produce a DHP of purity very high for the excision. None of the patents or other literature in the art suggests or discloses that impurities such as KHP present in the caustic extract are expected. If the extraction methods or methods are not efficient, then it is expected that impurities from the hydroperoxidation process will interfere with the isolation of a very high purity DHP necessary for a highly efficient cleavage operation. None of the techniques teaches or suggests a process by which, in a continuous operation, a very high purity can be produced from the diisopropylbenzene oxidation materials. In an attempt to produce a high purity DHP material, US Pat. No. 4,059,637 describes a method in which four extractors of the mixer-settler type are used. The caustic solution containing DHP used in the 637 patent contained DHP and HHP in a ratio of approximately 98.8: 4.2, even after extraction of MIBK at 20 ° C was carried out on the solution. According to this patent, this extraction of cold MIBK from caustic extraction was carried out separately as a discontinuous process rather than integrated with the extraction operation of the mixer-settler. This procedure produced a product containing low purity DHP by the cleavage reaction. Thus, techniques used in the art to separate a high purity DHP from the DIPB oxidation materials have disadvantages. One process only fully describes a continuous method to obtain a high purity DHP from oxidized, although the nature of the impurities extracted in the caustic extractions and with MIBK is identified and characterized. In addition, methods described in the art for preparing DCL from DIPB oxidation materials give rise to safety concerns. There remains, therefore, a need for processes that provide safe and efficient preparation of products such as a high purity DHP feed for use in the preparation of DHB as well as DCL.

BRIEF DESCRIPTION OF THE INVENTION The present invention has met the needs described above by providing a novel process for the preparation of a dihydric phenol, such as resorcinol or hydroquinone, from a cleavage feed containing high purity DHP and at the same time time also effectively utilizes the impurity of HHP in the oxidation product of DIPB for the manufacture of dicarbinol. This method generally comprises the steps of oxidizing diisopropylbenzene with molecular oxygen in the presence of a basic catalyst to obtain an oxidation reaction mixture, also referred to herein as "oxidized", comprising, inter alia, diisopropylbenzene dihydroperoxide (DHP) ) and diisopropylbenzene hydroxyhydroperoxide (HHP); feed the oxidized in a Karr Column, also referred to here as "caustic extraction column"; simultaneously and simultaneously remove DHP and HHP from the oxidized in a countercurrent operation; continuously generate a caustic enriched with DHP / HHP, also referred to herein as "enriched caustic", and a recycle stream, recycle stream which can be fed directly back to the oxidation reactor; continuously feed the rich caustic in a second Karr Column, also referred to herein as a "cold MIBK column", for the simultaneous and continuous generation of caustic enriched with DHP and the separation of HHP from the caustic enriched with DHP achieved by effecting this extraction operation with MIBK at a low temperature, also referred to herein as "cold MIBK extraction"; continuously feed the caustic enriched in DHP in a third column of Karr also referred to here as "column of hot MIBK", for the continuous generation of a DHP of very high purity to obtain a solution of MIBK, here referred to as "hot MIBK solution" ", to be fed at a cleavage step for the continuous generation of dihydroxybenzene and the continuous generation of a poor caustic containing very low levels of hydroperoxides without extracting. Prior to cleavage, the hot MIBK solution is preferably concentrated; the concentrate is then fed into a continuous cleavage reactor where the DHP is cleaved in the presence of a catalyst to produce the corresponding dihydric phenol, such as resorcinol or hydroquinone, and acetone. The HHP present in the cold MIBK extract obtained after the second extraction of Karr's Column is decomposed by treatment with an aqueous alkaline solution under atmospheric and aqueous conditions to obtain the corresponding dicarbinol. Therefore, an object of the present invention is to provide an improved process for the production of polyphenols, such as resorcinol or hydroquinone, and dicarbinol from diisopropylbenzenes. A further object of the present invention is to provide a process for the continuous separation of DHP b from the DIPB oxidation material and the generation of an oxidation recycling feed and a rich caustic flow from the caustic extraction using the operations of the Column of Karr. A further object of the present invention is provide a process for continuous separation and ^ Highly efficient impurities such as HHP, KHP, MHP and other oxidation impurities from the caustic flux rich in DHP / HHP performing an extraction with MIBK at cold temperature in a Karr Column. Another object of the invention is to provide a process for the production of a caustic rich in DHP for the extraction with MIBK at high temperature in a - Column of Karr. ^ fc Another object of the present invention is To provide a process for the continuous production of a feed of the very high purity DHP material from the cleavage step of the hydroperoxidation process by making extractions with MIBK on the caustic extract solution using the operations of the Karr Column.

Yet another object of this invention is to provide an aqueous, non-hydrogenated, safe, effective and efficient process for the conversion of HHP to DCL: These and other objects of the invention will be apparent from the following description of the invention.

BRIEF DESCRIPTION OF THE DRAWING Figure 1 is a schematic flow chart for a preferred embodiment of the process for producing dihydric phenol and dicarbinol from diisopropylbenzene according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method for manufacturing dihydroxybenzene and dicarbinol from diisopropylbenzene, comprising; a) "oxidizing diisopropylbenzene with oxygen in the presence of a basic catalyst to obtain an oxidation reaction mixture or" oxidized "comprising diisopropylbenzene dihydroperoxide (DHP), diisopropylbenzene hydroxyhydroperoxide (HHP), acetylisopropylbenzene hydroperoxide (KHP), and one or more members selected from the group consisting of diisopropylbenzene monohydroperoxide (MHP), isopropylbenzenecarbonol (MCL), diisopropylbenzene dicarbinol (DCL), acetyl -isopropylbenzene monocarbinol (KCL) and other organic peroxides; b) feed the oxidized, a caustic solution and an organic solvent into a Karr Column of caustic extraction; c) generating simultaneously and simultaneously two flows from the Karr Column of caustic extraction from step b), the first caustic extraction stream comprises DHP, HHP and KHP extracted in a countercurrent operation, and the second caustic extraction stream comprises one or more members selected from the group consisting of MHP, MCL, DCL, KCL, other peroxides • organic, the organic solvent fed to the Karr Column of caustic extraction and 'diisopropylbecene; d) continuously feeding the first caustic extraction stream from step c), an organic solvent cooled to a temperature of between approximately 10 and 30 ° C, and an alkaline solution in a second Karr Column; e) generate continuously and simultaneously two flows from the second Karr extraction column, the first cold extraction flow ^? comprises a cold organic solution comprising HHP and KHP, and the second cold extraction stream comprises caustic enriched with DHP; f) continuously feeding the caustic enriched with DHP from step e) and the organic solvent that has been heated to a temperature between about 40 and 85 ° C in a third Karr extraction column; g) Generating two flows from the third Karr Extraction Column, the first flow comprising a hot organic solution comprising high purity DHP and the second comprising a poor caustic comprising low levels of non-extracted hydroperoxides; h) concentrating the hot organic solution of step g) and feeding the concentrate into a continuous cleavage reactor where the DHP is cleaved in the presence of an acid catalyst to produce a solution comprising the corresponding dihydroxybenzene and acetone; and i) decompose the HHP present in a cold organic extract step e) by treatment with an aqueous sodium solution • under non-hydrogenated atmospheric pressure and aqueous conditions to obtain the corresponding dicarbin'ol. The process for the production of a dihydric phenol, such as resorcinol or hydroquinone, and Dicarbinol according to the present invention generally involves the production of diisopropylbenzene dihydroperoxide (DHP) and diisopropylbenzene hydroxyhydroperoxide (HHP) from diisopropylbenzene fl (DIPB) and the subsequent conversion of DHP to dihydric phenol corresponding and the HHP to the corresponding dicarbinol. Preferably the DIPB used here, and from which DHP and HHP are produced, is any of the m-diisopropylbenzene (m-DIPB), p-diisopropylbenzene (p-DIPB), or mixtures thereof.

