The way to get gidroperekisi ethylbenzene

 

(57) Abstract:

The invention relates to the petrochemical industry and can be used in the process of joint production of propylene oxide and styrene. The purpose of the invention: improved conversion of ethylbenzene and selectivity education gidroperekisi ethylbenzene and reducing the consumption of catalyst. This goal is achieved by way of liquid-phase oxidation of ethylbenzene to gidroperekisi ethyl benzene at elevated temperature with oxygen in the presence of a catalyst and catalytic additives. As a catalyst and initiator additives used and the condensed part of the flow of exhaust air from the stage of oxidation of ethyl benzene, treated with sodium hydroxide, and/or use flow generated during the washing and/or neutralization of the reaction products from acidic impurities. Supplement take in quantity 0,00003-of 0.003 wt.% in the calculation of the sodium from the reaction mass. 1 C.p. f-crystals.

The invention relates to the petrochemical industry and can be used in the process of joint production of propylene oxide and styrene.

It is known that the gidroperekisi alkylaromatic hydrocarbons are suitable oxidation which provide for the selection of the target product known techniques [1].

A method of obtaining the gidroperekisi ethyl benzene in the liquid phase [2], in which the liquid reaction product derived from the reaction zone, separating non-condensable inert gases which are returned to the reaction zone to control the reaction temperature. The target product is removed from the liquid phase of the last reaction zone. Unreacted ethylbenzene recycle.

The closest way to obtain organic hydroperoxides is the way of the oxidation of alkylaromatic hydrocarbons by molecular oxygen in the liquid phase in the presence of a catalyst. The oxidation reaction is also thermally initiate unstable compounds, such as peroxides or hydroperoxides [3].

To increase the conversion of ethylbenzene and selectivity education gidroperekisi ethylbenzene and reducing the consumption of catalyst is proposed a method of liquid-phase oxidation of ethylbenzene to gidroperekisi ethyl benzene at elevated temperature with oxygen in the presence of a catalyst and catalytic additives. As a catalyst and initiator additives used and the condensed part of the flow of exhaust air from the stage of oxidation of ethylbenzene, obrabotan from acidic impurities. Supplement take in quantity 0,00003-of 0.003 wt.% in the calculation of the sodium from the reaction mass.

From the literature it is not known on the application in the process of obtaining gidroperekisi ethylbenzene as a catalyst and initiator supplements these threads, which allows to make a conclusion about conformity of the present invention, the criteria of "novelty" and "inventive step". The possibility of using the proposed technical solutions in the industrial method of obtaining gidroperekisi ethylbenzene shows the invention according to the criterion of "industrial applicability".

The claimed invention the following examples.

Example 1

The oxidation of ethylbenzene with oxygen is carried out on laboratory nepreryvnolitoy poster installation, made of metal at a temperature of 155oC, a pressure of 4.5 ATM, space velocity air 150 h-1and duration of experience 1 h using a catalyst - initiator additives. The catalyst-initiator additive was prepared as follows: the exhaust air downstream of the reactor for the oxidation of ethylbenzene is passed sequentially through the chillers - condensers, air-cooled, water, ammiano enzimaticescoe analysis, sent to the oxidation reactor for use as a catalyst and initiator of oxidation of ethylbenzene. According to analysis of the composition of this stream contains a mixture of compounds such as NaOH(2 wt%), Na2CO3,(2 wt%), sodium benzoate (1 wt. %), nagarajuna acid (of 0.0005 wt.%), peracetic acid (0,0005 wt. %), hydrogen peroxide (0.5%), Gidropress ethylbenzene (0.2 wt. %), formic acid (0,001% by weight), acetic acid (0,001% by weight), benzoic acid is 0.05 wt.%), the acetophenone and methylphenylcarbinol 0.05 wt.% each. The content of the catalyst - initiator additives in the reaction mass 0,00005 wt.% in the calculation of the sodium.

After the experience of the contents of the gidroperekisi ethylbenzene (GPEB) in the reaction mass oxidation, determined by the method iodometric titration of 14.7 wt.%. The selectivity of the formation of hydroperoxide 91 mol.%.

Example 2

The oxidation of ethylbenzene with oxygen is carried out on nepreryvnolitoy laboratory bench installation made of metal at a temperature, pressure, air flow and duration, as in example 1. The content of the catalyst-initiator additives in the reaction mass oxidation of 0.003 wt.% in the calculation of the sodium. The thread ispart to two-stage washing with water to extract the composition of the oxidized product ion of sodium and organic acids. While getting the aqueous phase containing hydrogen peroxide, Gidropress ethyl benzene, formic and benzoic acid, ethylbenzene, acetophenone and methylphenylcarbinol and H2CO3. In the resulting aqueous phase is injected aqueous NaOH solution to neutralize acids and is sent to the oxidation reactor for use as initiating additive obtain hydroperoxide.

