Method of producing phenol compounds, extraction of phenol from split products and device to this end

FIELD: chemistry.

SUBSTANCE: present invention relates to production of phenol, method of extracting phenol from products of splitting cumene hydroperoxide and to a device for extracting phenol from products of splitting cumene. The method of producing phenol involves the following stages: i) oxidation of cumene, obtaining a reaction mixture containing cumene hydroperoxide and unreacted cumene; ii) splitting products obtained from stage i), obtaining a mixture of splitting products containing at least phenol, acetone, hydroxyacetone, unreacted cumene and water; iii) treatment of the mixture of splitting products obtained on stage ii) through distillation, which involves separation of the mixture of splitting products into at least three fractions using a single fractional distillation stage through: putting the mixture of splitting products into a distillation column, removal of the first fraction, containing acetone, from the upper part of the distillation column, removal of the second fraction, containing phenol, from the lower part of the distillation column, and removal of the third fraction, containing at least unreacted cumene, hydroxyacetone and water, in form of an off-stream. The outlet opening of the off-stream is higher the area for putting in the mixture of splitting products into the distillation column, characterised by removal of heat from the distillation column. The section for removing heat is higher than the outlet opening of the off-stream of the third fraction.

EFFECT: increased energy efficiency of methods using old technology, while maintaining quality standards and total output of end products.

25 cl, 6 dwg, 1 ex

 

The present invention relates to an improved process for the preparation of phenolic compounds and to an improved method of extraction of phenol from mixtures of fission products. The present invention also relates to an improved installation for implementing this method.

How cleavage of cumene hydroperoxide to phenol and acetone, acid catalyzed, for a long time had a significant industrial value. Upon receipt of phenol from alcylaryl compounds, such as cumene, by way of the hawk the oxidized cumene to cumene hydroperoxide (CHP) in the first stage reaction known as oxidation, and then CCP focus to the content of 65 to 90 wt.%, using vacuum distillation, known as concentration. In the second stage reaction, known as splitting, CCP split on phenolic compounds and ketone by treatment with acid, usually sulfuric acid. Along with phenol as phenolic compounds and acetone as the ketone product of cleavage also contain additional compounds that are formed on the stages of the reaction, prior to splitting, and that the splitting are split only partially or not at all are split. The most important compounds which can be contained in the product splitting in addition to phenol is the acetone, are, in particular, α-methylsterol (AMC), cumene and acetophenone. In addition, the cleavage product may contain small amounts of dimethylphenylcarbinol (DMPC), formed during the oxidation. Other impurities include such compounds as methylbenzofuran (ICF), hydroxyacetone, mesityloxide (MO) and carbonyl compounds such as acetaldehyde and 2-phenylpropionic aldehyde. After neutralization product of the breakdown and eventual removal of the aqueous phase product of the fission process using distillation.

There are various ways of handling mixtures of fission products through distillation (Ullmann''s Encyclopedia of Industrial Chemistry, 5th completely revised edition, Vol. A19, 1991, VCH Verlagsgesellschaft mbH, Weinheim). In principle, all of these methods include the initial neutralization of mixtures of fission products with an aqueous solution of sodium hydroxide, amines or aqueous solution of peroxide. After separation of the phases the organic portion of the neutralized cleavage product mixtures are transferred into the first column, in which through the upper part of the column of the remaining cleavage product is distilled off the crude acetone. This crude acetone is usually treated with alkali in the scrubber and re-purified by distillation. However, the processing is sometimes performed in the column. CBM product of the first column is subjected to distillation in the second to the column, from the top of which are selected AMS and cumene and usually is directed to the hydrogenation, which again receive the cumene. AMS and cumene can be separated by azeotropic distillation in the presence of water. CBM product found in the second column, is subjected to distillation in a column for the crude phenol.

The crude phenol can be further cleaned using extractive distillation using water or by treating the cation-exchanger with subsequent distillation. In the latter case, the compounds that are difficult to separate from phenol by distillation, for example mesityloxide and hydroxyacetone, are condensed with the formation of high-boiling compounds.

Prior

This method is described, for example, in U.S. patent US 5064507 (transferred to the company Allied). In this method, the cleavage product is first separated from the crude acetone column for the crude acetone. CBM product is transferred to the column for cumene in which the cleavage product is separated AMS and cumene. But the column runs in a mode that some part of the AMS remains as product, because it is required as a reagent or solvent for further processing of phenol to remove MBF and other impurities. This CBM product is introduced into reaction with an amine, preferably hexameta what endjamina, in the reactor, with the reactor performance ideal displacement, for the conversion of carbonyl compounds, such as acetal (hydroxyacetone) or MO in the high-boiling products. The thus treated product is further treated with distillation. However, to obtain the purified final product of a phenol - this product should be skipped in 4 columns and two zones of the reaction. In this way the initial cost of the apparatus required to remove hydroxyacetone of phenol, are relatively large.

In accordance with DE-AS 1105878 (Phenolchemie) neutralized cleavage product, which is separated from the crude acetone column for the crude acetone, refer to the column for hydrocarbons, which in the presence of water, the hydrocarbons boiling below phenol, such as AMS and cumene is distilled off with the selection of the upper part of the column. From the bottom of the column select organic phase and sent to the upper part below the line of the column in which water is separated from the phenol and high-boiling products, which are formed in the lower part of the column. Then a mixture of phenol and high-boiling products direct in the column for the crude phenol. The remnants formed in the column for the crude phenol and in the column for distillation of pure phenol, then mo is but to send in the cracking furnace, in which the remains are processed and extracted portion of the phenol. These valuable lessons products can be re-directed to the column for hydrocarbons.

In the patent EP 0032255 (UOP) described a method of processing product of fission, in which the organic part of almost neutralized (pH≈6) product splitting again washed with water and then the organic part is sent to the column for the crude acetone, in which the crude acetone is separated from the remaining product splitting. Residues remaining in the lower phase, sent directly to the column for cumene in which the crude phenol is formed as a cubic product, which, in turn, is directed to purifying distillation. A mixture selected from the upper part of the column for cumene, which mainly contains AMS, cumene and water, is directed into the tank for phase separation, which separates the aqueous phase. The organic phase is sent to the column leaching, in which a mixture of organic substances is treated with sodium hydroxide to remove all of phenol, still contained in the mixture AMS to cumene in the form of peroxide sodium. The mixture AMS to cumene, which is purified from phenol, through the upper part of the column is directed to the hydrogenation.

In U.S. patent US No. 4262150 (UOP) used the same system of columns, as described in the patent EP 003255 (UOP). Unlike EP 0032255 is that to neutralize the product splitting is used extraction column, and not one or more combinations of mixers and plants for the separation of phases.

In U.S. patent US No. 3322651 (transferred UOP) described the use of nitrogen-containing compounds, particularly amines, for the purification of phenol, obtained by splitting the CCP. However, the added amines also must be removed from the product and they are quite expensive.

In U.S. patent US No. 5510543 (GE) described a method of processing product of the cleavage of the CCP, in which the neutralizer pH value of the product of cleavage is brought to equal from 4.0 to 4.9 by addition of base, in particular sodium hydroxide solution. In the neutralizer, the cleavage product is separated into an aqueous phase and an organic phase. The organic phase is sent to a column, called a separator, in which the cleavage product by distillation is separated into enriched acetone fraction and enriched with phenol fraction. Enriched with phenol fraction is withdrawn from the bottom of the column and is directed to the purification of phenol, which may, for example, include one or more additional distillations. Enriched with acetone fraction is withdrawn from the upper section of the column and sent to the column for acetone and in this case this fraction re the introduction to the column is added to the basis in such quantity, to the value of the pH of the fractions was equal to about 9, so were neutralized organic acids, which are also found in this fraction. The mixture formed in the bottom phase of the column, which in addition to water and contains hydrocarbons, and organic acid salts, send in the device for phase separation in which a mixture is separated into the organic phase and aqueous phase. The organic phase can be subjected to additional processing to extract cumene.