The oxidation of DIPB, such as m-DIPB or p-DIPB, is generally carried out in the liquid phase in the presence of an oxygen-containing gas, which can be any of pure oxygen, such as molecular oxygen , or a mixture containing oxygen, such as air. The oxidation reaction can be carried out by a continuous or batch method, depending on the needs and preferences of the user. This oxidation reaction can be carried out in the presence or absence of one or more basic catalysts; preferably, a • basic catalyst such as sodium hydroxide or sodium carbonate. The presence of these basic substances in the oxidation reaction increases the efficiency of the oxidation, such as by increasing the oxidation rate retarding the development of excessive acidity due to the formation of carboxylic acids, including but not limited to formic acid, acetic acid, and the like, which prevent the oxidation reaction. The preferred pH for • the oxidation reaction is in the range of about 7 to 11. The product of the DIPB oxidation obtained, for example, by a continuous oxidation process described in British Patent No. 727,498 or by the batch oxidation process described in US Pat. No. 4,237,319, is suitable to be used in the methods of the present invention; the DIPB oxidation methods taught in other patents or publications may also be used, including, but not limited to, an anhydrous, non-alkaline process taught in U.S. Patent No. 4,935,551. The oxidation reaction can be conducted over a wide range of temperatures, preferably between about 80 and 120 ° C. For practical purposes, when the reaction is conducted in the presence of an aqueous caustic solution, the oxidation reaction is preferably carried out at about 90 ° C + 5 ° C, and at a pressure of about 20-80 psi (137.9-551.6 kPa). The oxidation of DIPB results in an oxidation comprising both of the desired DHP and HHP in addition to numerous oxidation by-products. These by-products include, for example, hydroperoxides such as isopropylbenzene monohydroperoxide (MHP) and acetylisopropylbenzene hydroperoxide (KHP), carbinoles such as isopropylbenzenecarboxol (MCL) and diisopropylbenzene dicarbinol (DCL); acetones such as acetyl-isopropylbenzene benzene (MKT) and acetyl-isopropylbenzene monocarbinol (KCl); and other organic peroxides formed from the reaction of hydroperoxide carbinoles, collectively referred to herein as "organic peroxides". The formation and accumulation of these by-products in the oxidation reaction only affects the oxidation rate of DIPB but also has an adverse influence on the separation of the DHP from the oxidized by the extraction methods carried out later in the process. The oxidized is then subjected to caustic extraction. The caustic extraction according to the present invention is carried out using a Karr Column. As will be appreciated by those skilled in the art, a Karr Column is a column having a system of oscillating plate deflectors. A caustic solution, the oxidized and an organic solvent are fed to the Karr Column in a "countercurrent" manner. Suitable organic solvents include, but are not limited to, toluene and m-xylene; Preferably, the organic solvent is DIPB. The caustic predominantly removes the DHP although the DIPB or other organic solvent removes the impurities. It is a feature of the present invention that the complete or nearly complete separation of the DHP from the product of the DIPB oxidation and the removal of the oxidation impurities from the caustic extract is carried out by caustic extraction and treatment of the DIPB simultaneously in a single extractor from Karr's Column. When the caustic extraction is carried out, the following conditions should be verified in the Karr Column: the speed of agitation, the temperature; and the oxidized feed rates, the caustic solution and the caustic solvent. Agitation should be carried out at a rate that allows at least one phase of the solution or mixture to disperse. Preferably, a stirring speed between about 50 and ^^ 300 revolutions per minute, more preferably 5 between approximately 100 and 150 revolutions per minute. If the agitation speed is too fast then an overflow of the column will occur resulting in poor extraction. On the other hand, a slow stirring speed will reduce the mixing between oxidized and caustic resulting in a poor separation of DHP. The extraction temperature, that is, the temperature of the solution within the "column, is preferably anywhere in the range of about 10 to about 80 ° C. If the temperature is greater than about 80 ° C, then dihydroperoxide tends to decompose in the presence of caustic resulting in a reduced DHP yield.Column temperatures less than about 10 ° C prevent proper mixing of oxidized and caustic.

Ideally, based on extensive extraction tests with a Karr Column, the temperature is preferably maintained between 25 and 40 ° C. The feed rates of oxidized, caustic and organic solvent will vary depending on several factors, such as the amount of oxidized that is being treated and the amount of DHP and HHP present in the oxidized. The optimization of these feeding speeds can be determined by a person skilled in the art based on the conditions and needs of the user. It has been found, according to the present invention, that when this operation of the Karr Column is used with the extraction conditions described above, the corresponding dihydroperoxide can be recovered easily and efficiently from the oxidation mixture in the solution. caustic Since the impurities hydroperoxide, such as MHP, MCL, etc., extracted in the • Caustic extraction is predominantly removed by treatment with solvent, organic or washed, a cycle of oxidation that transports those impurities is ready to feed back to the oxidation reactor. This fraction recycled and a caustic DHP reaction can therefore be obtained simultaneously in a single Karr Column. With this improvement, the oxidation and extraction steps of the hydroperoxidation process can be easily carried out in ^ fc series for the production and continuous extraction of the flow of DHP / HHP caustics for use in the production of dihydric phenol and dicarbinol by the methods of this invention. Verifying the composition of both the oxidation and the oxidation recycling before and after the extraction of the caustic, it can be observed that all or almost All the KHP and KCL present in the oxidized are extracted in the caustic. Those impurities will affect the purity of the final DHP if they are not removed. The present invention provides for the removal of those impurities, which are effectively extracted in the cold MIBK extraction described below, and therefore a DHP with a very high purity can be obtained. As stated above, the two flows resulting from the first or the Karr column for caustic extraction include recycling, which contains impurities, and a caustic DHP fraction, which will also typically contain HHP, KHP and KCL . Although the recycle is sent back to the DIPB oxidation reactor, the DHP / HHP caustic fraction is cooled to a temperature between about 10 to 30 ° C and fed to a second Karr column. Preferably, the caustic fraction is fed directly, without delay, to the second Karr column once the desired temperature is reached. Is cooling done to minimize? avoid the decomposition of hydroperoxides, which can be accelerated by high temperatures. Although it is preferred to feed the caustic fraction directly or "continuously" into the second column of Karr, it will be understood that this feeding does not have to be done directly. To minimize or prevent the decomposition of hydroperoxides, the caustic solution containing these hydroperoxides should be cooled to as low a temperature as possible if the next extraction is not carried out directly after the extraction of the caustic. In addition to the DHP / HHP rich caustic from the first Karr column, the second Karr column is also fed with an organic solvento such as acetone, preferably methyl isobutyl ketone (MIBK), and a sodium hydroxide solution. The solvent is used to extract the HHP and other impurities such as KHP, KCL, MHP or other organic peroxides which are known to affect the final purity of DHP. The three solutions should be fed to the second Karr column in a countercurrent fashion. Two flows are obtained after cold MIBK extraction: a caustic fraction with DHP; and a fraction of cold MIBK containing HHP, KHP, KCL, MHP and / or other oxidation products. The HHP, used for the production of dicarbinol, is therefore obtained directly and continuously from the extraction with cold MIBK of the caustic extract using the extraction of the second Karr column. As with the extraction of the first Column of Karr (caustic extraction), the appropriate conditions should be maintained in the second Karr Column, including temperature, agitation speed and feed rates. The most important condition is the temperature inside the column. For efficient operation, the temperature of the column, that is, the temperature of the solution within the column, should be within the range of 10 ° C to 30 ° C, preferably between about 10 ° C and 20 ° C. . Due to these temperature ranges, this step is known as the cold MIBK extraction step. The term "cold" as used in this context refers to a temperature between about 10 ° C and 30 ° C. if the temperature is much higher than about 3Q ° C, the DHP can move to the MIBK layer; Cooler temperatures of approximately 10 ° C may make it difficult to perform the operation since precipitation may occur. "The agitation speed in the second Karr column should be such that at least one phase of the solution is dispersed, and preferably it is maintained in the range of 100 and 400 revolutions per minute, more preferably in approximately 250 revolutions. per minute The feed rate of the rich caustic extract, the MIBK or other organic solvent, and the sodium hydroxide solution can be optimized based on the conditions and needs of the user.In cold MIBK extract analysis reveals that all or almost all the KHP, KCL, MHP and / or other impurities present in the caustic feed, fed to the second Karr Column are completely extracted in the cold MIBK solution.

