RU2341510C2 - Method of obtaining phenol and ketone from hydroperoxide of alkylaromatic hydrocarbon (versions) - Google Patents

Abstract

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

Description

The invention relates to the field of processing of alkyl aromatic hydroperoxides to produce phenol and ketones.

Known [M. Kharasch, J. Org. Chem., 1950, 15, p. 748] a method for producing phenol and ketone, in particular acetone, by decomposition of dialkylphenyl hydroperoxides in the presence of liquid strong acids. The main disadvantage of this method is the use of highly corrosive catalyst and the absence of an effective technological solution to the problem of removing reaction heat (the reaction is highly exothermic).

Known methods [US Pat. US 2661375, 1953, US Pat. Germany 944013, 1956] the process of decomposition of alkylaromatic hydroperoxides to produce phenol and ketone in the presence of aqueous solutions of sulfuric acid by contacting two mutually insoluble phases. The disadvantages of these methods are the use of highly corrosive catalyst and the need for special devices for mixing phases.

Known methods for carrying out the process of decomposition of alkyl aromatic hydroperoxides to produce phenol and ketone by catalysis with sulfuric acid using homogenizers. In [Ind. Chem., 1960, No. 36, p. 215], phenol partially recycled in the process was used as a homogenizer. One of the disadvantages of the method is the difficulty of effective heat removal and the presence of adverse reactions of phenol.

It has been proposed [US Pat. Canada 507550, 1954, US Pat. US 2761877, 1956] and a method for the production of phenol and acetone by the decomposition of dimethylphenyl hydroperoxide in the presence of sulfuric acid was implemented in industry, in which most of the acetone released from the reaction mixture was returned to it in an amount many times higher than the amount of the starting hydroperoxide and phenol formed. To remove the heat of a strongly exothermic reaction from the reaction zone, a significant part of the acetone is evaporated, then condensed and returned to the reaction zone. The method turned out to be more effective than the previous ones and is used in industry, including in Russia [Handbook of petrochemistry, L., Chemistry, 1978, v.2, p.184]. The disadvantages of the method are:

- corrosiveness of sulfuric acid and the formation of harmful wastewater during its neutralization after the reaction zone;

- the formation of a large number of by-products as a result of acetone reactions, present in large numbers in the reaction zone and having significant reactivity in the presence of an acid catalyst;

- the inability to lower the temperature in the reaction zone by evaporation of acetone below 60 ° C without using vacuum, which leads to the formation of by-products: α-methylstyrene and its oligomers, mesityl oxide, cumylphenol and other high-boiling by-products.

We have found methods that allow to obtain phenol and ketones by decomposition of alkyl aromatic hydroperoxides without the formation of a high amount of by-products and resins, and also practically without corrosion of equipment.

We declare:

A method of producing phenol and ketone from an aromatic hydrocarbon hydroperoxide by decomposing it in the presence of a catalyst with strong acidity in one or more reaction zones, followed by separation of the reaction mixture by distillation and possibly partial recirculation to the reaction zone (s) of one or more reaction components mixtures, characterized in that the decomposition is carried out in the presence of an inert low-boiling solvent containing mainly hydrocarbon (s) with a boiling point below 70 ° C, preferably below 40 ° C, but not lower than minus 1 ° C, which is partially evaporated directly from the reaction (s) zone (s) and partially distilled from the resulting reaction mixture, in a liquid state, is returned to the reaction (s) zone ( s) and maintain in it (them) a temperature of from 1 to 70 ° C, preferably from 10 to 45 ° C.

