The catalyst for the production of phenol and acetone

 

(57) Abstract:

Use of invention: relates to the petrochemical industry, in particular to catalysts for the production of phenol and acetone. The essence of the invention: a catalyst for production of phenol and acetone by decomposition of gidroperekisi cumene apply hydrated niobium pentoxide Nb2O5n H2O and/or phosphate niobium Nb2O5m P2O5n H2O, where m is 0.5 to 5.0. table 1.

The invention relates to the field of organic chemistry and petrochemicals, and in particular to catalysts for the production of phenol and acetone.

Phenol is widely used in the production of phenolaldehyde resins, nitro - and chlorophenols and other products. Acetone is used as solvent paints and varnishes. Worldwide, over 90% of the phenol is produced by decomposition of cumene hydroperoxide. Process for production of phenol and acetone by decomposition of hydroxyperoxide cumene requires the presence of acid catalysts [1,2,3] Proposed perchloric acid on the data [2] cultural and solid metallasiloxanes catalysts [3] and others. However, in industry as a catalyst is used only sulfuric acid [1] Its shortcomings the resinification of the reaction products,about, for its separation from the reaction mass necessary stage neutralization with alkali, which complicates the technology increases the amount of waste and wastewater, leads to the consumption of alkali. In addition, water in the amount of 2% of a catalyst poison.

These disadvantages can be avoided if instead of sulfuric acid as an acid catalyst to use heterogeneous catalysts hydrated niobium pentoxide, niobium NbO5nH2O calcined at 100-300aboutWith and/or niobium phosphate of General formula Nb2O5mP2O5nH2O (m 0,5-5), calcined at 100-150aboutC. the Amount of water n in these catalysts is not limited, it is not constant and depends on the temperature of calcination. Concentration of the water activity of the catalysts depends a little, but to completely remove the water unacceptable, because they lose the properties of the catalyst. Hydrated niobium pentoxide, niobium loses water at temperatures above 300aboutWith, and niobium phosphate at temperatures above 500aboutC. These catalysts have high activity and selectivity, not osmolar reaction products have a long service life, not poison water can easily be separated from the reaction mass by filtration, decantation, flaking. This is IBIA Nb2O5nH2O was known as the hydration catalyst and the esterification of [4] and niobium phosphate as catalyst for dehydration [5] However, neither hydrated niobium pentoxide, niobium Nb2O2nH2O, no phosphate niobium has never been used for production of phenol and acetone by decomposition of cumene hydroperoxide. In this regard, the invention consists in the application of hydrated niobium pentoxide, niobium or niobium phosphate as a catalyst for production of phenol and acetone by decomposition of cumene hydroperoxide. The aim of the invention is to increase the service life of the catalyst, its activity and selectivity even in the presence of water, environmental improvement and simplification of process.

The method of obtaining catalysts of hydrated niobium pentoxide, niobium and niobium phosphate is simple and is carried out by known techniques [4,6] the test samples of Nb2O2nH2O progulivali at 100-300aboutWith, and phosphate niobium in the range of 100-500aboutC for 2 h

The decomposition of cumene hydroperoxide to phenol and acetone as follows. In the reactor of the standard type with a stirrer (three-neck flask, autoclave, tubular reactor and the like) Pamesa stirring until the required temperature, then enter the hydroperoxide in the amount of 6% by weight of solvent. Mixing lead to complete decomposition of the cumene hydroperoxide. After the reaction, the stirring of the reaction mixture to stop the reaction mass is rapidly cooled, the catalyst is separated by known methods, for example by filtration, decantation, centrifugation, and then use it again in the decomposition process, and the reaction mass analyzed. The completeness of the decomposition of cumene hydroperoxide exercise iodometrically, the selectivity for production of phenol and acetone by GC. As raw materials use of purified, for example, 100% cumene hydroperoxide. Application of Nb2O5nH2O and/or niobium phosphate as catalyst for the production of phenol and acetone are illustrated by the following examples.

P R I m e R 1. In thermostatic three-neck flask with stirrer, thermometer and reflux condenser is placed 22,0 g of acetone as a solvent, 0.1 g of hydrated niobium pentoxide, niobium, heated at 100aboutWith, and heated to 50aboutWith under stirring. Then give 1.4 g of cumene hydroperoxide. Stirring is carried out for 1 minute Then stop stirring, the reactor was rapidly used again for the decomposition of cumene hydroperoxide, and the reaction mass analyzed by GEH. Conversion of the hydroperoxide was 100% yield of phenol and acetone turned on the hydroperoxide of about 100% as a by-product was detected cumylphenol in the form of traces. When the catalyst test for 5 cycles in the reaction for production of phenol and acetone was not observed reduction in activity and selectivity.