The resulting caustic extract after extraction in the second Karr column contains almost exclusively DHP, with barely detectable amounts of HHP present in the caustic. The DHP present in the caustic solution is in the form of a disodium salt and may undergo decomposition at elevated temperatures and prolonged storage. As stated above, this solution of caustic extract is therefore preferably used directly in the following case to obtain a high purity DHP. As used here, the • The term "high purity" when used to describe DHP means that DHP has a purity of 99.7% or greater. According to the process of the present invention, high purity DHP can be produced by subjecting the fraction DHP caustic from extraction with cold MIBK to a second extraction with organic solvent, preferably a second extraction with MIBK. This second extraction with MIBK is an extraction with MIBK in "hot" which is carried out in a second operation of the column of • 20 Karr. "Hot" as used in this context refers to a temperature between about 40 and 85 ° C. The MIBK or other organic solvents are heated to a temperature within this range before being fed to the third column of Karr, together with the caustic fraction with DHP of cold MIBK extraction. This "hot" MIBK extraction is preferably carried out in a countercurrent fashion, where the preheated MIBK is preferably passed from the bottom of the column and the caustic solution from the top. In this way, the DHP salt is not exposed to conditions of higher temperature which is known to cause DHP decomposition. Due to the uniform temperature gradient inside the column, the conversion of salt from DHP to DHP can be easily achieved during extraction. , 10 For efficient extraction of the column, it It prefers to operate the column with the solution inside the column at temperatures between about 40 and 85 ° C. controlling the operating conditions of the third Karr column such as temperature, speeds of feed and stirring speed, a purity of DHP of 99.7% can be achieved. It will be appreciated that the higher the purity of DHP fed in the cleavage step, the greater the purity of the dihydroxybenzene obtained. As stated above, ? the temperatures are preferably maintained between about 40 and 80 ° C, more preferably between about 45 and 70 ° C. MIBK feed rates and caustic solution can be optimized based on user conditions and needs. The stirring speed is such that at least one phase of the solution or The mixture will be dispersed, preferably between about 100 and 400 revolutions per minute, preferably about 250 revolutions per minute. The hot and cold extraction steps of the present invention provide a flow of DHP of very high purity to feed into the cleavage step. In addition, this DHP flow of very high purity is produced in an efficient manner. Both the present methodology and the product obtained are superior to those reported in the art, such as U.S. Patent No. 4,059,637. This patent describes a process in which four extractions were used in a mixer-settler for the extraction of DHP from a caustic solution previously treated with MIBK to remove the HHP and other impurities. Prior to DHP extraction, the DHP content and the HHP content of the caustic solution as a material is 11.3 and 0.5%, respectively, and the ratio of DHP: HHP equal to 95.8: 4.2. In this multi-stage extraction, an extraction of a temperature difference between adjacent plates was established by fixing a heating or cooling device to each plate, for example, circulating hot water or cold water through the jacket of the extractors. Since each of the four mixer-settlers is an individual operation, the operation of the four mixer-settlers requires the use of many pumps, tanks, mixers and motors. In addition, to maintain the temperature of each plate in each mixer-settler, it may be necessary to heat or cool water. Despite the equipment requirements and conditions, the final purity of the DHP material obtained from this operation is very poor; the DHP and HHP content in the product is only approximately 4.83% and 0.38%, respectively, in 211 parts of MIBK extract, which corresponds to a ratio of DHP: HHP of 92.8: 7.2. The final relationship is therefore not much greater than the initial relationship. In contrast, the present invention provides a flow of DHP in which the DHP content is 99.7% or greater, using a much smaller equipment and labor-intensive process. After extraction with hot MIBK, the concentration of DHP in the MIBK is typically between about 6 to 12% by weight and the amount of water typically between about 1 and 3% by weight. Preferably, the hot DHP / MIBK solution is concentrated before the cleavage step, since if this hot MIBK extraction solution is fed directly to the cleavage reactor it often has adverse effects on the performance of the resorcinol or hydroquinone. Also, it is more economical to use a concentrated DHP solution to maximize the production of resorcinium or hydroquinone in the cleavage unit. The hot MIBK solution can be concentrated by any means known in the art. In a preferred method the solution is fed continuously into a vacuum evaporator and ^^ concentrated. After evaporation, the concentration of DHP in the solution is typically increased to between about 20 and 40% by weight and is preferably about 30% by weight. The water content is typically reduced to about 0.3% by weight. Although this concentration of DHP is suitable for the cleavage feed, higher DHP concentrations may be used if desired. Similarly, although a water content of about 0.3% -. in weight does not seem to affect the rate of excision, this concentration can be lowered by applying more stringent evaporation conditions.15 To effect the acidic cleavage of the DHP contained in the concentrated MIBK solution, any conventional techniques can be used. of cleavage can be carried out by any of a process ^^ continuous or batch. The reaction can take place within a wide range of temperatures, for example, between about 30 and 100 ° C. It has been found convenient to carry out the reaction at the boiling point of the reaction mixture, which is typically in the range of about 60 to 80 ° C depending on the acetone content in the cleavage reactor. By this method, the heat of reaction dissipates through reflux. The cleavage of DHP is more conveniently carried out using one or more acidic catalysts such as sulfuric acid, sulfur trioxide, phosphoric acid, hydrochloric acid, boron trifluoride, p-toluene sulphonic acid, and the like. The reactor used in the cleavage operation can be comprised, for example, of a stirred reactor or a tubular reactor. The stirred reactor or backmixing reactor for carrying out the reaction mixture are well known. According to the process of the present invention, a continuous cleavage reaction is carried out using a stirred reactor. In this type of continuous scission operation, the reactor is preferably charged with a mixture of resorcinol or hydroquinone (depending on which dihydroxybenzene is being produced), a sulfur trioxide catalyst dissolved in acetone, and MIBK and the temperature is raised to the boiling point of the mixture applying heat. The incorporation of resorcinol or hydroquinone in the initial charge typically improves the rate of the cleavage reaction. The DHP / MIBK and sulfur trioxide dissolved in acetone are then fed to the reactor at the desired rate and the reaction product is continuously stirred at approximately the same speed. In a preferred embodiment, the DHP is fed in the form of a MIBK solution and the sulfur trioxide is fed into an acetone solution. Under these conditions, the cleavage of > 99.5% DHP with a residence time in the cleavage reactor of between about 5 to 10 minutes. Once the DHP has been cleaved or rearranged to the corresponding dihydric phenol, the product of the cleavage reaction must be neutralized to remove the acid; the dihydric phenol can then be recovered. The recovery of a polyhydric alcohol, such as resorcinol, hydroquinone, etc., from the cleavage reaction mixture by, for example, distillation, extraction and crystallization, is described in the art. According to the process of the present invention, the yield of resorcinoi from the cleavage reaction is between about 94 and 95% and the purity of the resorcinol after distillation is about 99.7% or more. The effective successful separation of DHP- and HHP from the caustic solution by continuous extractions with MIBK in hot and cold with Karr's Column yields a raw HHP material for the production of dicarbinol (DCL). The DCL is used in the manufacture of various organic and polymeric materials for various applications. The present invention establishes that an aqueous process for the conversion of HHP to DCL can be effectively used. This method takes the HHP obtained from the extraction with MIBK cold, and removes the MIBK from the reaction mixture. The mixture is then refluxed in an aqueous alkaline solution. The removal of the MIBK, previously reported in the literature, allows an aqueous alkaline solution to be effectively used for the conversion of HHP to DCL. The aqueous alkaline solution is preferably an aqueous sodium hydroxide or an aqueous sodium sulfide solution. Using this methodology, complete decomposition of the HHP can be achieved in relatively short reaction times, such as 1 to 2 hours. The solutions of sodium hydroxide and sodium sulfite not only decompose the HHP to DCL but are also thought to decompose the other hydroperoxides, namely KHP and MHP, in their corresponding carbinols (KCl and MCL), although the inventors do not wish to limit themselves to this. In the case of the decomposition of sodium sulfite, according to the process of the present invention, the conversion of HHP to DCL can be achieved even in the presence of MIBK solvent.After decomposition, the DCL product is then easily filtered and purified for commercial markets The process of the present invention therefore provides an improved and safe aqueous process for the manufacture of DCL from HHP material.