In addition, methods have been developed, in which the individual fractions generated during the processing of the cleavage product using distillation, treated in a special way. Thus, in U.S. patent US No. 5487816 (UOP) describes how the Department of AMC from the mixture, which contains phenol, AMS and water and which is formed as a cubic product in the column for the crude acetone. Column for crude acetone in this case, acts in such a way that the cumene product selected from splitting in the upper part of the column for the crude acetone together with acetone. A mixture containing AMC and phenol, are divided into the column in such a way that in the lower part of the column mainly phenol, which can be subjected to further processing, and in the upper part of the column select mix AMC, water and small amounts of phenol, and the mixture condenses and by adding the OS is ESD reagent is its pH adjusted to greater than 6. As a consequence, the phenol is primarily contained in the aqueous phase, and AMC is contained in the organic phase, in which the impurities contained only a small amount of phenol. The phases are separated from each other by means of the apparatus for phase separation. The organic phase can be used for hydrogenation, and the aqueous phase can be loaded back into the column in the form of phlegmy.

In U.S. patent US No. 4370205 (UOP) swab taken from the bottom of the column for the crude acetone, unlike the method described in U.S. patent US No. 5487816 (UOP), also still contains cumene. Therefore, it is suggested a different configuration of columns. In particular, use two columns operating under practically the same conditions that produced CBM product basically is a phenol, and from the upper part of the column are selected mainly AMS and cumene. The crude phenol selected as the cubic product of the first column is passed to the subsequent processing stage, and the crude phenol selected as the cubic product from the second column, refer back to the first column. The product taken from the top of the second column, is treated with sodium hydroxide solution in the wash column. The product taken from the top of the first column, which contains AMS and cumene can be used for the hydrogenation.

In the patent GB 1021759 (Mitsui) described the treatment of a mixture of cleavage products, which is obtained by using the acid catalyzed cleavage of the CCP and from which the catalyst is removed by neutralization and purification. To obtain a phenol having a low content of hydroxyacetone, the division performed by loading a mixture of fission products in the distillation column through the side inlet and fractionation of this mixture by using a single stage of separation, so as to obtain a top fraction containing water, acetone, hydroxyacetone and cumene, and the bottom fraction containing phenol with content hydroxyacetone constituting less than 100 million-1. Depending on the composition of the mixture of products of cleavage of the hydroperoxide load in such quantity that the ratio of cumene to phenol content in the download column was not less than 0,28 parts by weight of cumene to 1 parts by weight of phenol, since the method is based on the separation of azeotropic mixtures of hydroxyacetone with cumene from phenol. This way you can separate hydroxyacetone from phenol. However formed, the top fraction, which contains not only water, cumene and hydroxyacetone, and acetone. The top fraction can also be contaminated with phenol. These products must also be separated from each other.

In U.S. patent US 4251325 (transferred to BP Chemicals) treatment fraction, which mainly freed from low-boiling substances, water and acetone is, optimized by operating the column for cumene so that the mixture containing cumene, AMS and hydroxyacetone, were selected from the top and the mixture is almost completely cleared from the crude phenol remaining in the bottom product and therefore does not require expensive removal during the processing of phenol. This method gives the phenol containing less than 30 million-1hydroxyacetone. The disadvantage of this method is that the injected mixture should almost not contain water, so the acetone fraction containing low-boiling substances, as well as the main part of the water contained in the mixture of fission products must be removed from the mixture of products of cleavage at the previous stage of separation. The processing of such acetone fraction by methods of the prior art is relatively uneconomical because it requires large expenditures for equipment.

In U.S. patent US No. 4333801 (UOP) described the treatment fraction, which contains AMS, cumene, phenol, water, and impurities, such as hydroxyacetone. The method basically consists in removing faction AMC/cumene, with a very low concentration of phenol, from all factions. This is accomplished by operation of the column for cumene so that the mixture containing cumene and AMS, were selected from the upper part of the column and this mixture Conde who was sirvaluse and went into the tank for phase separation. All the water that may be contained, separated and discarded. Part of the organic phase is returned to the upper part of the column in the form of phlegmy. Another part of the organic phase is fed into the machine for washing, in which the remains of phenol, which will interfere with the hydrogenation, are removed from this phase, so that this phase can be used for the hydrogenation. From the side outlet of the column for cumene is selected fraction containing AMS and cumene, and the azeotropic mixture of water with phenol, and this fraction also condenses and goes into the tank for phase separation. The aqueous phase, which may contain phenol, is sent to the machining stage. The organic phase, which contains cumene, AMS and as much phenol as it remains in the organic phase in accordance with the phase equilibrium between the organic and aqueous phases, turns into steam and vapour state is loaded back into the column for cumene above the side outlet. The fraction of the crude phenol is withdrawn from the bottom of the column.

The method of distillation of phenol with energy recovery are described in U.S. patent US No. 5131984 loaded crude phenol should be cleaned from the main quantity of acetone, cumene and AMS using a conventional method, which limits the possibility of energy recovery.

A similar method is described in U.S. patent US No. 522234 (Allied), but with the difference that in the column of additional water from the upper part of the column is withdrawn mixture, which mainly contains water and phenol, and the mixture is partially condensed and is returned to the column.

In U.S. patent US No. 4340447 described method and device for producing pure acetone from a mixture of reaction products of cleavage of the CCP.

From German patent application DE 10060505 A1 and international application WO 02/46133 A1, and DE 10060503 A1 and WO 02/46132 A1, the disclosure of which is included in the present invention for links, well-known method for separating phenol from a mixture comprising at least cumene, phenol and hydroxyacetone, and in this way phenol containing hydroxyacetone which is less than 30 million-1separated from the mixture at relatively low energy costs, lower equipment costs and in the presence of water. In them it is stated that a mixture comprising at least phenol, water, hydroxyacetone and cumene can be processed using one stage fractional distillation with subsequent separation of the phases and obtaining phenol containing hydroxyacetone which is less than 30 million-1and this stage fractional distillation can be performed at a lower energy costs and lower equipment costs than in conventional methods. In addition, reported that the application order of execution stages of the method also lets you select the ü from the above mixture of phenol, with content hydroxyacetone constituting less

30 million-1.

Accordingly, it is proposed a way of separating phenol from a mixture comprising at least hydroxyacetone, cumene, water and phenol, which comprises fractionating the mixture through at least one stage fractional distillation and at least one stage of separation of the phases, carried out in such a way that they get at least one comprising a phenol fraction containing less than 300 million-1hydroxyacetone.

In addition, in the German patent application DE 10060505 A1 and international application WO 02/46133 A1 proposed installation for separation of phenol from a mixture comprising at least hydroxyacetone, cumene, water and phenol, which comprises at least one distillation column, which is given such dimensions that the fraction containing at least cumene and/or α-methylsterols, you can select from the upper part of the column and the fraction containing phenol with content hydroxyacetone, amounting to less than 300 million-1you can select from the bottom of the column, and at least one apparatus for the separation of the phases, designed to separate the aqueous phase from the organic phase.