As methods that contribute to the effective implementation of the method according to claim 1, we also declare methods, characterized in that:

- as the composition or composition of the specified solvent is used predominantly saturated (e) hydrocarbon (s), preferably not containing (e) tertiary carbon atoms;

- n-pentane and / or isopentane, and / or cyclopentane, and / or n-butane, and / or isobutane are used as or composition of said inert solvent;

- when the reaction mixture is separated, the solvent is isolated by distillation and recycled to the reaction zone (s), possibly with a part of the formed ketone, the content of which in the recycle stream is limited to a concentration of not more than 50% by weight, preferably not more than 25% by weight .;

- an alkyl aromatic hydrocarbon hydroperoxide, a recyclable low boiling inert solvent and possibly a recycle ketone are supplied to the successive points of the reaction zone (s) in two or more streams;

- isopropylbenzene hydroperoxide is decomposed and phenol and acetone are obtained as products;

- decomposition is subjected to sec-butylbenzene hydroperoxide, and phenol and methyl ethyl ketone are obtained as products;

- when using a fine-grained catalyst, its entrainment is prevented by the holding device (s) with aperture size smaller than the minimum particle size of the catalyst.

We also independently declare:

A method of producing phenol and ketone from alkyl aromatic hydrocarbon peroxide by decomposing it in the presence of a strong acid catalyst in one or more reaction zones, followed by separation of the reaction mixture by distillation, characterized in that a low-boiling solvent is used, which, after separation from the reaction mixture, is possible with part of the ketone, recycle to the reaction (s) zone (s), and the sulfocationic catalyst in the H + form, stable in liquid media containing large quantities of al ilaromaticheskie hydroperoxides, ketones, hydrocarbons and phenol, at temperatures up to 70 ° C, a fine-grained or coarse-grained form, possibly ranging from 1.5 to 25 mm in the form of mass transfer packing.

As methods that contribute to the effective use of this method, we also declare methods, characterized in that:

- the decomposition of the specified hydroperoxide using the specified sulfocationite catalyst is carried out in the presence of an inert low-boiling solvent containing mainly hydrocarbon (s) with a boiling point below 70 ° C, preferably below 40 ° C, but not lower than minus 1 ° C, which is partially evaporated from the reaction ( n) zones (zones) and partially distilled from the resulting reaction mixture, in a liquid state, return to the reaction (s) zone (s) and maintain temperature (1) to 70 ° C, preferably 10 to 45 ° C;

- alkyl aromatic hydrocarbon hydroperoxide and a recyclable low-boiling inert solvent, possibly with ketone, are fed to the successive points of the reaction zone (s) in two or more streams;

- isopropylbenzene hydroperoxide is decomposed, and phenol and acetone are obtained as products;

- decomposition is subjected to sec-butylbenzene hydroperoxide and phenol and methyl ethyl ketone are obtained as products;

- when using a fine-grained sulfocationic catalyst, its entrainment is prevented by the holding device (s) with aperture size smaller than the minimum particle size of the catalyst.

The proposed methods make it possible to use hydrocarbons with a low boiling point as an inert solvent, including C ₄ hydrocarbons (n-butane, isobutane), C ₅ hydrocarbons (n-pentane, isopentane, cyclopentane) and their mixtures and to keep sufficiently low in the reaction zones temperatures up to + 1 ° C, at which the formation of by-products is reduced.

Various types of reactors can be used as reactors for the decomposition of alkyl aromatic hydroperoxide, which allow evaporation of the solvent from the reaction zone (s) and return of its condensate to the reaction zone (s), in particular, horizontal direct-flow (with a vapor space above liquid), vertical reactors and / or stirred reactors.

Structurally partitioned reactors can be made in the form of several separate reaction apparatuses connected by corresponding flows through the vapor and liquid phases.

Small amounts of liquid acids can be used as catalysts, however, it is preferable to use porous sulfocationic catalysts: coarse-grained (including those molded in the form of a mass-transfer nozzle) or fine-grained when placed in microcontainers with a large number of openings (for example, mesh), or suspended ("boiling") state.

If there is a mixture of hydroperoxides as a raw material, it is possible to decompose hydroperoxides without prior separation, for example, decomposition of a mixture of isopropylbenzene hydroperoxide and sec-butylbenzene hydroperoxide (to produce phenol and acetone from isopropylbenzene hydroperoxide and phenol and methyl ethyl ketone from sec-butylbenzene hydroperoxide).