The organic solvent used in the "cold" and "hot" extractions in the second and third Columns of Karr can be recycled and reused. This organic solvent, which is preferably MIBK, can be recovered from the HHP flow generated during cold MIBK extraction before the decomposition step. The MIBK can be recovered, for example, through the distillation of the HHP flow. Similarly, the residual MIBK in the poor caustic can be recovered through the distillation of the poor caustic flow generated during the "hot" extraction in the third Karr Column. The MIBK, or other organic solvent, recovered, can then be recycled to the second and third extraction steps in the Karr Column. This recycling also contributes to the economy and efficiency of the methods of the present. It will be appreciated that the present invention provides means for the preparation of DHP and HHP using Karr Columns. These columns of Karr oscillating plates have several advantages over known methods for obtaining a pure DHP fraction, namely: high efficiency and high capacity (high volumetric efficiency) are achieved in a single compact unit. And the elimination of many pumps, mixers and motors required, for example for the operations of the mixer-settler. Only one Karr Column is required for each of the three extraction steps, as opposed to the multiple mixers and settler required in the methodologies reported in the art. The ability to easily reverse phases during extraction is another advantage of the methods herein. The experimental work showed that when the aqueous phase rich in DHP was dispersed in both Karr Columns with "cold" and "hot" MIBK, which coalesced at the interface was good and the solvent involvement was negligible. In the operations with a single Karr Column of the present invention, the temperature of the aqueous alkaline layer increases gradually as the layer passes in countercurrent media through the plates. Therefore, the operation of the Karr Column avoids a large and non-uniform temperature difference between the adjacent plates and a uniform temperature gradient from the bottom to the top of the column can be achieved. Preferably, the Karr Columns used in the methods herein are connected and operate in series. Thus, the present invention provides an advantage over the technique in that all the steps described herein can be carried out continuously, with the product of one column being sent directly, or without appreciable delay to the next column. The ability to carry out such a continuous, efficient method has not been previously reported in the art. Karr oscillating plate extraction columns as used in the present invention can be obtained from KOCH Process Technology, 1005 Parsippany Blvd., Parsippany, NJ 07054. RMP spectroscopy was used to characterize the oxidation products of the initial DIPB solution. by the resonance method. proton magnetic (RMP). The present invention is therefore also directed to a method for using the RMP to determine the composition of the different flows "generated by the methods of the present invention." In addition to the crude (oxidized) oxidation product, RMP methods were developed for characterize the product of recycling: MIBK cold and hot extraction products, the excision feed and the product of the split, and the product obtained in the different stages of distillation in the recovery of the high purity resorcinium. of the RMP technique allowed the characterization of all the components of the hydroperoxidation process of DIPB including the organic peroxides, which were not previously identified.This characterization was not previously reported in the art.

For a qualitative characterization of the different flows described above, an RMP analysis was carried out. The RMP analysis according to the present invention uses the five most common organic portions produced from the oxidation of DIPB to identify the compounds present in each flux; those organic structures are: aryl-C (= 0) -CH3 aryl-C (CH3) 2-OOH aryl-C (CH3) 2-OH ***** aryl-CH (CH3) 2 aryl-C (CH3) = CH2 The portion of the structure shown in bold represents the hydrogens (protons) that were actually used to determine the structures present in each flow or product. The RMP spectra were obtained for the oxidized, the recycled flows, the extraction flows with MIBK in cold and in hot. The identification of each peak of each spectrum was determined by comparing the locations of the peaks with those obtained using standards for each component of the flows. To determine the molar ratio of the components in each flow or product, the value of the integral was determined for the structure that was being measured. Measuring the height of the integral for each peak, and dividing the height by the number of protons that gives rise to that integral, the mole fraction of each compound was determined. The number of protons that results in the integral or peak will be 3, 6 or 12, as shown in the formulas of the above organic structures and as would be known to those skilled in the art. The organic composition of these flows is then found by a "Weight Ratio" method by which the weight fraction of each component is determined, and the normalized total is equal to 100. Typically, the ratio, by weight, will be very close to the weight percent values, as long as the sample is not high in water, organic material, or compounds that do not contain hydrogen. The methods of RMP for analyzing the cleavage product and the distillation samples differed / since there are compounds not assigned or unknown in those products that can not be measured or compared against known standards. A method of "Internal Standard / RMP" can be used to analyze those flows, in which a heavy portion of the sample is "added" with a known amount of an organic compound or "internal standard". Any organic compound can be used, as long as compatibility problems do not arise. Preferred for this use is methylene chloride, which is compatible with the products and which produces only one peak in the spectrum. When methylene chloride is used, between approximately 20 and 30 mg per 200 mg of sample should be used. The weight of each analyte is then found according to the following formula: analyte weight = (weight of organic compound (Ns / Na) (Ms / Ma) (As / Aa) where Ns = number of protons of the internal standard (2 for methylene chloride) Na = number of. protons of the analyte for the measured structure Ms = molecular weight of the standard (85 for methylene chloride) Ma = molecular weight of the analyte As = area of the standard integral Aa = area of the analyte integral The weight of the analyte is divided by the weight of the sample to give the weight percent of each analyte in the total composition. Before carrying out the RMP analysis on the DHP / HHP and caustic flows rich in DHP from the Karr Column of caustic extraction and the Karr Column from cold MIBK extraction, the flows must be subjected to an extraction to remove the NaOH. The extraction is carried out using an organic solvent, such as benzene. For example, a known amount of the flow should be treated with dry ice to bring the flow to a pH within the range of about 9 and 9.5, and extracted with benzene. The sample can then be tested, or it can be further treated by distilling the benzene and the remaining residue analyzed by the RMP methods. Other flows and products can be analyzed directly. The RMP spectrum at 200 MHz can be acquired, for example, on a Varian Gemini 200 FT-NMR spectrometer, commercially available from Varian Associates, Palo Alto, CA, preparing from 3 to 5% (by weight) of the unknown in acetone-d6 ((CD3) 2C = 0). The typical acquisition parameters are the following: pulse width = 8 microseconds (one impulse of 30 degrees); impulse delay = 3 seconds; acquisition time = 4 seconds; and number of transients = 100. The spectra are "divided" into sections of 0.3 ppm (60Hz) wide with total integration for each and the accuracy of the measurement. Other parameters can be optimized besides it is based on the needs and devices of the user. It will be appreciated that the spectrum can be obtained at more than 200 MHz, depending on the needs and equipment of the user. Spectra obtained using less than 200 MHz will typically have an inadequate resolution.