The advantage of the described method is that selected for distillation separation stage simplifies subsequent processing of the mixture of the products of the splitting of the mode or separate fractions, obtained from a mixture of cleavage products. In particular, joint remove hydroxyacetone, AMS and cumene containing phenol residue of a mixture of cleavage products greatly simplifies the processing of the fractions containing phenol as they are unnecessary stage, carried out in the framework of the conventional method in which hydroxyacetone remains enriched in phenol fraction and removed from it by the reaction of hydroxyacetone with phenol to obtain compounds which have a higher boiling point than phenol, and can be separated from the phenol by distillation.

Compared with conventional previous methods, the proposed method is much more favorable energy balance and leads to greater total yield of phenol based on the content of phenol in the mixture of cleavage products. The proposed installation is considerably simplified, since less and the required number of distillation columns, and the number of devices necessary to reduce the content of various products in the fractions.

Summary of invention

Although the method and installation of the proposed applications DE 10060505 A1 and WO 02/46133 A1, represent a significant innovation in comparison with previously known methods and installations and lead to an increase of the ratio climbed the CSO actions and decrease energy costs and reduce capital equipment costs, than previously, yet energy efficiency is unsatisfactory and there continue to be a need to reduce production costs without affecting product quality.

Therefore, the present invention is to further improve the energy efficiency of the methods of the prior art while maintaining quality standards and the total yield of the desired end products.

These and other problems are solved using the method of producing phenolic compounds, including stage i) oxidation alcylaryl connection with obtaining a reaction mixture comprising alkylarylsulfonate and unreacted alcylaryl connection; (ii) the product obtained in stage i), the reaction of cleavage, leading to a mixture of fission products, comprising at least one phenolic compound, the ketone, the corresponding hydroxyketone and unreacted alcylaryl connection; (iii) processing of mixtures of fission products obtained in stage (ii), by distillation, which involves separating the mixture of cleavage products of at least three fractions using one stage fractional distillation by loading a mixture of fission products in the distillation column, removing the first fraction, Lucaya ketone, from the top of the distillation column, removing a second fraction comprising phenol compound, from the bottom of the distillation column and removing a third fraction comprising unreacted alcylaryl connection and hydroxyketone, as side product, and the outlet side of the shoulder strap is located above the section loading a mixture of fission products in the distillation column, characterized by the abstraction of heat from the distillation column, and a plot of discharge of heat is located above the outlet side product of the third faction.

Using a method corresponding to the present invention, even in a highly integrated way, such as, for example, known from German patent application DE 10060505 A1 and international patent application WO 02/46133 A1 can be greatly improved from the point of view of the required energy expenditure and investment of money capital in the installation. In the method corresponding to the present invention, using an internal irrigation, resulting in better reflux number, and the head of the column, in which removal of the first fraction, can be made much smaller and for removing the first fraction from the mixture of cleavage products require a much smaller refrigerators.

In the most preferred embodiment, this is about the invention of the heat released from the distillation column is used to heat the second distillation column, intended for the production of purified ketone of the first fraction. In a typical industrial applications of the present invention to heat the cubic product in the second column purification does not require additional heat, such as heating steam, and this leads to preserve a significant part of the energy lost during the cooling process, and that does not require energy for heating the cubic product in column cleanup.

In particular, if the transfer of heat from the distillation column to the second column purification is carried out by steam extraction at the site of heat, steam in the refrigerator located in the lower part of the second column, and the transfer of thermal energy kubulau product located in the second column, by condensation of vapor in the refrigerator with the subsequent return of condensed liquid in the distillation column, it is optimized to save energy, and internal reflux the number of distillation columns. Heat transfer can be adjusted by regulating the amount of steam taken on a plot of heat dissipation. This arrangement allows the use of small and light head part of the column, which reduces capital costs and operating costs because there is no heat exchanger, located in a remote place, and in particular allows the use of inexpensive and durable construction columns that can withstand the impact of high wind speed.

However, it may be favorable loading of the cubic product in the second column for purification through a heat exchanger located on a plot of heat the first column.

The preferred application of the present invention is a method in which the reaction mixture of cleavage products is part of the mixture of cleavage products obtained acid catalyzed cleavage of alkylhydroperoxide.

The method corresponding to the present invention, has an important economic value, if arylalkyl compound is cumene, phenol compound is phenol and the ketone is acetone and the hydroxy ketone is hydroxyacetone.

In the acceptable variant of the method the mixture of cleavage products additionally contains water.

In a preferred industrial embodiment of the method corresponding to the present invention, the stage of heat from the distillation column causes the temperature in the upper part of the column, equal to less than 65°C, preferably from about 55 to 60°C at normal pressure.

In another preferred embodiment of the method, the communication is relevant to the present invention, the mixture of cleavage products before being loaded into a distillation column is heated to a temperature exceeding 70°C at normal pressure, preferably to a temperature exceeding 100°C., more preferably to a temperature equal to from 110 to 180°C., most preferably to a temperature of approximately 140 to 146°C.

The above and other problems are also solved using the method of separation of phenol from a mixture of fission products, comprising at least acetone, cumene, water and phenol, into at least three fractions using a single-stage fractional distillation by loading a mixture of fission products in the distillation column, removing a first fraction comprising the acetone from the top of the distillation column, removing a second fraction comprising substituted or unsubstituted phenol, from the bottom of the distillation column, and removing a third fraction, optionally including hydroxyacetone and cumene, as side product, and the outlet side product lies above the area of the loading mixture of fission products in the distillation column, the mixture of products of cleavage before being loaded into a distillation column is heated to a temperature exceeding 100°C. at normal pressure, preferably to a temperature ravneet 110 to 180°C. most preferably to a temperature of approximately 140 to 146°C. At this temperature a mixture of cleavage products at least partially converted to steam, resulting from the cleavage product in the distillation column receives additional heat energy.

Compared with the methods known from the prior art, the method of separation corresponding to the present invention, and provides a reduction of the requirements for the installation, and improvement of the separation efficiency.

In the most preferred embodiment of the present invention, thermal energy to pre-heat gain in the cooling cleavage product after subsequent heat treatment of the cleavage product obtained acid catalyzed cleavage of cumene hydroperoxide to neutralize the mixture of cleavage products.

This subsequent heat treatment is described, for example, in German patent application DE 10021482 A1 and EP 1151985 A1. From these documents of the prior art, which are included in the present invention for a link, the method further heat treatment of the cleavage product obtained acid catalyzed cleavage of cumene hydroperoxide, generally known such as described above. Upon receipt of phenol from cumene is using the described method of Hawkeye the oxidized cumene to cumene hydroperoxide (CHP) in the first stage of the reaction, known as oxidation, and then CCP focus to the content of 65 to 90 wt.%, using vacuum distillation, known as concentration. In the second stage reaction, known as splitting, CCP liquor phenol and acetone by treatment with acid, usually sulfuric acid. At this stage dimethylphenylcarbinol (DMPC), formed during the oxidation, partially broken by the equilibrium reaction for α-methylsterol (AMC) and water, and another part DMFC interacts with the CCP with the formation of dicumylperoxide (DCT); the rest remains in the product splitting. After neutralization product of splitting this mixture of products is usually treated with distillation.

During the splitting part of the AMS forms a high-boiling compounds (dimers, cumylphenol), which are discarded as residue in the distillation. AMC still contained after neutralization, hereroense in the cumene during the distillation and recycled to the oxidation. DMFC, which is not reacted during cleavage, enters the remainder as high-boiling compounds, and part of it then interacts in the columns with hot phenol with the formation of AMC, which, in turn, the formation of high-boiling secondary components. DCT is stable under normal temperatures splitting (from 50 to 70°C). In the columns with hot phenol on which undergoes thermal decomposition with the formation of side products. On the other hand, in the presence of acids at temperatures above 80°C DCT can be converted into phenol, acetone and AMS. Therefore, the residual DMPC and DCT formed by cleavage, it is advisable immediately after splitting to enter in the reaction by a given rise of temperature in the presence of the acid used as catalyst for the splitting. In this way DMFC almost completely transformed into AMS, and DCT completely transformed into phenol, acetone and AMS.

