Method for production of phenol and its derivatives

 

(57) Abstract:

Field of use - getting intermediates of organic synthesis, the monomers for polymerization, antioxidants, agents for the photographic process. The inventive reagent 1 - benzene, BF C6H6or phenol, BF C6H6O or chlorobenzene, BF C6H5Cl, or toluene, BF C7H8. Reagent 2: nitric oxide (1). Product - phenol, BF C6H6O or pyrocatechin, BF C6H6O2or chlorophenol, BF C6H5ClO , or cresol, BF C7H8O reaction Conditions: temperature 325 - S, the presence of pentasil formula XFe2O3SiO2where x = 0,0019 - 0,017, in pure form or in the form of a mixture with a binder, aluminum oxide and silicon in amounts of 20 to 25 wt. % pentasil, volume feed rate of 0.12-0.6-1, the molar ratio of organic compounds to nitric oxide 1 : (1 to 19). 3 table.

The invention relates to organic synthesis, in particular, to a method for production of phenol and its derivatives by one-step catalytic oxidation of the corresponding aromatic compounds

+ N2O __ OH where R = H, OH, Cl, CH3etc.

Oxygen-containing derivatives of the be the valuable products and find wide application in various fields. Most large-scale product of this class is phenol, the majority of which is for the production of phenolic resins, synthesis of adipic acid, caprolactam, phenols, nitro - and chlorophenols, phenolsulfonic etc. Diatomic phenols used in photography, as well as antioxidants and modifiers for the stabilization of plastics. Cresols - to obtain a cresol-formaldehyde resins; chlorophenols for receiving herbicides.

There is a fundamental possibility of obtaining oxygen-containing benzene derivatives by direct oxidation of benzene and its derivatives. However, all attempts to carry out these reactions with acceptable selectivity, which repeatedly have been made for several decades has not led to success. For example, the main products of the oxidation of benzene with molecular oxygen in dependence of the conditions are either maleic anhydride (on selected catalysts), or products of complete oxidation, while phenol is formed in trace quantities. Direct oxidation of benzene derivatives, for example, toluene, the oxidation process primarily affects the functional group with the formation of benzaldehyde and benzoic acid to oradatabase benzene derivatives. In the case of phenol, the most widespread so-called komorny process, which accounts for more than 90% of the world production of phenol [1] . This method is a multistage and its effectiveness largely depends on the possibility of implementing acetone.

The known method for production of phenol by the oxidation of benzene with nitric oxide (1) 550-600aboutWITH:

C6H6+ N2O = C6H5OH + N2.

In this case, as the catalyst use of vanadium oxide, molybdenum and tungsten. To improve the selectivity in the reaction mixture was added water vapor. The best results are achieved on the catalyst 4,3% V2O5/SiO2at 550aboutWith the following reaction mixture: benzene 8.2 percent , nitrogen oxide 16.9% of water, which is 30.7% . The conversion of benzene in these conditions is X = 10,7% , the selectivity S = 71,5% , which corresponds to a yield of phenol Y = 7,7% (Y = XS).

However, when implementing this process, the phenol get enough high yield, the method requires a high temperature, and introducing into the reaction mixture of water, which leads to additional energy consumption for evaporation and complicates the selection of the target product.

For example, a method of obtaining a diatomic phenols, which is similar semolina process for production of phenol and which is characterized by multi-stage and the need to implement resulting in even larger amounts of acetone.

There are a number of ways to get diatomic phenols and chlorophenols and phenolsulfonic, which is based on the alkaline fusion of the corresponding chloro - and sulfadiazine benzene. However, these techniques require the use of aggressive reagents concentrated acids and alkalis and are accompanied by the formation of 1 ton of the product of several tons of alkaline and acidic runoff that causes significant environmental harm.

the treatment of the phenol (2) by direct oxidation of benzene with nitric oxide (1) at a temperature of 325-425aboutIn the presence of catalysts zeolites of type pentasil alumosilicates composition Fe2O3y. Al2O3SiO2where x = 2,810-4- 1,210-3, y = 110-2. The use of these catalysts provides the output of phenol up to 20% with a selectivity of 85-100% . The disadvantage of this method [2] is not a high yield of phenol. To increase the yield of the target product is proposed a method for production of phenol or its derivatives of the General formula where R = H, OH, Cl, or CH3by oxidation of compounds of General formula R where R has the above significance, nitric oxide (1) when 325-425aboutWith the presence of iron pentasil characterized in that to achieve the goal of the invention use pentasil composition:

Fe2O3SiO2where X = 0,0019-0,017, in pure form or in the form of a mixture with a binder, aluminum oxide or silicon taken in the amount of 20-25 wt. % of patasala, and the process is conducted at a volumetric feed rate of the raw material of 0.12-0.5 s-1and the molar ratio of organic compounds to nitric oxide from 1: 1 to 1: 19.