The method of analysis of RMP offers advantages over other analytical techniques for the analysis of hydroperoxidation materials, namely: the technique is not destructive; all samples are analyzed in deuterated solvents which provides an internal reference to ensure correct chemical deviation values; the technique is based on the measurement of the integrals and arise from the different types of different protons in the mixture - since all the protons organically bound to a carbon atom will "respond" in an equivalent way, there is no need to determine a " response factor "for each compound; all components "are measured from a single spectrum (changes in instrumental conditions will not affect the analysis), once the values of chemical deviations for a standard have been determined, there will be no need to analyze the standard concurrently during the analysis "of unknown mixtures; and rapid analysis, typically 15 minutes or less of instrumental time is required. As an aid to understanding the process of the present invention, the simultaneous extraction of DHP / HHP from the oxidized and its subsequent separations by the cold and hot MIBK extractions using the Karr Column operations are described with reference to the flow chart schematic illustrated in Figure 1, with the understanding that this is an exemplary embodiment of the present invention. Referring to Figure 3, three Karr Columns are connected in series and are referred to as the Karr Column of Caustic Extraction 2, Karr Column of Extraction with MIBK in Cold 4 and Karr Column of Extraction with Hot MIBK 6. The oxidation material DIPB 8 or the oxidized material from the Oxidation Reactor of DIPB 10, DIPB of washing and 8% aqueous sodium hydroxide were fed to the Column of Karr of Caustic Extraction 2 in such a way that the DIPB solution and caustic flowed concurrently into the caustic extraction column. Organic recycling ("oxidation recycling") 12 collected from the column will be returned directly to the DIPB 10 Oxidation Reactor for further oxidation. The aqueous caustic solution enriched with DHP and HHP ("caustic rich in DHP / HHP") 14 separated by the Column of Caustic Extraction Karr 2 is sent to the- Column of Extraction Karr with MIBK in Cold 4 after being cooled through a cooler (not shown). In the Karr Column of Extraction with cold MIBK 4, the caustic rich in DHP / HHP 14, and the MIBK solvent and the 8% hydroxide solution were introduced in such a way that both the MIBK and the caustic wash passed concurrently to the column. From this column, the MIBK solution containing HHP is recovered ("Cold MIBK Extraction") 16 and the HHP converted to DCL 18 by the use of an aqueous solution of sodium sulfite or sodium hydroxide, during this conversion, The MIBK solvent is also recovered for recycling (not shown). The aqueous caustic extract enriched with DHP ("Rich in DHP Caustic") 20 is separated from the Karr Column of Extraction with MIBK in Cold 4 and is pumped directly to the Karr Column of Extraction with Hot MIBK 6. In this column , the Rich Caustic in DHP 20 and the previously heated MIBK are pumped in such a way that the hot caustic solution and the MIBK solvent pass concurrently with each other. The Hot MIBK Extract 22 obtained from this extraction contains DHP with a purity exceeding 99.7%. the impurity of HHP present in this DHP material is typically 0.3%; The weight ratio of DHP / HHP in the MIBK extract is therefore approximately 99.7: 0.3. The Hot MIBK Extract 22 is subsequently concentrated (not shown) and cleaved in the presence of an acid catalyst to produce the dihydric phenol, such as resorcinium, and acetone 24. Poor caustic 26 collected from the Karr Column of Extraction with MIBK in Caliente 6 it can be recycled after the separation of the dissolved MIBK.

EXAMPLES The present invention is further described in more detail by means of the following Examples. The Examples provided below should not be taken as limiting the scope of the invention. All parts, percentages and relationships are by weight.

EXAMPLE 1 Preparation of the Diisopropylbenzene Oxidation Mixture 300 parts of m-diisopropylbenzene (m-DIPB) were mixed with 30 parts of diisopropylbenzene monohydroperoxide (MHP, initiator) and 10 parts of 4% aqueous sodium hydroxide (catalyst) in a 1-liter Parr reactor and oxidized by passing air at a rate of 20 liters / hour with good agitation. The temperature of the oxidation reaction mixture was maintained at about 90 ° C. Oxidation was continued until the product had 79 to 75% hydroperoxide (determined by iodometric titration and calculated as diisopropylbenzene monohydroperoxide) The NMR analysis of this oxidation material (oxidized) showed the presence of approximately 15-18% dihydroperoxide of diisopropylbenzene (DHP), and 3 to 5% of diisopropylbenzene hydroxyhydroperoxide (HHP) in addition to the oxidation byproducts shown in Table 1, below, and unreacted DIPB.

Continuous and Simultaneous Separation of DHP and HHP from the Oxidation Product of m-DIPB The oxidized obtained from the oxidation of m-DIPB was collected at room temperature and pumped to a Karr Column (Caustic Extraction Column) at a rate of 100 parts / hour. Separately, m-diisopropylbenzene and 8% aqueous sodium hydroxide were pumped into the column at a rate of 13.5 parts / hour and 88.8 parts / hour, respectively, such that both liquids passed concurrently into the column. During this operation, the temperature of the column was kept between 25 to 40 ° C and two "" phases were separated, namely one organic and one aqueous, continuously. The organic phase was collected at the rate of 91.8 parts / hour, and contained the majority of the monohydroperoxide (MHP) as well as oxidation products not extracted by the caustic solution. This recyclable organic phase can be effectively returned to the oxidizer for continuous or batch oxidation. The aqueous phase rich caustic extract) enriched with DHP, HHP, KHP or other impurities extractable by caustic was collected at the rate of 110.5 parts / hour. The rich caustic extract obtained from the first Karr Column (caustic extraction) was collected and pumped to the second Karr Column (column of cold MIBK) at a rate of 110.5 parts / hour. The temperature of the column of the second was maintained between approximately at a temperature of 10 to 30 ° C during the extraction. The solutions of methyl isobutyl ketone and 8% aqueous sodium hydroxide were pumped respectively to the column at the rate of 58.5 parts / hour and 51.0 parts / hour. When those two solutions were concurrently passed into the column, the HHP, KHP and all the oxidation impurities present in the caustic were extracted into the organic phase. The organic phase enriched in HHP (cold MIBK extract) was collected at a speed of 63.5 parts / hour. It was found that the aqueous caustic extract separated from this operation of the Karr Column contained 99.8% of ^ DHP. - Without any isolation or recovery, the caustic extract rich in DHP obtained from the cold MIBK column was pumped directly to a third Karr Column (column of cold MIBK). Separately, the previously heated methyl isobutyl ketone solvent was pumped into this column at a rate of 134.5 part s / hour such that the ^^ solvent passed concurrently to the caustic solution. HE mounted a uniform temperature gradient across the column, so that the temperature of the column was between about 30 and 70 ° C. The DHP present in the caustic was extracted efficiently with minimal decomposition and the MIBK extract (hot MIBK extract) was collected at a speed of 151.5 parts / hour. It was determined that the purity of the DHP obtained from this extract was 91.7%. The aqueous caustic (poor caustic) recovered at the rate of 139.5 parts / hour of this column can be recycled back to the caustic extraction column after the removal of the incoming MIBK. Table 1 summarizes the compositions of different flows according to the methods of Example 1. yabla 1 Simultaneous Extraction and Separation of DHP and HHP from the DIPB Oxidation Mixture Using Karr Columns Composition of the Different Flows Results of the NMR Analysis (weight ratios) Extract of MIBK Extract Recycling Material MIBK in Hot Cold Oxidation (Free of (Free of Component of M-DIPB Oxidation Solvent MIBK) Solvent MIBK) 1. DIPB 26.6 43.2 2. MHP 38.8 44.9 7.2 3. DHP 18.2 0 1.1. 99.7 4. HHP 4.3 2.2 77.8 0.3 TABLE 1 (continued) Extract of MIBK Extract Recycling Material MIBK in Hot Cold Oxidation (Free of (Free of Component of M-DIPB Oxidation Solvent MIBK) Solvent MIBK) . MCL 3.5 5.4 6. DCL 0.6 0.6 0.7 7. MKT 0.4 O.'T 8. KHP 1.0 0 12.5 9. KCI o.2"" - o: 0.7 . Peroxides 6.0 3.4 organic The hot MIBK extract obtained from the third Karr's column was concentrated at 30% by weight of DHP. During this concentration, the water content of the DHP / MIBK solution was reduced from 3.0% to 0.3% by weight. This material was used in the next continuous excision operation.