The application of the invention is illustrated in the drawing and examples. These figures and examples do not exclude the possibility of applying other technical solutions subject to the conditions (features) contained in paragraph 1 and / or paragraph 5 of the claims.

According to the drawing, the alkyl aromatic hydroperoxide (with an admixture of unoxidized alkyl aromatic hydrocarbon and possibly by-products) enters through line 1. Perhaps a solution of a strong acid enters through line 2. The hydroperoxide and possibly acid are mixed in whole or in part with a stream of condensed solvent evaporated from the reaction zone P (lines 4, 4a). The specified condensate (stream 4) or its mixture (stream 5) is completely or partially sent to the reaction zone P through line 5. Perhaps part of the condensate (stream 4b) and / or part of the acid and / or part of the hydroperoxide along line 6 (and further 6a, 6b, 6c) are fed in the desired proportions to various points of the reaction zone R. A stream of evaporated solvent (mixed with ketone) is withdrawn from line 3 from reaction zone P, which is condensed and then recycled to zone P along line 4.

The reaction zone P has compartments separated by partitions with holes in which a heterogeneous catalyst, in particular sulfocationite, is placed (when used).

The reaction mixture is withdrawn from the reaction zone P via line 7, which, if necessary, is neutralized in the apparatus “N” and fed through line 8 to the distillation column K-1. The steam stream discharged from above K-1 is condensed, and water is peeled off in a CO separator-settler.

A part of the organic layer, containing predominantly a solvent, is returned to K-1 as reflux, and the rest is returned via line 10 (hereinafter 10a and possibly 10b and 10c) to reaction zone R. The aqueous layer from CO is withdrawn via line 11.

The bottom residue of the K-1 column through line 12 is fed to the distillation column K-2. On top of K-2, a distillate stream (mainly containing ketone) is discharged along line 13. Next, stream 13 is discharged through line 13a and / or fed via line 13b for purification to the SD separation unit.

Bottom K-2 output stream 14 containing phenol and impurities, which is fed to the site of the SD.

The SD unit contains several distillation columns, the connection order of which may vary. Phenol is discharged from line 15 through line 15, alkyl benzene is discharged through line 16 (which is preferably recycled to the alkyl aromatic hydroperoxide production step), heavy impurities are discharged through line 17. It is also possible that ketone is taken out of the UR assembly via line 18 (if it was sent to the UR for purification) and impurities separated from the ketone are taken out through line 19.

Examples.

In the examples, the concentrations are indicated in% wt.

Example 1

According to the drawing, the initial stream of isopropylbenzene hydroperoxide (HYPERIZE) containing HYPERIZE-90% (100 kg / h), as well as isopropylbenzene - 2.5%, acetophenone - 1.5%, dimethylphenylcarbinol (DMFK) - 6.0% is subjected to processing according to the drawing.

The HYPERISIS stream is mixed with a stream of a return inert solvent (n-pentane, Tbk = 36.1 ° С) containing ~ 21% of a return acetone (Tbk = 56.3 ° С) and a stream of sulfuric acid (catalyst) supplied in such quantity so that the concentration of sulfuric acid in the mixture was ~ 0.2%. The mixed stream is fed through line 5 to reactor R.

The composition of the mixed stream (for organic substances): n-pentane - 62.0%, acetone - 16.2%, HIPERIZ-19.8%, isopropylbenzene - 0.5%, acetophenone - 0.3%, DMFK - 1, 2% Part of the acetone is fed to reactor P separately.

The reactor P is a horizontal cylindrical tank with partitions ~ 2/3 of the height, with openings. A temperature of 42 ° C. is maintained in the reactor by evaporation of a part of the solvent (admixture of acetone), its condensation and return to the reactor.