This subsequent heat treatment of the cleavage product is already described in U.S. patent US 2757209, which is used at temperatures above 100°C., preferably from 110 to 120°C. the aim of this subsequent thermal processing was complete dehydration DMFC in AMS. In contrast, in the U.S. patent US 4358618 described subsequent heat treatment, aimed at the complete transformation of the DCT, formed by splitting, phenol, acetone and AMS using temperature components from 120 to 150°C. In U.S. patent US No. 5254751 described the subsequent thermal processing, pursuing the same goal as in the U.S. patent US 4358618, when using temperature comprising from 80 to 110°C. Finally, in the German patent application DE 19755026 A1 subsequent processing is carried out at temperatures above 150°C. it is Clear that in these descriptions vary greatly optimal range of the zone temperature, set for subsequent heat treatment of the cleavage product formed during the production of phenol.

In the disclosure contained in U.S. patent US 5463136, noted that effective cooling and, in particular, the temperature control is necessary for inhibition of the reaction in transport pipes to avoid the formation of bubbles and fumes that will cause cavitation in pumping the pump and therefore lead to a shutdown of the system. In addition, effective cooling is necessary as a first stage stopping the reaction to neutralize the reaction product. In U.S. patent US 2663735 alternatively, the application of the proposed cooling water to remove heat of reaction by evaporation of the acetone and temperature regulation by filing acetone in a reactor.

All previously disclosed methods, the cleavage product is first heated by steam in a heat exchanger to further heat treatment and, after a sufficient time of reaction, is cooled in heat exchangers water. Depending on the temperature selected for the subsequent heat treatment, it requires significant amounts of steam and cooling water. We found that the increased deposition of high-boiling by-products (contamination) in the heat exchangers during the subsequent thermal treatment is TKE usually occurs at temperatures above 100°C, in particular above 120°C, and this is due to a dramatic decrease in heat transfer. The equipment for heating the product ferry formation of deposits of organic matter especially in largely occurs on the hot surfaces of the heat transfer from the product, so that this equipment must be cleaned at relatively short intervals of time, comprising a few weeks. This blockage is exacerbated with increasing temperature.

Therefore, in the German patent application DE 10021482 A1 and European patent application EP 1151985 A1 a method and subsequent heat treatment of the cleavage product formed by the cleavage of cumene hydroperoxide, which is characterized not only by high selectivity, but low energy cost and high reliability, because excluded clogging. This way the subsequent heat treatment of the cleavage product formed by acid catalyzed cleavage of cumene hydroperoxide to phenol and acetone, which are subject to heat treatment of the cleavage product is heated in the reactor and in which the heat of reaction of at least one exothermic reaction occurring in the reactor is used to heat the cleavage product, subject to a heat treatment in the reactor, provides high is kind of selectivity subsequent processing while reducing energy costs and a longer period of operation of heat exchangers, because excluded clogging. The method described in DE 10021482 A1 and EP 1151985 A1, proposed for subsequent heat treatment of the cleavage product formed by acid catalyzed cleavage of cumene hydroperoxide to phenol and acetone, which are subject to heat treatment of the cleavage product is heated in the reactor in which the heat of reaction of at least one exothermic reaction occurring in the reactor is used to heat the cleavage product, subject to a heat treatment in the reactor.

Similarly, the proposed reactor for the production of phenol and acetone using acid catalyzed cleavage of cumene hydroperoxide, which has at least two sections, of which at least one section provided with a device for discharge of the heat and at least one other site has the characteristics of an ideal displacement. The described apparatus has the advantage that the actual splitting of the CCP and the subsequent heat treatment can be combined in a single reactor, the description of which is included in the present invention for reference. The method described in DE 10021482 A1 and EP 1151985 A1, has as compared with conventional prior methods have the advantage that heat the cleavage product, subject to subsequent thermal treatment t is buesa a much smaller amount of steam. If the heat of reaction released during subsequent thermal treatment of the cleavage product enough, it is possible to completely eliminate the use of steam for heating the product splitting. Unlike methods or other equipment in which steam or other suitable heat transfer medium continuously used for heating the product of cleavage, using a method corresponding to the present invention, for processing product splitting clogging occurs to a much lesser extent or not at all happening.

In a preferred embodiment of the method corresponding to the present invention, the first fraction contains at least 75% of ketone contained in the product of the cleavage-stage distillation.

In a particularly preferred embodiment of the method corresponding to the present invention, receive at least one fraction comprising phenol, containing less than 300 million-1preferably less than 30 million-1hydroxyacetone.

Preferably, if you get even one fraction comprising at least hydroxyacetone, cumene and water, and this last fraction is separated into the organic phase and aqueous phase. Preferably, if the organic and/or aqueous phase at least partially returned to the column.

In predpochtitel the nom embodiment of the method, relevant to the present invention, the mixture of cleavage products includes α-methylsterols, and/or a mixture of fission products has the concentration of phenol comprising from 20 to 90 wt.%.

Preferably, if the method corresponding to the present invention, the mixture of fission products has a concentration of hydroxyacetone factor of around 300 million-1up to 5 wt.%.

The method corresponding to the present invention, can be used as a superior method of producing phenol, comprising conducted using distillation processing of the mixtures obtained as part of mixtures of products of cleavage at the cleavage of cumene hydroperoxide (CHP) in acetone and phenol, followed by treatment of the mixture of cleavage products. The method corresponding to the present invention, it is preferable to apply for separation of phenols from a mixture that includes at least acetone, cumene, water and phenol, and is a mixture of cleavage products obtained by splitting the CCP.

These and other problems are also solved with the help of installation for separation of phenol from a mixture comprising at least acetone, cumene, water and phenol, comprising at least one distillation column, which is given such dimensions that at least one fraction containing cumene and/or α-methylsterols, you can otobrat the side of the outlet of the column, located above the side inlet designed to load a mixture of fission products, and the fraction containing phenol with content hydroxyacetone, amounting to less than 300 million-1you can select from the bottom of the column, and an outlet in the upper part of the column for removing the first fraction comprising acetone, characterized in that the distillation column further includes an intermediate heat exchanger or side outlet for condensation, located above the side outlet and below the upper part of the column.

Install the appropriate version of the present invention, requires construction costs, much smaller than previously proposed, because it requires a much smaller upper part of the column and to remove the first fractions of a mixture are less costly refrigerators, and is characterized by at least a similar separation efficiency. Since the intermediate heat exchanger, apparently, increases the internal reflux the number of columns, can be expected to increase separation efficiency.

In a preferred embodiment, the setting corresponding to the present invention, further includes at least one apparatus for the separation of the phases, designed for the separation of the aqueous phase anorganisch phases.

In a preferred embodiment, the installation corresponding to the present invention, the column has not less than 20 plates.

The lower part of the installation corresponding to the present invention, can be further simplified by placing the device for preheating upstream from the lateral inlet near the column for preheating the mixture of cleavage products before loading to the column.