P R I m m e R 2. Obtain phenol and acetone lead analogously to example 1, except that the solvent contains 3.3 grams of water 15% For a reaction time of 1 min, the conversion of cumene hydroperoxide was 100% selectivity of about 100% in the form of footprints was discovered by-product of cumylphenol. The catalyst retained its activity and selectivity for the 5 cycles tests, despite the presence in the reaction mass of water in the amount of 15% As it is known, boric acid poisoned water at its contents up to 2% niobium pentoxide, niobium allows the process of production of phenol in the presence of water, which is an important factor, since it eliminates the need for drying the source of cumene hydroperoxide. When using hydrated niobium pentoxide, niobium water content in the catalyst, and the reaction mass is not limited.

P R I m e R 3. the Biya, calcined at 150aboutC, and the reaction is carried out at 65aboutC for 1.5 min. In the solvent used equimolar mixture of phenol and acetone. Conversion of cumene hydroperoxide was 100% selectivity for phenol 99.9% of as a by-product was detected cumylphenol. The catalyst was tested for 5 cycles, its activity and selectivity did not fall.

P R I m e R 4. Obtain phenol and acetone carried out analogously to example 1, only take 0.3 g of hydrated niobium pentoxide, niobium, calcined at 300aboutC, and the reaction is carried out at 75aboutC for 3 minutes In the solvent used equimolar mixture of phenol and acetone. Conversion of the hydroperoxide was 100% selectivity of the formation of phenol 99,2, acetone 99.6% of the Catalyst was tested for 5 cycles, while it did not reduce its activity and selectivity.

P R I m e R 5. Obtain phenol and acetone carried out analogously to example 1, only take 0.1 g of niobium phosphate composition of Nb2O2mP2O5nH2O, heated at 100aboutWith, and reaction carried out for 1 min at 50aboutC. Conversion of cumene hydroperoxide was 100% selectivity of about 100% in cachestate and activity did not change.

P R I m e R 6. Obtain phenol and acetone carried out analogously to example 5, only the solvent contains 3,3 water 15% For a reaction time of 1 min, the conversion of cumene hydroperoxide was 100% selectivity of about 100% as a by-product obtained cumylphenol in the form of traces. The catalyst was tested for 5 cycles, its activity and selectivity has not changed, despite the content of 15% water in the reaction mass. As you know, sulfuric acid reduces its activity even in the presence of 0.1% water, and water availability, 2% catalyst H2SO4you catch fully. Consequently, in the manufacturing process of the reaction mass should not contain moisture, and it causes additional energy consumption for drying the source of cumene hydroperoxide. When using phosphate-niobium content n water in the catalyst, and the reaction mass is not limited, and the need for drying of the raw materials disappears.

P R I m e R 7. Obtain phenol and acetone carried out analogously to example 5, only take 0.3 g of niobium phosphate composition of Nb2O53P2O5nH2O calcined at 150aboutC, and the reaction is carried out at 60aboutC for 2 minutes In the solvent used, equimolar,3% acetone 99.6% of the Side product cumylphenol. The catalyst was tested for 5 cycles, its selectivity is not changed.

P R I m e R 8. Obtain phenol and acetone carried out analogously to example 7, only take 0.3 g of niobium phosphate composition of Nb2O55P2O5nH2O calcined at 500aboutC, and the reaction is carried out at 80aboutC for 3 minutes Conversion of cumene hydroperoxide was 100% selectivity of the formation of phenol to 98.6% acetone 99% by-product of cumylphenol. The catalyst was tested for 5 cycles, its activity and selectivity did not change.

P R I m e R 9. Obtain phenol and acetone carried out analogously to example 1, only take 0.05 g Nb2O5nH2O, heated at 100aboutWith and 0.05 g of Nb2O50,5 P2O5nH2O, heated at 100aboutC, the reaction is carried out at 50aboutC for 1 min, the Conversion of cumene hydroperoxide 100% selectivity for production of phenol and acetone to about 100% as a by-product was detected cumylphenol in the form of traces. The catalyst was tested for 5 cycles, its activity and selectivity has not changed. Examples of the application of hydrated niobium pentoxide, niobium and/or niobium phosphate are summarized in table.

Application gidratirovanaO5nH2O,

where m 0,5 5,0,

as a catalyst for the production of phenol and acetone.

 

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