In the reactor, the HYPERISE is completely decomposed mainly with the formation of phenol and acetone. From the reactor, 505 kg / h of the mixture with the content of organic substances are removed: n-pentane - 62.0%, acetone - 23.46%, phenol - 12.24%, isopropylbenzene - 0.50%, acetophenone - 0.03%, DMFK - 0.1%, α-methylstyrene - 1.05%, mesityl oxide - 0.15%, as well as a small amount of heavy boiling impurities and water (~ 0.2%).

From the K-1 column, 390 kg / h of a stream containing 79% n-pentane and 21% acetone are withdrawn from above and returned to the reactor. VAT residue K-1 in an amount of 109 kg / h served in the column K-2. From the K-2 column, a stream 13, containing mainly acetone, is removed from above, and a mixture of high-boiling components is below.

After the subsequent separation, ~ 61.0 kg / h of phenol and 37.7 kg / h of acetone of commercial grade purity are obtained in the SD unit.

Example 2

Processing according to the drawing is subjected to the initial flow of HYPERISE, in quantity and composition similar to that specified in example 1 (in it 100 kg / h of HYPERISE). The sulfuric acid content in the liquid in the reactor is ~ 0.2%.

In contrast to example 1, n-butane is used as an inert solvent (bp = minus 0.5 ° C). In the reactor, the concentration of n-butane is maintained at 60.6% and the temperature is 20 ° C. The concentration of HYPERISE in the stream entering the reactor is 30%. In this case, the complete decomposition of HYPERISE occurs mainly with the formation of phenol and acetone.

333 kg / h of the mixture are withdrawn from the reactor containing 60.6% n-butane, 18.5% phenol, 17.6% acetone, 0.75% isopropylbenzene, 0.45% acetophenone, 0.2% DMF, 1, 6% α-methylstyrene, less than 0.01% mesityl oxide, a small amount of heavy boiling impurities and water (traces).

218 kg / h of a stream containing 94% n-butane and 6% acetone are distilled off from K-1 column and returned to the reactor. From column K-2, 38.0 kg / h of practically pure acetone are distilled off.

Upon rectification of the bottom residue of the K-1 column in the UR unit, 61.3 kg / h of commercial grade phenol are obtained.

Example 3

Processing according to the drawing is subjected to the initial flow of HYPERISE, in quantity and composition similar to that specified in example 1 (in it 100 kg / h of HYPERISE).

Amberlist-35 fine-grained sulfonated cation exchanger (particle size 0.4-1.2 mm, static exchange capacity SOE = 5.4 mg-equivN + / g) is used as a catalyst in the reactor.

A temperature of 65 ° C. is maintained in the reactor by evaporation, subsequent condensation, and acetone recovery.

The load on the catalyst is 12 kg of liquid mixture per 1 kg of catalyst per hour. At the entrance to the reactor, the concentration of HYPERIS is maintained at 30-36%, acetone at 60-70%.

333 kg / h of mixture containing 77.2% acetone, 18.6% phenol, 1.55% α-methylstyrene, 0.75% isopropylbenzene, 0.80% acetophenone, 0.2% mesityl oxide and ~ are removed from the reactor 0.2% of heavy boiling impurities and water.

From the K-1 column, 223 kg / h of a stream containing predominantly acetone are distilled off, condensed and returned to the reactor. Column K-2 is used to distill off boiling impurities from acetone. 37.9% acetone is withdrawn as the product, and the rest of its amount is recycled to the reactor.

As a result of the separation of the bottom residue of the K-1 column in the UR unit, 61.1 kg / h of phenol of commercial purity are obtained.

Example 4

Processing according to the drawing is subjected to the initial flow of HYPERISE, in quantity and composition similar to that specified in example 1 (in it 100 kg / h of HYPERISE).

The catalyst used in the reactor is fine-grained sulfonic cation exchanger KU-2-8 hC (particle size 0.4-1.1 mm, static exchange capacity SOE = 4.7 mg-eqN + / g). The solvent used is n-pentane. In the reactor P, the concentration of n-pentane is maintained at ~ 52% and the temperature is 44 ° C. The concentration of HYPERISIS at the inlet to the reactor (relative to the sum of the incoming flows) is 30%. The feed of introduced HYPERISE and a solvent (mixed with acetone) is distributed between the first three successive sections of the reactor in a 4: 2: 1 mass ratio. The load on the catalyst is 13 kg / h of liquid mixture per 1 kg of catalyst.