In a preferred embodiment of the present invention, the installation is characterized by the fact that the device for preheating included in the General cooling circuit with a heat exchanger located downstream from the outlet of the reactor subsequent thermal processing. This implementation allows the use of cooling water or steam generated by cooling subjected to subsequent processing products for pre-heating of the material loaded in the column, eliminating the need for heat removal from the cooling water and the need for thermal energy, which is otherwise required for the corresponding heating of the material loaded in the column.

In the most preferred embodiment of the present invention, the installation is characterized by the fact that heat e is manic, located downstream from the outlet of the reactor subsequent thermal processing, forms a device for preheating, located upstream from the lateral inlet of the column. Thus, the mixture of cleavage products after cooling to neutralize and intermediate storage in order to remove salts is loaded through a heat exchanger located downstream from the outlet of the reactor subsequent heat treatment, and is fed to a distillation column. Thus neutralized mixture of cleavage products creates a cooling environment for the mixture of cleavage products before neutralization and simultaneously preheated to approximately the temperature corresponding to the subsequent thermal treatment of the cleavage product, obtained by acid catalyzed cleavage of cumene hydroperoxide. Therefore, you can save large quantities and cooling water, and heat, which greatly improves the economic efficiency of application of the installation corresponding to the present invention, compared with plants of the prior art.

Below the way and setting corresponding to the present invention, in an example described in relation to by using distillation processing with the art, the obtained acid catalyzed homogeneous splitting of the CCP, and then processing the mixture of cleavage products, and the method is not limited to this embodiment. This mixture is obtained as part of a mixture of cleavage products by allocating fractions of the crude acetone from a mixture of cleavage products.

The method corresponding to the present invention for the extraction of phenol from a mixture comprising at least acetone, cumene, water and/or hydroxyacetone and phenol, includes fractionation of the mixture using at least one stage fractional distillation and optionally at least one stage of separation of the phases, so get at least one fraction containing phenol, preferably containing less than 300 million-1hydroxyacetone. This fraction containing phenol, it is preferable to obtain the way in which one stage fractional distillation and optional single-stage phase separation.

Preferably, in order to highlight the phenol mixture had a concentration of phenol comprising from 20 to 90 wt.%, particularly preferably from 40 to 70 wt.%. The mixture may have a concentration of hydroxyacetone, component

300 million-1up to 5 wt.%.

In addition to the above compounds, the mixture may further comprise other compounds, such as α-m is Telstra (AMC), the cumene, water, phenylbutane, methylbenzofuran (ICF), dimethylphenylcarbinol (DMPC), Cresols, such as o-cresol, mesityloxide (MO), n-propylbenzoyl, isopropylphenol, carbonyl compounds such as 3-methylcyclopentene, (methyl)isobutylketone or 2-phenylpropionic aldehyde, second-butylbenzoyl, tert-butylbenzoyl, methylbenzol, such as xylene, acetophenone (AF), ketones, acids or aldehydes.

The method corresponding to the present invention can be implemented in different ways, but they all include at least one stage of distillation.

In the embodiment, the method corresponding to the present invention, the mixture fractionary using at least one stage fractional distillation, preferably only one stage of distillation, so that they formed a first fraction comprising the acetone, the second fraction comprising phenol, preferably containing less than 300 million-1hydroxyacetone, and a third fraction comprising at least hydroxyacetone, cumene and water, and this latter fraction is separated into the organic phase and the aqueous phase is at the stage of phase separation.

In this embodiment of the method corresponding to the present invention, the mixture from which you want to allocate the phenol is first loaded into a distillation apparatus, preferably in a distillation column. Distillati the authorized column should be given this configuration, to be able to fractionate the mixture to obtain at least one fraction containing acetone, one fraction containing phenol, and at least one other fraction, comprising at least cumene, water and hydroxyacetone. The mixture is preferably loaded into the column through the side inlet opening, preferably in the position in which column has the ability to divide constituting from 25 to 85%, particularly preferably from 40 to 60%. Column operates so that the fraction containing phenol, can be extracted in liquid form in the lower part of the column. The fraction containing phenol, which is separated in the lower part of the column and preferably has a concentration of hydroxyacetone, less than 300 million-1preferably be directed to further processing as a crude phenol.

The temperature in the lower part of the column is preferably equal to from 120 to 230°C., particularly preferably from 180 to 195°C. the Temperature in the upper part of the column is preferably equal to less than 65°C., particularly preferably from about 55 to 60°C at normal pressure. The temperature in the upper part of the column is always chosen so that the temperature in the upper part of the column was lower than the temperature at the bottom. The pressure in the column may be from 0.1 to 4 bar. Preferably, the distillation column is operated at atmospheres the second pressure. The required temperature in the upper part of the column set by the abstraction of heat from the distillation column through a heat exchanger located in the column.

In the embodiment, the method corresponding to the present invention, a third fraction comprising unreacted arylalkyl connection (cumene) and hydroxyacetone, is removed as a side product, and the outlet side of the shoulder strap is located above the section loading a mixture of fission products in the distillation column and the area of heat dissipation is located above the outlet side of the ring for a third faction. The outlet side of the shoulder strap is preferably positioned above the loading position of the mixture.

Alternative or in addition, to reduce the amount of energy needed to heat the cubic product, the mixture of cleavage products before being loaded into a distillation column is heated to a temperature exceeding 70°C at normal pressure, preferably to a temperature exceeding 100°C., more preferably to a temperature equal to from 110 to 180°C., most preferably to a temperature of approximately 140 to 146°C.

Most preferably, if thermal energy required for the pre-heat gain in the cooling product is the splitting after subsequent heat treatment of the cleavage product, the obtained acid catalyzed cleavage of cumene hydroperoxide. This product must be cooled to a temperature equal to from about 150 to about 40°C to inhibit subsequent uncontrolled reaction mixture of fission products to neutralize.

In variants of the method corresponding to the present invention, it is preferable that the phenol obtained from the loaded mixture, not only contained less than 300 million-1hydroxyacetone, preferably less than 30 million-1but contained few impurities, such as phenylbutane, methylbenzofuran (ICF), mesityloxide (MO), n-propylbenzoyl, isopropylphenol, carbonyl compounds such as 3-methylcyclopentene, (methyl)isobutylketone or 2-phenylpropionic aldehyde, second-butylbenzoyl, tert-butylbenzoyl or methylbenzol, such as xylene. These impurities are separated from the mixture together with α-methylstyrene (AMS), cumene and water through the outlet side product of distillation columns.

Fractions obtained in accordance with the present invention, can be further processed by methods known from the prior art.

The method corresponding to the present invention for the extraction of phenol from a mixture of fission products, comprising at least hydroxyacetone, cumene, water and phenol, prefer the LNO be carried out on the installation, relevant to the present invention.

This installation for separation of phenol from a mixture comprising at least acetone, cumene, water and phenol, includes at least one distillation column, which is given such dimensions that at least one fraction containing cumene and/or α-methylsterols, you can select from the side outlet of the column located above the side inlet designed to load a mixture of fission products, and the fraction containing phenol with content hydroxyacetone, amounting to less than 300 million-1you can select from the bottom of the column, and an outlet in the upper part of the column for removing the first fraction comprising acetone and water distillation column further includes an intermediate heat exchanger located above the side outlet. Preferably, if the installation further includes at least one apparatus for the separation of the phases, designed to separate the aqueous phase from the organic phase.

Preferably, if the device for preheating is located upstream from the lateral inlet near the column for preheating the mixture of cleavage products before being loaded into a distillation column.

In accordance with the present invention device is istwo for preheating included in the General cooling circuit with heat exchanger, located downstream from the outlet of the reactor subsequent thermal processing. This implementation allows the use of cooling water or steam generated by cooling subjected to subsequent processing products for pre-heating of the material loaded in the column, eliminating the need for heat removal from the cooling water and the need for thermal energy, which is otherwise required for the corresponding heating of the material loaded in the column.