Continuous Excision of the DHP Material In a glass reactor equipped with a mechanical stirrer, thermometer, reflux condenser and an overflow or overflow arrangement, a solution containing resorcinium, methyl isobutyl ketone and 0.06 parts by weight of S03 dissolved in solution Acetone at the weight ratio of 8:52:40 was charged and heated to reflux. Solutions containing 30% w / w of DHP in methyl isobutyl ketone (hot MIBK extract solution) and 0.06% w / w sulfur trioxide in dry acetone were fed into the reactor at a rate of 50.0 parts / hour and 26.9 parts / hour, respectively, such that the total residence time was 10 minutes. The temperature of the content of the cleavage reactor was maintained at the boiling point. The product of the reactor cleavage overflowed to the collectQr in which the acid catalyst was immediately and continuously neutralized. The product harvested, after steady-state conditions, gave a yield of 94% resorcinol based on DHP fed.

Manufacture of DCL from HHP (Decomposition of Sodium Sulfide with an Azeotropic Distillation Method The extract of MIBK cold content of the second Karr column was concentrated to approximately 40% by weight of HHP material in the MIBK. By doing this operation, most of the MIBK solvent can be recovered and recycled effectively.

The reactor, equipped with a mechanical stirrer, thermometer and Dean-Stark condenser, was loaded with 100 parts of 40% HHP in methyl isobutyl ketone (cold MIBK extract with a content of 77.8% HHP) and 140 parts of aqueous solution. of sodium sulphite at 20%. The contents of the reactor were heated to reflux and all the MIBK solvent present in the reactor was completely removed by azeotropic distillation. After removal of the solvent, the contents of the reactor were refluxed for a period of 2.0 hours and cooled to precipitate the DCL. The white precipitate separated from the aqueous solution was filtered, washed with water and then dried. The yield was 26.7 parts with a purity of 94.2%. From the results of this experiment, all the HHP present in the cold MIBK extract was completely decomposed to DCL. From this example, it is evident that both resorcinol and dicarbinol can be produced simultaneously from diisopropyl benzene.

EXAMPLE 2 In this example, the two methods developed for the decomposition of HHP to DCL by the aqueous solution of sodium sulfite are described.

A cold MIBK extract obtained from the Karr Column was concentrated to approximately 40% by weight of HHP material and used in the following two experiments: Decomposition of HHP to DCL by Aqueous Sulfite Sulfite A. Azeotropic Method In a three-necked flask equipped with a mechanical stirrer, thermometer and Dean-Stark: condenser, 100 parts of HHP / MIBK and 140 parts of 20% aqueous sodium sulfite solution were added. The contents of the flask were then heated and refluxed During this period of reflux, by means of Dean-Stark separation means, all the MIBK solvent present in the solution was removed, after which, "the contents of the flask it was refluxed for an additional 2.0 hours and then cooled. The solid material stopped after cooling was filtered, washed with water, dried and analyzed to determine its composition by NMR analysis. The yield was 28.4 parts with a purity of 94.2%. The results are summarized in Table 2, below.

B. Reflux Method A three-neck flask equipped with a mechanical stirrer, thermometer and reflux condenser, was added 100 parts of concentrated HHP / MIBK solution and 140 parts of 20% aqueous sodium sulfide solution. The contents of the flask were heated and refluxed for 2.0 hours. After this reflux, the reaction mixture was cooled and the separated white precipitate was filtered, washed with water, dried and analyzed by NMR to determine its composition. The yield was 21.6 parts and the purity was 97.6%. The results of this experiment are summarized in Table 2.

Table 2 Decomposition of HHP to DCL Using Aqueous Solution of. Na2S03 Azeotrope Method Reflux Materials Used (parts) 1. HHP / MIBK 100 100 Solution 2 . Solution of_Na2S03 '140 140 (20% by weight) Conditions 1. Reflux temperature 101 95-100 (° C) 2. Reflux time 2.0 (hours) Table 2 (continued) Azeotrope Method Reflux NMR analysis of the Control * Components of the Organic Phase (weight ratio, L-Lysine solvent) 1. DHP 0.0 0 0 2. HHP 77.9 0 0 3. KHP 10.6 0 0 4. MHP _ 9.6 0 0 5. KCL "0.9 5. 8 1 .9 6. DCL 0.7 94. 2 97. 6 7. MCL 0 0 0. 4 MIBK (% by weight) 61.0 0 0. 1 * Cold MIBK Extract was concentrated to approximately 39% by weight solids and used in the Decomposition Process. When analyzing the results of Table 2, it is observed that the decomposition of HHP using an aqueous solution of sodium sulfite can be successfully used for the safe and efficient conversion of HHP to DCL. By this method, it was observed that the HHP material was completely converted to its corresponding carbinol under atmospheric conditions. With this method, even before purification, when it was obtained it was highly pure.

^ EXAMPLE 3 In this example, the processes for producing DCL directly from the MIBK extract using aqueous sodium hydroxide solution are described.

Experiment No. In a three-necked flask equipped with a mechanical stirrer, thermometer and reflux condenser, 100 parts of cold MIBK extract, obtained from the operation of the Karr column, and 24 parts of aqueous caustic solution were added. 4% and refluxed for a period of 5.0 hours. After this period of reflux, the solution was cooled, and both aqueous and organic layers were separated, and the organic layer analyzed ^^ to determine its composition was by NMR analysis.

After analyzing the results, it was observed that the concentration of HHP in the MIBK layer remained unaffected indicating that the decomposition of the HHP under the above conditions.

Experiment No. 2 Experiment No. 1 was repeated using 8% aqueous sodium hydroxide solution instead of 4% aqueous solution. The separated MIBK phase after the reflux period was analyzed by NMR to determine its composition. Again, no changes were observed in the concentration of HHP. The results obtained from experiments 1 and 2 are summarized in Table 3, below. After further investigation, it was discovered that the decomposition of the HHP could be effectively completed by removing the MIBK from the reaction mixture beforehand. With this discovery, a method for effectively decomposing HHP to DCL was developed, therefore, using the method described in experiment No. 3, DCL could be manufactured in a safe and economical way. are that it is aqueous, ^^ is carried out under atmospheric conditions instead of 20 not high pressure conditions, and is carried out without the use of hydrogen.

Table 3 Decomposition of HHP to DCL using aqueous NaOH (Reflux of HHP / MIBK with NaOH solution Experiment No. 1 No. 2 Materials used (parts) 1. HHP / MIBK 100 100 solution 2. NaOH solution (% in 24 (4%) 24 (8%, weight) Conditions 1. Reflux temperature 90-95 90-95 (° C) 2. Reflux time 5.0 5.5 (hours) Control NMR analysis * Components of the Organic Phase (weight ratio, solvent-free) 1. DHP 14.7 8..5 3.5 2. HHP 66.8 66.2 69.4 3. KEP 7.7 8.8 8.1 4. KCL 0.9 2.4 3.0 . DCL 2.2 5.7 7.3 Table 3 (continued) Experiment No. 1 No 2 6. MHP 7.7 8. 4 7. 9 7. DKT - 0. 8 8. MIBK solvent (% in 95.4 95. 7 95. 7 weight) ^ HHP / J IBK solution used in the Decomposition Process.

Experiment No. 3 100 parts of concentrated HHP / MIBK and 44.4 parts of 20% aqueous sodium hydroxide were added to a three-necked flask equipped with a mechanical stirrer, thermometer and Dean-Stark condenser. The contents of the flask were heated and refluxed. During this initial reflux period, all of the MIBK solvent was completely removed as an azeotrope. After this, the contents of the reactor were refluxed for an additional period of one hour. The solution was then cooled and the separated white precipitate was filtered, washed with distilled water, dried and analyzed by NMR to determine its composition. The yield was 26.4 parts with a purity of 94.6%. The results of this experiment are summarized in Table 4 and clearly suggest that an aqueous solution of sodium hydroxide can also be used effectively for the complete decomposition of HHP.