340 kg / h of the reaction mixture containing 52.2% n-pentane, 25.8% acetone, 18.7% phenol, 0.75% isopropylbenzene, 0.77% acetophenone, 1.4% α-methylstyrene are removed from the reactor , 0.1-0.15% DMFK, 0.1% mesityl oxide and 0.1-0.2% heavy boiling impurities and water.

From the K-1 column, the 215 kg / h stream containing 78% n-pentane and ~ 22% acetone is distilled off, condensed and returned to the reactor P. After distillation of the bottom residue in the K-2 column and separation in the SD zone, 61.5 kg / h of phenol and 38.3 kg / h of acetone are obtained.

Example 5

Processing according to the drawing is subjected to the initial flow of HYPERISE, in quantity and composition similar to that specified in example 1 (in it 100 kg / h of HYPERISE).

A KU-2FPP coarse-grained molded sulfocationic catalyst (pellets in the form of cylinders 6-10 mm long, 4-6 mm in diameter, static exchange capacity SOE = 3.3 mg-equivN + / g) is used as a catalyst in the reactor.

The solvent used is n-pentane. In the reactor P, the concentration of n-pentane was maintained at ~ 52%, and the temperature was 45 ° C. The concentration of HYPERISIS at the input (relative to the sum of the incoming flows) is 30%.

The load on the catalyst is 4 kg / h per 1 kg of catalyst.

335 kg / h of the reaction mixture containing 51% n-pentane, 24.7% acetone, 18.7% phenol, 0.75% isopropylbenzene, 0.8% acetophenone, 1.5% α-methylstyrene, 0 are removed from the reactor , 2% DMFK, 0.1-0.2% mesityl oxide and 0.2-0.3% heavy boiling impurities and water.

From the K-1 column, 204 kg / h of a stream containing 79% n-pentane and ~ 21% acetone are distilled off, condensed and returned to the reactor. After distillation of the bottom residue in the K-2 column and separation in the SD zone, 61.3 kg / h of phenol and 38.1 kg / h of acetone are obtained.

Example 6

Processing according to the drawing is subjected to the initial stream of sec-butylbenzene hydroperoxide (its content is 100 kg / h, which is 85% of the flow value). The content of other impurities: 2-phenylbutanol-2 - 7%, sec-butylbenzene - 4.0%, alkylaromatic ketone - 4.0%.

As a catalyst in the reactor, a coarse-grained molded sulfate cation-ion exchange resin catalyst KIF (granules in the form of cylinders 5-8 mm long, 4-6 mm in diameter, static exchange capacity SOE = 3.6 mg-equivN + / g) is used.

The solvent used is n-pentane. The temperature in the reactor is 55 ° C, the concentration of hydroperoxide at the inlet to the reactor R (relative to the sum of the incoming flows) is 30%.

332 kg / h of reaction mixture containing 60.2% n-pentane, 17.3% acetone, 16.9% phenol, 1.4% sec-butylbenzene, 1.4% alkyl aromatic ketone, 1.8% are removed from the reactor 2-phenylbutene-2, 0.5% 2-phenylbutanol-2, 0.4% heavy boiling impurities and water.

215 kg / h of a mixture containing 93% n-pentane and ~ 7% methyl ethyl ketone are distilled off from the column K-1, condensed and returned to the reactor.

Upon rectification of the bottom residue of the K-1 column in the K-2 column, 41.5 kg / h of methyl ethyl ketone are obtained. As a result of the separation of the bottom residue of the K-2 column in the UR zone, 55.5 kg / h of phenol are obtained.