However, in the most preferred embodiment of the present invention a heat exchanger located downstream from the outlet of the reactor subsequent thermal processing, forms a device for preheating, located upstream from the lateral inlet of the column. Thus, the mixture of cleavage products after cooling to neutralize and intermediate storage in order to remove salts is loaded through a heat exchanger located downstream from the outlet of the reactor subsequent heat treatment, and is fed to a distillation column. Thus neutralized mixture of cleavage products creates a cooling environment for the mixture of cleavage products before neutralization and at the same time p is evritania is heated approximately to the temperature appropriate subsequent thermal treatment of the cleavage product, obtained by acid catalyzed cleavage of cumene hydroperoxide. Therefore, you can save large quantities and cooling water, and heat, which greatly improves the economic efficiency of application of the installation corresponding to the present invention, compared with plants of the prior art.

Preferably, if the distillation column comprises at least 20, more preferably from 40 to 100 theoretical plates. In a particularly preferred embodiment, the installation corresponding to the present invention, it contains a side exhaust hole through which can be selected fraction including at least one organic acid, which is located between the loading position of the mixture and the lower part of the column. Organic acid contained in the faction, can be, for example, acetic acid, formic acid or butyric acid, or a mixture containing not less than one of these acids.

Preferably, in an apparatus for the separation of the phases, the installation corresponding to the present invention, include at least one of the decanter.

In a way consistent with the present invention, receive phenol. Preferably, if the phenol possess the AET content hydroxyacetone, constituting less than 300 million-1especially preferably less than 30 million-1. In a way consistent with the present invention, it is also possible to obtain a mixture containing cumene and/or AMC, having a reduced content of hydroxyacetone.

The method corresponding to the present invention, and install the appropriate version of the present invention, as the example presented in figure 1-6, the method or the installation is not limited to these options for implementation.

Figure 1 shows the diagram of the first variant implementation of the method and installation of the present invention;

figure 2 presents a diagram of another embodiment variant of implementation of the present invention with a different mode subsequent heat treatment;

figure 3 presents a diagram of a variant of implementation of the present invention using a dedicated device for preheating;

figure 4 presents the scheme of the preferred alternative implementation of the present invention;

figure 5 presents a diagram of an alternative implementation of the present invention and

figure 6 presents a diagram of an alternative implementation of the preferred in comparison with the embodiment presented in figure 3.

Figure 1 shows the schema version done by the means and method of installation of the present invention. Install the appropriate version of the present invention, includes the distillation column 1, which has a lateral inlet opening 2, through which the mixture of cleavage products can be downloaded for phenol recovery. In the upper 3 and lower 4 parts of the column 1 can be selected, respectively, the first fraction And containing vapors of acetone, and the second fraction, containing phenol. The distillation column 1 installation corresponding to the present invention, in the lower part 4 of the column has a heat exchanger 5, which in column 1 it is possible to apply thermal energy.

From the outlet side of the ring 6, which is located above the intake opening 2, it is possible to select a third fraction containing at least cumene, hydroxyacetone and water, and preferably pass through the apparatus for phase separation 7. Part of the organic and the aqueous phase formed in the apparatus for phase separation can be returned to the distillation column through the pipes 8. The remaining portion of the organic phase, which contains at least the cumene and/or α-methylsterol can be sent to further processing. Similarly a portion of the aqueous phase D in liquid or vaporous form can be returned to the distillation column 1 through the pipe 9. The remaining part of the aqueous phase D through the pipe 10 can be sent n the disposal or processing. In addition, the distillation column 1 further includes an intermediate heat exchanger 11, located in column 1 on the outlet side of the ring 6. The intermediate heat exchanger 11 reduces the temperature in the upper part 3 of the column 1 to the value, preferably less than 65°C., particularly preferably from about 55 to 60°C., at normal pressure, which leads to condensation of part of the vapor, improving internal irrigation. The temperature in the upper part 3 of the column 1 always choose so that the temperature in the upper part 3 was lower than the temperature in the lower part 4. Contained in column 1 wysokiej compounds are condensed with an intermediate heat exchanger 11 and because of this increased internal reflux the number of the column 1. As a consequence, improves the separation of the first fraction And comprising acetone, from the upper part 3 of the column 1 and the head of the column can be made much smaller, which reduces the amount of monetary investment. In addition, a reflux condenser 12 for the first fraction And comprising acetone taken in the upper part 3 of the column 1, can be made much smaller than before, which reduces capital and operational costs and saves significant amounts of cooling water.

The first fraction And comprising a pair of acetone and taken from column 1, the pipe 18 is upravliaetsa in column 13 for cleaning the execution takes place in a known manner additional purification through distillation. Pure acetone E can be extracted through the side discharge outlet 14 of the column 13. The waste stream F is selected at the bottom of column 13 to reset or processing.

The hot end of the intermediate heat exchanger 11 of the column 1 through the pipe 15 is connected with the lower heater 16 purification columns 13 to boot from the intermediate heat exchanger 11 cooling water having a temperature above about 65°C, the heater 16 for heating the cubic product in column 13. The cooling water is returned via a return pipe 17 into the intermediate heat exchanger 11 after passing through the heater 16. In a typical industrial method, the amount of energy needed for cooling in the upper part 3 of the column 1 can be greatly reduced and at the same time the crude acetone can be completely away without using steam, which otherwise would be required to heat the cubic product purification columns 13.

However, in the preferred embodiment of the present invention, is presented in figure 4, instead of embedding in column 1 of the intermediate heat exchanger 11 is used to direct the flow of vapor from the column through the side hole of the extraction steam 31 and feed them at the bottom of the heater 16 purification columns 13. The heater 16 pairs received through the hole of the steam extraction 31, condense and samuraiblue effectively heated bottom product of the column purification 13. Then the condensate is returned to the distillation column and is loaded through the return side inlet 32. It is assumed that in this case is most evident effect energy savings of the present invention. In addition, in this case does not require the location of a large heat exchanger in the upper part of the distillation column 1, which is for industrial column may have a height of about 15 m, which hinders its maintenance and cleaning. In addition, the upper part of the column 1 is greatly simplified and reduced, which leads to a more robust design that can withstand the impact of high wind speed.

In an alternative embodiment, presented on figure 5, the condensate from the bottom of the purification columns 13 through an optional three-way valve 33 or separator waste stream F is fed to the cold end of the intermediate heat exchanger 11 and is returned to the column cleanup 13 after heating the heat abstracted from the intermediate heat exchanger 11.

Figure 2 presents a diagram of another variant of the method corresponding to the present invention. The scheme of the reactor for a method and subsequent heat treatment of the cleavage product obtained by the cleavage of cumene hydroperoxide, known from German patent application DE 1002482 A1 and European patent application EP 1151985 A1, indicated by the number 20. This way the subsequent heat treatment of the cleavage product formed by acid catalyzed cleavage of cumene hydroperoxide to phenol and acetone, which are subject to heat treatment of the cleavage product is heated in the reactor and in which the heat of reaction of at least one exothermic reaction occurring in the reactor is used to heat the cleavage product to be heat treated in the reactor 21, provides high selectivity subsequent processing while reducing energy costs and a longer period of operation of the heat exchangers 22 and 23, as excluded clogging.