A distinctive feature of the proposed method is the use as catalyst of zeolite type pentasil simpler sinteticheski zeolite composition 8,210-3Fe2O3SiO2with the structure of ZSM-5 at 2 cm3loaded into the reactor, heated to 350aboutAnd with a speed of 1 cm3/s serves the reaction mixture composition: benzene - 5 mol. percent , nitrogen oxide by 20 mol. % , the rest is helium. The composition of the reaction mixture from time to time (1 every fifteen minutes) analyzed by chromatograph. In addition to phenol and carbon dioxide other carbon-containing compounds in the reaction products is not detected. Averaged over 3 hours of work process indicators are: Conversion of benzene, X, To 15.4% , the Selectivity to phenol, S, 99% , the Yield of phenol, Y, 15.3% OF

P R I m e R s 2-11. Phenol get, as in example 1, except that along with the temperature range in volumetric feed rate of the mixture on the catalyst for what at a flow rate of reaction mixture (1 cm3/(C) change catalyst loading 1-8 cm3. Characteristics of the catalyst, the temperature, the contact time of the reaction mixture with the catalyst and the results of the tests are presented in table. 1.

P R I m e R s 12-15. Phenol get as in example 1, except that in the experiments changing the ratio of reactants C/C) from 2: 1 to 1: 19. In table. 2 shows the conditions of the experiments and the results ispgateway influence on the yields of phenol.

P R I m e R s 16-32. Phenol get, as in example 1, except that vary the chemical composition of the catalysts, their structure and the temperature of the reaction. Examples 22-30 are characterized by the fact that the catalyst additionally as a binder contains 20-25 wt. % , Al2O3or SiO2. Characteristics of the catalyst, the reaction temperature and the test results are presented in table. 3.

P R I m e R 33. The zeolite composition 8,210-3Fe2O3SiO2with the structure of ZSM-5 at 2 cm3loaded into the reactor, heated to 350aboutAnd with a speed of 1 cm3/s serves the reaction mixture composition, mol. % : phenol 2; nitric oxide - 20; the rest is helium. The composition of the mixture after the reactor is analyzed by the chromatograph. The main products of the reaction are pyrocatechin and benzoquinone. The process indicators, averaged over 3 hours, make up, % : Conversion of phenol 8.0 Selectivity for pyrocatechin 81.0 Selectivity for benzoquinone 17,0 Total output of products of partial oxidation of 7,8

P R I m e R 34. Pyrocatechin and benzoquinone get as in example 33, except that the catalyst loading was increased to 4 cm3. The process indicators are, % : Conversion of phenol is of the FL partial oxidation of 10.6

P R I m e R 35. The zeolite composition 8,210-3Fe2O3SiO2with the structure type ZSM-5 at 2 cm3loaded into the reactor, heated to 350aboutAnd with a speed of 1 cm3/s serves the reaction mixture composition, mol. % : chlorobenzene 5; nitric oxide 20; the rest is helium. The composition of the mixture after the reactor periodically (1 every 15 minutes) analyzed by chromatograph. The main products of the reaction are chlorophenols. Averaged over three hours indicators of process is % : Conversion of chlorobenzene 17,0 Selectivity for para - chlorophenol 39,0 Selectivity for ortho - chlorophenol 60,0 Total output horfe - NOlow 16,8

P R I m e R 36. The zeolite composition 8,210-3F2O3SiO2with the structure type ZSM-5 at 2 cm3loaded into the reactor, heated to 350aboutAnd with a speed of 1 cm3/s serves the reaction mixture composition, mol. % : toluene 5; nitric oxide 20; the rest is helium. The composition of the mixture after the reactor is analyzed by the chromatograph. The main oxidation products are the Cresols (approximately equal amounts of ortho - para - and meta-isomers) and diphenylether (product of oxidative dimerization of toluene). The process indicators, averaged over three hours, make up, % : Conversion Tanich benzene 10,6

As can be seen from the examples, the proposed method is simple technology, is carried out in one stage does not require the use of aggressive reagents, provides higher yields of the target products up to 35% . In addition, the proposed method allows to obtain a number of oxygen-containing benzene derivatives such as phenol, diatomic phenols, Cresols, chlorophenols, etc., (56) Hedder D. , Nechvatal A. , Guoy A. Industrial. organic. chemistry. M. : Mir, 1977, S. 198-205.

USSR author's certificate N 4673039, class C 07 C 39/06, 1989.

METHOD for production of PHENOL OR ITS DERIVATIVES of General formula

OH

where R is H, OH, Cl, or CH3,

by oxidation of compounds of General formula

< / BR>
where R has the above meaning,

nitrogen oxide (I) at 325 - 425oWith the presence of iron Pancasila, characterized in that, to increase the yield of the target product, use pentasil composition

x Fe2O3SiO2,

where x = 0,0019 - 0,017,

in its pure form or in the form of a mixture with a binder, aluminum oxide, or silicon, taken in an amount of 20 to 25 wt. % Pancasila, and the process is conducted at a volumetric feed rate of the raw material of 0.12 - 0.6 s-1and the molar ratio of organic compounds and the

 

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