Claims (14)

1. A method of producing phenol and ketone from an aromatic hydrocarbon hydroperoxide by decomposing it in the presence of a catalyst with strong acidity in one or more reaction zones, followed by separation of the reaction mixture by distillation and possibly partial recirculation to the reaction zone (s) of one or more components of the reaction mixture, characterized in that the decomposition is carried out in the presence of an inert low-boiling solvent containing mainly hydrocarbon (s) with a boiling point of e 70 ° C, preferably below 40 ° C, but not lower than minus 1 ° C, which is partially evaporated directly from the reaction (s) zone (s) and partially distilled from the resulting reaction mixture, in a liquid state is returned to the reaction (s) zone (s) and maintain in it (them) a temperature of from 1 to 70 ° C, preferably from 10 to 45 ° C. 2. The method according to claim 1, characterized in that the quality or composition of the specified solvent is used predominantly saturated (e) hydrocarbon (s), preferably not containing (e) tertiary carbon atoms. 3. The method according to claim 1, characterized in that the quality or composition of the specified inert solvent use n-pentane, and / or isopentane, and / or cyclopentane, and / or n-butane, and / or isobutane. 4. The method according to claim 1, characterized in that when the reaction mixture is separated, the solvent is isolated by distillation and recycled to the reaction (s) zone (s), possibly with part of the formed ketone, the content of which in the recycled stream is limited by a concentration of not more than 50 wt.%, preferably not more than 25 wt.%. 5. The method according to claim 1, characterized in that the alkyl aromatic hydrocarbon peroxide, a recyclable boiling inert solvent and possibly a recycle ketone are fed to the successive points of the reaction zone (s) in two or more streams. 6. The method according to claim 1, characterized in that isopropylbenzene hydroperoxide is decomposed and phenol and acetone are obtained as products. 7. The method according to claim 1, characterized in that the decomposition is subjected to sec-butylbenzene hydroperoxide and phenol and methyl ethyl ketone are obtained as products. 8. The method according to claim 1, characterized in that when using a fine-grained catalyst, its ablation is prevented by the retaining device (s) with aperture size smaller than the minimum particle size of the catalyst. 9. A method of producing phenol and ketone from alkyl aromatic hydrocarbon peroxide by decomposing it in the presence of a strong acid catalyst in one or more reaction zones, followed by separation of the reaction mixture by distillation, characterized in that a low-boiling solvent is used, which, after separation from the reaction mixture, possibly with a portion of the ketone is recycled to the reaction (s) zone (s) and catalyst sulfokationitny in H ⁺ form, stable in liquid media containing large amounts of alkylaromatic hydroperoxides, ketones, hydrocarbons and phenol, at temperatures up to 70 ° C, a fine-grained or coarse-grained form, possibly ranging from 1.5 to 25 mm in the form of mass transfer packing. 10. The method according to claim 9, characterized in that the decomposition of the specified hydroperoxide using the specified sulfocationite catalyst is carried out in the presence of an inert low boiling solvent containing mainly hydrocarbon (s) with a boiling point below 70 ° C, preferably below 40 ° C, but not lower minus 1 ° C, which is partially evaporated from the reaction zone (s) and partially distilled from the resulting reaction mixture, is returned to the reaction zone (s) in a liquid state and the temperature in it (them) is maintained from 1 to 70 ° C, preferred tion of 10 to 45 ° C. 11. The method according to claim 9, characterized in that the alkyl aromatic hydrocarbon hydroperoxide and a recyclable boiling inert solvent, possibly with ketone, are fed to the successive points of the reaction zone (s) in two or more streams. 12. The method according to claim 9, characterized in that isopropylbenzene hydroperoxide is decomposed and phenol and acetone are obtained as products. 13. The method according to claim 9, characterized in that the decomposition is subjected to sec-butylbenzene hydroperoxide and phenol and methyl ethyl ketone are obtained as products. 14. The method according to claim 9, characterized in that when using a fine-grained sulfocationite catalyst, its entrainment is prevented by the retaining device (s) with holes smaller than the minimum particle size of the catalyst.