The mixture of products of the splitting of G leaves the reactor 21 at a temperature of approximately 150°C and must be cooled to approximately 40°C for inhibition of the reaction to neutralize (not shown). Usually through heat exchangers 22 and 23 conduct two-stage cooling in which the first heat exchanger 22 provides a significant reduction temperature of about 57°C, and the second heat exchanger 23 effectively maintains the temperature of the flow of the mixture of the products of the splitting of G equal to 40°C.

In prior art heat from the heat exchanger 22 dumped into the environment. In accordance with the present invention and scheme, PR is stavlennii figure 3, the heat exchanger is connected with a device for preheating 24 above the inlet 2 of the column 1, so that hot water or steam escaping from the heat exchanger 22, passes through the pipe 25 into the device for preheating 24 at a temperature equal to about 148°C. and Then cold water from the device for preheating 24 at a temperature of approximately 57°C, directly or crawl through the pipe 26 is returned to the heat exchanger 22. Thus, for loading into the column 1 through the inlet 2 of the neutralized mixture products of the splitting of G' is pre-heated to a temperature of approximately 145°C., Respectively, to maintain the temperature of the cubic product of the column 1 at the value required to perform the separation, requires considerably less energy supplied by the heat exchanger 5.

However, the boot stream G', which is fed to a distillation column 1, it is preferable to use directly for cooling flow of the mixture of the products of the splitting of G coming from the reactor 21. The boot stream G' after neutralization and storage in the intermediate tank to remove salts, which is an intermediate drive the production flow has a temperature, generally about equal to or less than 40°C. the Boot stream G' through the pipe 26 is directed into the heat exchanger 2, located near the inlet 21 of the reactor and withdrawn from the heat exchanger at a temperature of approximately 150°C, and loaded into the distillation column 1 through the pipe 25 leading to the side of the inlet opening 2 of the distillation column 1. This implementation provides an additional improvement of the energy efficiency and the use of thermal energy that can be obtained from the subsequent heat treatment in the reactor 21.

In a typical industrial way you can save a large part of the energy required for cooling the mixture of cleavage products to neutralize, and at the same time the boot stream G' distillation column 1 can be subjected to considerable pre-heating without the use of steam, which otherwise would be required for additional heating of the cubic product of the column 1.

1. The method of producing phenol, comprising:
i) oxidation of cumene with obtaining a reaction mixture comprising cumene hydroperoxide and unreacted cumene;
ii) the product obtained in stage i), carrying out the cleavage reaction, leading to a mixture of fission products, including, at least, phenol, acetone, hydroxyacetone, unreacted cumene and water;
iii) processing the mixture of cleavage products obtained in stage (ii),by distillation, which includes the separation of a mixture of fission products, at least three fractions using a single-stage fractional distillation through:
download mixture of fission products in the distillation column,
removal of the first fraction comprising the acetone from the top of distillation columns,
removing a second fraction comprising phenol, from the bottom of the distillation column, and
removing a third fraction comprising at least unreacted cumene, hydroxyacetone and water, in the form of a side of a shoulder strap, and the outlet side of the shoulder strap is located above the section loading a mixture of fission products in the distillation column, characterized by the abstraction of heat from the distillation column, and a plot of discharge of heat is located above the outlet side product of the third faction.

2. The method according to claim 1, in which heat is withdrawn from the distillation column is used to heat the second distillation column, intended for the production of purified acetone from the first fraction.

3. The method according to claim 1, wherein the third fraction is separated into the organic phase and aqueous phase.

4. The method according to claim 1, in which stage of abstraction of heat from the distillation column causes the temperature in the upper part of the column, less than 65°C., preferably from 55 to 60°C, when n is rmalina pressure.

5. The method according to one of claims 1 to 4, in which the mixture of cleavage products before being loaded into a distillation column is heated to a temperature exceeding 70°C at normal pressure, preferably to a temperature exceeding 100°C., more preferably to a temperature equal to from 110 to 180°C., most preferably to a temperature equal to from 140 to 146°C.

6. The method according to claim 1, wherein the first fraction contains at least 75% of acetone contained in the product of the cleavage-stage distillation.

7. The method according to claim 1, wherein receiving includes phenol fraction containing less than 300 million-1preferably less than 30 million-1hydroxyacetone.

8. The method according to claim 1, in which the mixture of cleavage products includes α-methylsterol.

9. The method according to claim 1, in which the mixture of fission products has the concentration of phenol comprising from 20 to 90 wt.%.

10. The method according to claim 1, in which the mixture of fission products has a concentration of hydroxyacetone factor of around 300 million-1up to 5 wt.%.

11. Method of extraction of phenol from a mixture of the products of the cleavage of cumene hydroperoxide, including, at least, acetone, cumene, water and phenol and hydroxyacetone, separated into three fractions using a single-stage fractional distillation through:
download mixture of fission products in the distillation column,
deletion is of first fraction, including acetone, from the top of distillation columns,
removing a second fraction comprising phenol, from the bottom of the distillation column, and
removing a third fraction comprising at least hydroxyacetone, cumene and water, in the form of a side of a shoulder strap, and the outlet side of the shoulder strap is located above the section loading a mixture of fission products in the distillation column, the mixture of products of cleavage before being loaded into a distillation column, heated to a temperature equal to from 110 to 180°C. at normal pressure, preferably to a temperature equal to from 140 to 146°C, while implementing the abstraction of heat from the distillation column, and a plot of discharge of heat is located above the outlet side product of the third faction.

12. The method according to claim 5, in which thermal energy to pre-heat gain in the cooling cleavage product after subsequent heat treatment of the cleavage product obtained acid catalyzed cleavage of cumene hydroperoxide to neutralize the mixture of cleavage products.

13. The method according to claim 11, in which the first fraction contains at least 75% of acetone contained in the product of the cleavage-stage distillation.

14. The method according to claim 11, in which the receiving includes phenol fraction, with whom containing a series of less than 300 million -1preferably less than 30 million-1hydroxyacetone.

15. The method according to claim 11, in which the third fraction is separated into the organic phase and aqueous phase.

16. The method according to item 15, in which the organic phase and/or aqueous phase, at least partially returned to the column.

17. The method according to claim 11, in which the mixture of cleavage products includes α-methylsterol.

18. The method according to claim 11, in which the mixture of fission products has the concentration of phenol comprising from 20 to 90 wt.%.

19. The method according to claim 11, in which the mixture of fission products has a concentration of hydroxyacetone factor of around 300 million-1up to 5 wt.%.

20. Installation for separation of phenol from a mixture of the products of the cleavage of cumene hydroperoxide containing, at least, acetone, cumene, water and phenol, hydroxyacetone and α-methylsterols, including one distillation column, which is given such dimensions that one fraction containing hydroxyacetone, water, cumene and/or α-methylsterols, you can select from the side outlet of the column located above the side inlet designed to load a mixture of fission products, and the fraction containing phenol with content hydroxyacetone, amounting to less than 300 million-1you can select from the bottom of the column, and an outlet in the upper part of the column for deletion is of first fraction, including acetone, characterized in that the distillation column further includes an intermediate heat exchanger located above the side outlet and below the upper part of the column.

21. Installation according to claim 20, further comprising at least one apparatus for the separation of the phases, designed to separate the aqueous phase from the organic phase.

22. Installation according to claim 20, in which the column has at least 20 plates.

23. Installation according to any one of p-22, additionally comprising a device for preheating, located upstream from the lateral inlet near the column for preheating the mixture of cleavage products before loading to the column.

24. Installation according to item 23, wherein the device for preheating included in the General cooling circuit with a heat exchanger located downstream from the outlet of the reactor subsequent thermal processing.

25. Installation according to any one of p-22, in which a heat exchanger located downstream from the outlet of the reactor subsequent thermal processing, forms a device for preheating, located upstream from the lateral inlet of the column.