Table 4 Decomposition of HHP to DCL Using Aqueous NaOH Solution (Dean-Stark Distillation of MIBK) Method Materials Used (parts) 1. HHP / MIBK 100.0 Solution 2. NaOH solution (20% in 4.4 weight) Conditions 1. Reflux temperature (° C) 95-105 2. Reflux Time (hours) 1 Control NMR Analysis * Components of the Organic Phase (weight ratio, solvent-free) 1. DHP 0.0 0 2. HHP 77.9 0 3. KHP 10.6 0 Table 4 (continued) Method 4 MHP 9.6 O 5. KCL 0.9 2.6 6. DCL 0.7 94.6 7. DKT OO 8. MCL O 2.8 9. MKT OO 10. MIBK (% by weight) 61.0 0 * Cold MIBK extract was concentrated to approximately 30% by weight solids and used in the Decomposition Process.

EXAMPLE 4 Preparation of the Diisopropylbenzene Oxidation Mixture One Parr reactor was loaded with 100 parts of m-diisopropylbenzene (m-DIPB), 10 parts of oxidation recycling (initiator) and 2 parts of 5% sodium carbonate solution (catalyst). The above mixture was heated to 95 ° C and oxidized past a fine stream of air to the stirred solution rapidly. Oxidation was continued until the oxidation mixture in the reactor had 75% by weight of hydroperoxide (calculated as diisopropylbenzene monohydroperoxide by iodometric titration). The result of the analysis of this oxidation material of m-DIPB (oxidized is seen in Table 5, below.

Continuous and Simultaneous Separation of DHP and HHP from the Oxidation Product of m-DIPB The oxidized obtained from the oxidation of m-DIPB was cooled to room temperature and pumped into a Karr Column (Caustic Extraction Column) at a rate of 100 parts / hour. Separately, m-diisopropylbenzene and 8% aqueous sodium hydroxide were pumped into the column at a rate of 12.8 parts / hour and 73.6 parts / hour, respectively, such that both liquids passed concurrently into the column. During this operation, the temperature of the column was kept between 25 to 40 ° C and two phases, namely one organic and one aqueous, were continuously separated. The organic phase was collected at the rate of 93.5 parts / hour, and contained most of the monohydroperoxide (MHP) as well as non-extractable oxidation products by the caustic solution. This recyclable organic phase can be. effectively returned to the oxidizer for continuous or batch oxidation. The aqueous phase (rich caustic extract) enriched with DHP, HHP, KHP and other impurities, extractable by caustic shown in Table 5 were collected at the rate of 91.0 parts / hour. The rich caustic extract obtained from the first Karr Column was cooled and pumped into the second Karr Column (column of cold MIBK) at a rate of 91.0 parts / hour. This temperature of the column of the second was maintained between approximately at a temperature of 10 to 30 ° C during the extraction. The solutions of methyl isobutyl ketone and 8% aqueous sodium hydroxide were pumped respectively into the column at the rate of 63.4 parts / hour and 52.0 parts / hour. When those two solutions were concurrently passed into the column, the HHP, KHP and all the oxidation impurities present in the caustic were extracted into the organic phase. The organic phase enriched in HHP (cold MIBK extract) was collected at a rate of 68.6 parts / hour. It was found that the aqueous caustic extract separated from this, operation of the Karr Column contained 99.8% DHP. Without any isolation or recovery, the DHP rich caustic extract obtained from the cold MIBK column was pumped directly into a third Karr Column (column of cold MIBK). Separately, the previously heated methyl isobutyl ketone solvent was pumped into this column at a rate of 138.0 parts / hour such that this solvent was concurrently passed into the caustic solution. A uniform temperature gradient was maintained across the column, so that the temperature of the column was between about 30 and 70 ° C. The DHP present in the caustic was extracted efficiently with minimal decomposition and the MIBK extract (hot MIBK extract) was collected at a rate of 150. 0 parts / hour. It was determined that the purity of the DHP obtained from this extract was 99. 7% The aqueous caustic (poor caustic) recovered at the speed of 127. 6 parts / hour of this column can be recycled back to the caustic extraction column after the removal of the incoming MIBK. Table 5 summarizes the results of the previous experiment. Table 5 Extraction and Separation. Simultaneous DHP and HHP of the DIPB Oxidation Mixture Using Karr Columns Composition of the Different Flows NMR Analysis Results (weight ratios) Extract of MIBK Extract Reciprocal Material in MIBK in Hot Cold Oxidation of (Free of (Free of Component of M-DIPB Oxidation Solvent MIBK) Solvent MIBK) 1. DIPB 24.9 44.0 2. MHP 38.2 42.7 8.7 3. DHP 18.7 0 - 1.4 99.7 4. HHP 4.3 2.7"76.2 0.3 TABLE 5 (continued) Extract of MIBK Extract Recycling Material MIBK in Hot Cold Oxidation of (Free of (Free of M-DIPB Component Oxidation Solvent MIBK) Solvent MIBK) . MCL 4.0 6.1 6. DCL 0.6 0.8 0.4 7. MKT 0.4 0.1 8. KHP 1.0, 0 12.4 9. KCL 0.2 0 0.9 . Peroxides 5.9 • ... 3.6 ^ organic The hot MIBK extract obtained from the third Karr Column was concentrated to 24.8% by weight of DHP. During this concentration, the water content of the DHP / MIBK solution was reduced from 3.0% to 0.3% by weight. This material was used in the next continuous excision operation.

Continuous Excision of the DHP Material In a glass reactor equipped with a mechanical stirrer, thermometer, reflux condenser and an overflow or overflow arrangement, a solution containing resorcinium, methyl isobutyl ketone and 0.06 parts by weight of S03 dissolved in solution Acetone at the weight ratio of 8:52:40 was charged and heated to reflux. Solutions containing 24.8% w / w of DHP in methyl isobutyl ketone (solution of hot MIBK extract) and 0.06% w / w sulfur trioxide in dry acetone were fed into the reactor at a rate of 100.0 parts / hour and 53.8 parts / hour, respectively, such that the total residence time was 5 minutes. The temperature of the content of the cleavage reactor was maintained at the boiling point. The product of the reactor cleavage overflowed into the manifold in which the acid catalyst was immediately and continuously neutralized. The product harvested, after steady state conditions, gave a yield of 91% resorcinol based on DHP fed.

Manufacture of DCL from HHP (Decomposition of Sodium Hidoxide with an Azeotropic Distillation Method The extract of cold MIBK obtained from the second Karr column was concentrated to approximately 40% by weight of HHP material in the MIBK. By doing this operation, most of the MIBK solvent can be recovered and recycled effectively.

A reactor, equipped with a mechanical stirrer, thermometer and Dean-Stark condenser, was charged with 100 parts of 40% HHP in methyl isobutyl ketone (cold MIBK extract with a content of 76.2% HHP) and 44.4 parts of 20% aqueous sodium hydroxide solution. The contents of the reactor were heated to reflux and all the MIBK solvent present in the reactor was completely removed by azeotropic distillation. After removal of the solvent, the contents of the reactor were refluxed for a period of about 1.0 hours and cooled to precipitate the DCL. The white precipitate separated from the aqueous solution was filtered, washed with water and then dried.The yield was 26.2 parts with a purity of 97.1% .From the results of this experiment, it was determined that all the HHP present in the extract of cold MIBK was completely decomposed.From this example, it is evident that both resorcinol and dicarbinol can be produced from diisopropylbenzene.