 

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13 cl, 4 ex

FIELD: chemical industry; methods of production of phenol and acetone.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the industrial process of production of phenol and acetone by the cumene method. The method is realized by decomposition of the technological cumene hydroperoxide in the in series connected reactors in two stages with formation on the first stage of the dicumylperoxide at the temperature of 40-65°С at presence as the catalytic agent of 0.003-0.015 mass % of the sulfuric acid with its subsequent decomposition on the second stage in the reaction medium at the temperature of 90-140°С. The process is conducted at the excess of phenol in the reaction mixture at the molar ratio of phenol : acetone exceeding 1, preferentially - from 1.01 up to 5. Excess of phenol is formed either by distillation (blowing) of acetone or addition of phenol in the reaction medium. The technical result of the invention is reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.

EFFECT: the invention ensures reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.

5 cl, 4 ex, 8 tbl

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to catalytic decomposition of organic hydroperoxides representing important compounds on organic synthesis. Decomposition of cycloalkyl hydroperoxides comprising from 6 to 12 carbon atoms results to formation a mixture of corresponding alcohols and ketones. Process is carried out in the presence of a solvent (alkane, halogen-containing hydrocarbon) at temperature from 20°C to 200°C. Catalyst comprises ruthenium as a catalytically active metal added to a solid carrier chosen from the following group: carbon prepared by pyrolysis of acetylene and metal oxides chosen from the group comprising zirconium, aluminum, lanthanum and manganese. The amount of catalyst expressed as the mole percents of ruthenium to the amount of moles of hydroperoxide to be decomposed is from 0.0001% to 20%. Preferably, the catalyst comprises one additional rare-earth element as a component of alloy. The carrier represents, as a rule, metal oxide with high specific surface above 10 m2/g but preferably, above 100 m2/g that is resistant against oxidation. The hydroperoxide concentration is in the range from 1 to 80 wt.-% with respect to the solution mass. Preferably, hydroperoxide represents cyclohexyl, cyclododecyl, tetraline, ethyl benzene or pinane hydroperoxide and hydrocarbon used in preparing the parent hydroperoxide is used as a solvent. Invention provides the development of the modified catalyst enhancing conversion and selectivity in decomposition of hydroperoxides.

EFFECT: improved method for decomposition.

8 cl, 24 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing phenol and acetone by acid-catalyzed cleavage of cumyl hydroperoxide. Method involves preliminary heating the reaction mixture to temperature above 100°C and then for thermal treatment of product heat in exothermic reaction is used, mainly the cleavage reaction of cumyl hydroperoxide that presents in the concentration from 5 to 10 wt.-%. The preferable residual content of dicumyl hydroxide in thermally treated product is 0.01-0.05 wt.-%. Stages in cleavage of cumyl hydroperoxide and the following thermal treatment can be carried out in a single reactor with two zones among that one zone is fitted with a device for heat removing and another zone has a feature of the flow-type pipe. Reactor is equipped by a device for circulation of part of product from thermal treatment zone to a feeding line for decomposition of product. Method provides improving energetic indices of process due to optimal consumption of heat energy in maintaining high selectivity of the decomposition process.

EFFECT: improved preparing method.

15 cl, 3 dwg

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to joint phenol-acetone production via selective decomposition of cumene hydroperoxide. Process is conducted in several in series connected reactors constructed in the form of shell-and-tube heat-exchangers, wherein part of decomposition product is recycled into reaction zone and mixed with feed stream to be decomposed, weight ratio of recycled stream to feed stream being less than 10. Reactors with tubular hydrodynamic characteristic have volumetric heat-exchange surface equal to or larger than 500 m2/m3. Preferably, residual concentration of cumene hydroperoxide is 0.1-0.3 wt % and its residence time in decomposition zone ranges from 0.5 to 10 min.

EFFECT: increased selectivity of decomposition at lesser recycle apparatus volume and reduced investment expenses.

11 cl, 1 dwg, 9 ex

The invention relates to an improved method of decomposition of the hydroperoxide with the formation of a mixture containing the corresponding alcohol and ketone, comprising the stage of: a) adding water in the amount of 0.5-20% in the mixture containing the hydroperoxide; (b) the deletion of specified volume of water in such a way that together with water removes water-soluble impurities; C) removing the remaining water in such a way that the reaction mixture is not more than 2% of water; and (d) decomposition of the specified hydroperoxide by contacting the reaction mixture with a catalytic amount of a heterogeneous catalyst containing gold, supported on a carrier

FIELD: chemistry.

SUBSTANCE: method of producing cumene includes interaction of benzene with acetone and hydrogen with catalytic compound added as containing one or more zeolite in acid form or preferentially acid form, copper and, optionally, one or more element chosen from elements of groups IIIA, VIB, VIIB. Additionally the given invention concerns method of producing phenol with using cumene prepared by the method as described, catalytic compound for production cumene, and also methods of producing catalytic compound for cumene.

EFFECT: application of the methods and catalytic compounds specified above allows simplifying considerably producing phenol from cumene, allowing for simultaneous one-stage reaction for all chemical transformations required to produce high-yield cumene from acetone, benzene and hydrogen with minimum amount of secondary reactions of various reagents, intermediate compounds and products.

69 cl, 16 ex, 2 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: one of method versions is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification and possibly partial recycling into reaction zone(s) of one or several components of reaction mixture. Decomposition is carried out in presence of inert easily-boiling solvent, which contains mainly hydrocarbons, whose boiling temperature is lower than 70°C, preferably lower than 40°C, but not lower than minus 1°C, which is partially evaporated directly from reaction zone(s) and partially distilled from obtained reaction mixture, is in liquid state returned to reaction zone(s) with supporting in it (them) temperature from 1 to 70°C, preferably from 10 to 45°C. Second method version is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification. Applied is easily-boiling solvent, which after separation from reaction mixture, possibly with part of ketone, is recycled into reaction zone(s), and sulfocationite catalyst in H+ form, resistant in liquid media, containing alkylaromatic hydroperoxides, ketones, phenol and hydrocarbons in large amount, at temperatures up to 70°C, in fine-grain or coarse-grain form, possibly, in form of mass-exchange filling with size from 1.5 to 25 mm.

EFFECT: obtaining phenol and ketones without formation of large amount of by-products and resins and practically without equipment corrosion.

14 cl, 1 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: at first stage by continuous method phenol is obtained by direct benzol oxidation with hydrogen peroxide with ratio of H2O2/benzol from 10 to 70% mol., in three-phase reaction system, which includes first liquid phase, consisting of benzol and organic solvent, second liquid phase, consisting of water, and solid phase, consisting of activated catalyst, which contains titanium silicate TS-1. At second stage phenol and benzol which has not reacted are separated from reaction mixture by fraction distillation. At third stage solvent and by-products, containing dioxybenzols, are separated from mixture, supplied from tail fraction of second stage distillation, by extraction with base obtaining water solution of dioxybenzols. At fourth stage obtained water solution of dioxybenzols is converted into phenol by hydrodeoxygenation with hydrogen in conditions of continuous operation at temperature from 250 to 500°C, pressure 0.1-10 MPa and in presence of catalyst containing element of group VIB or their mixture or element of group VIII of periodic system or their mixture and promoter. At fifth stage obtained by re-cycle at previous stage phenol is supplied to distillation stage.

EFFECT: increase of degree of benzol conversion and selectivity on phenol, elimination of diphenol formation and reduction of solvents quantity.

22 cl, 8 ex, 1 dwg

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