EXAMPLE 5 A Parr reactor was charged with 330.0 parts of p-diisopropylbenzene, 10.0 parts of oxidation recycling and 1. 0 parts of 4% aqueous sodium hydroxide and heated to 95 ° C. Oxidation of the above mixture started by passing a fine stream of air at a rate of 20 liters / hour in a rapidly stirred solution. It took approximately 14.0 hours for the oxidation reaction to reach a 75% hydroperoxide content calculated as 5 p-diisoproopylbenzene monohydroperoxide by iodometric titration. This oxidation material of p-DIPB could also be used to produce the corresponding dihydric phenol, namely hydroquinone, and dicarbinol by the process of this invention. Although particular modalities have been described of this invention above for purposes of illustration, it will be apparent to those skilled in the art that numerous variations of the details of the present invention can be made without departing from the invention as defined in the appended claims. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention. •

Claims (27)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property. A method for manufacturing dihydroxybenzene and dicarbinol from diisopropylbenzene, characterized in that it comprises: a) oxidizing diisopropylbenzene (DIPB) in the presence of a basic catalyst to obtain an oxidized one comprising dihydroperoxide "of diisopropylbenzene (DHP), hydroxyhydroperoxide of diisopropylbenzene (HHP) ), acetyl-isopropylbenzene hydroperoxide (KHP), and one or more members of the group consisting of diisopropylbenzene monohydroperoxide (MHP), isopropylbenzene monocarbinol (MCL), diisopropylbenzene dicarbinol (DCL), acetyl-isopropylbenzenecarbonol (KCL) and other peroxides organic, b) feed the oxidized from step a), a caustic solution and an organic solvent in a first Karr Column, c) generate two flows from the first Karr Column of step b), the first flow of caustic extraction comprises DHP, HHP and KHP extracted in a countercurrent operation, and the second caustic extraction stream comprises one or more s members selected from the group consisting of MHP, MCL, DCL, KCL, other organic peroxides, DIPB and an organic solvent from step b); d) feeding the first caustic extraction stream from step c) cooled to a temperature between about 10 and 30 ° C, an organic solvent and an alkaline solution in a second Karr Column; e) generating two streams from the second Karr Column, the first cold extraction stream comprising a cold organic solvent extract comprising HHP and KHP and the second cold extraction stream comprising caustic enriched with DHP; f) feeding "an organic solvent having a temperature between about 40 and 85 ° C and the caustic enriched with DHP from step e) into a third Karr Column; g) generating two flows from the third Karr Column, the first hot extraction stream comprises a hot organic solvent solution comprising high purity DHP, and the second hot extraction stream comprises poor caustic having low levels of non-extracted hydroperoxide, h) concentrating the hot organic stream solution from step g ) and feed the concentrate into a continuous scission reactor where the DHP is cleaved in the presence of an acid catalyst to produce a solution comprising the corresponding hydroxybenzene and acetone, and i) decompose the HHP present in the first cold extraction flow through e) by treatment in an aqueous alkaline solution under atmospheric pressure and aqueous conditions to obtain the corresponding dicarbinol 2. The method according to claim 1, characterized in that at least two successive steps selected from the group consisting of any of steps a) through g) are carried out continuously. The method "according to claim 1, characterized in that the oxidation of diisopropylbenzene is carried out using molecular oxygen 4. The method according to the claim 3, characterized in that the oxidation step is carried out using a continuous or batch method. 5. The method according to claim 1, characterized in that it includes carrying out the oxidation step at a temperature between about 80 and 120 - and a pressure between about 20 and 80 psi (137.8 and 551.2 kPa) and using it as a base catalyst. an alkaline solution selected from the group consisting of sodium carbonate and sodium hydroxide. 6. The method according to claim 1, characterized in that the organic solvent of step b) is DIPB. The method according to claim 1, characterized in that it also includes the step of recycling the second caustic extraction flow produced in step c) to the oxidation step of step a). 8. The method according to claim 1, characterized in that the organic solvent used in step d) and in step f) is MIBK. 9. The method according to the claim 1, characterized in that "1-a temperature of the solution of the Karr Column is between about 10 and 30 ° C. The method according to claim 1, characterized in that the temperature of the solution in the third column of Karr is between about 40 and 85 ° C. 11. The method according to claim 1, characterized in that the first caustic extraction flow from step c) is fed directly to the cold extraction of step d), and where the second cold extraction flow from step e) is fed directly to the hot extraction of step f) 12. The method according to claim 1, characterized in that it includes effecting the concentration of step h) by feeding the solvent solution hot organic in a vacuum evaporator 13. The method according to claim 1, characterized in that the temperature of the solution inside 5 of the cleavage reactor in step h) is between about 60 to 80 ° C. 14. The method according to claim 13, characterized in that the decomposition step i) is carried out at a temperature of between approximately 90 and 10 105 ° C. ^ P 15. The method according to the claim 1, characterized why- the first Karr Column, the second Karr Column and the third Karr Column are operated in series. 16. The method according to the claim 1, characterized in that it includes employing the method for producing a hot organic solvent solution having a purity of DHP of about 99.7% or greater. ^^ 17. The method according to the claim 20 1, characterized in that the aqueous alkaline solution of step i is selected from the group consisting of an aqueous solution of sodium sulfide and an aqueous solution of sodium hydroxide. 18. The method according to the claim 25, characterized in that the stirring speed in the first Karr Column is between approximately 50 and 300 revolutions per minute, the agitation speed in the second Karr Column is between approximately 100 and 400 revolutions per minute, and the speed of agitation in the 5th third Column of Karr is between approximately 100 and 400 revolutions per minute. 19. The method according to claim 1, characterized in that the acid catalyst of step h) is one or more members selected from the group consisting of 10 sulfuric acid, sulfur trioxide, phosphoric acid, hydrochloric acid, boron trifluoride, and p-toluene sulphonic acid. 20. The method according to claim 19, characterized in that the acid catalyst is sulfur trioxide. 21. The method according to Claim 15 1, characterized in that it includes employing the method to produce DCL having a purity greater than about 94%. 22. The method according to claim 8, characterized in that it also includes the step of recovering ^^ MIBK of the poor acoustic flow generated from step g) and from the decomposition flow in step i) to recycle it. 23. The method according to claim 1, characterized in that the organic solvent in the first cold extraction flow removed before the decomposition step of step i). 24. The method according to the claim 1, characterized in that it also includes the step of determining the composition of one or more flows selected from the group consisting of the oxidized, the first extraction flow of 5 caustic, the second caustic extraction flow, the first cold extraction flow, the second cold extraction flow, the first hot extraction flow, the second hot extraction flow, and the step diversion product h) using the RMP analysis. 25. The method according to claim 24, characterized in that the flow that is being analyzed is selected from the group "consisting of the oxidized, the first caustic extraction flow, the second caustic extraction flow, the first extraction flow in 15 cold, the second cold extraction flow, the first hot extraction flow and the second hot extraction flow and the RMP analysis comprising: a) obtaining an RMP spectrum for a flow; ^^ b) determine the integral of a peak that represents 20 each compound in the flux in the RMP spectrum; c) divide the integral of each peak by the number of hydrogens that give rise to each peak to obtain the mole fraction of each compound in the flow; and d) repeating steps a) through c) for each flow that is being analyzed. 26. The method according to claim 25, characterized in that the flow that is being analyzed is selected from the group consisting of the first caustic extraction flow and the second extraction flow of 5 Caustic, and also includes the step of extracting the caustic from the flow before performing the RMP analysis. 27. The method according to claim 24, characterized in that the flow that is being analyzed is the cleavage product, and the RMP analysis comprises: a) adding an internal standard to the cleavage-fe product b) obtaining a spectrum of RMP for the mixture of cleavage / metlene product; c) determine the weight of each analyte in the cleavage product according to the formula: analyte weight = (weight of the internal standard) (Ns / Na) (Ma / Ms) (Aa / As) where Ns = number of protons of the internal standard (2 for methylene chloride) ^^ Na = number of protons of the analyte for the 20 measured structure Ms = molecular weight of the standard (85 for methylene chloride) Ma = molecular weight of the analyte Aa = area of the standard integral 25 As = area of the analyte integral