The total content of sodium ion in the obtained thus initiating additive 2,11 wt. %, of which 1 wt.% accounted for NaOH; 0.7 wt.% - NaHCO3; 0.1 wt.% - Na2CO3; 0.1 wt.% - sodium benzoate; 0.01 wt.% - sodium formate and 0.2 wt.% - sodium salt of gidroperekisi ethylbenzene. Initiating additive also contains 0.01 wt.% hydrogen peroxide, 0.1 wt.% the gidroperekisi ethylbenzene, 0.01 wt.% - acetophenone, 0.01 wt.% - methylphenylcarbinol, 0.2 wt.% benzoic acid and 0.001 wt.% - ethylbenzene.

The rate of air flow of 110 l/h duration of the experiment 1 h

At the end of the experience contents GPIB in the reaction mass oxidation, determined by the method iodometric titration 14,85 wt.%. The selectivity of the formation of the hydroperoxide of 91.3 mol.%.

Example 3

The oxidation of ethylbenzene with oxygen is carried out on n the country air and duration, as in example 1. The content of the catalyst-initiator additives in the reaction mass oxidation 0,00005 wt.% in the calculation of the sodium. The catalyst and the initiator additive was prepared as follows.

Oxidized ethylbenzene is directed to a two-stage washing with water to extract the composition of the oxidized spans sodium ion and organic acids. While getting the aqueous phase containing hydrogen peroxide, Gidropress ethyl benzene, formic and benzoic acid, ethylbenzene, acetophenone and methylphenylcarbinol and H2CO3.

The total content of sodium ion in the thus obtained catalyst-initiator of 0.003 wt.%, in the form of sodium benzoate. The catalyst also contains 1 wt. % hydrogen peroxide, 0.5 wt.% the gidroperekisi ethylbenzene, 0.01 wt.% - acetophenone, 0.01 wt.% - methylphenylcarbinol, 0.2 wt.%. benzoic acid, 0.01 wt.% formic acid, 0,001 H2CO3and 0.001 wt.% - ethylbenzene.

The rate of air flow of 110 l/h duration of the experiment 1 h

At the end of the experience contents GPIB in the reaction mass oxidation, determined by the method iodometric titration of 14.9 wt.%. The selectivity of the formation of the hydroperoxide to 91.8 mol.%.

Example 4

Oxidation atilano of metal at a temperature pressure, air flow and duration, as in example 1. The content of the catalyst-initiator additives in the reaction mass oxidation 0,0003 wt.%. The catalyst and the initiator additive was prepared as follows.

Exhaust air downstream of the oxidation reactor are sent to wash in the scrubber, where it is subjected to the removal of acid impurities by treatment 2 wt.% aqueous solution of NaOH. The resulting output of the scrubber aqueous alkaline solution containing, according to the result of the analysis methods potentiometric titration and chromatography of 1.75 wt.% Na2CO3and 2 wt.% sodium benzoate, and 0.02 wt.% of acetophenone and 0.03 wt.% methylphenylcarbinol, is sent to the oxidation reactor for use as a catalyst - initiator additives oxidation of ethylbenzene.

The rate of air flow of 110 l/h

Dlitelnogo experience 1 h

At the end of the experience contents GPIB in the reaction mass oxidation, determined by the method iodometric titration of 14.5 wt.% The selectivity of the formation of the hydroperoxide to 91.1 mol.%.

Example 5

The oxidation of ethylbenzene with oxygen is carried out on nepreryvnolitoy laboratory bench setting and the ora-initiating additive in the reaction mass oxidation 0,0003 wt.% in the calculation of the sodium. The catalyst and the initiator additive was prepared as follows.

Exhaust air downstream of the oxidation reactor are sent to wash in the scrubber, where it is subjected to the removal of acid impurities by treatment 2 wt.% aqueous solution of Na2CO3. The resulting output of the scrubber aqueous alkaline solution containing, according to the result of analysis methods potentiometric titration and chromatography, 1.24 wt.% Na2CO3and 2.37 wt.% sodium benzoate, and 0.03 wt.% of acetophenone and 0.03 wt.% methylphenylcarbinol, is sent to the oxidation reactor for use as an initiator of oxidation of ethylbenzene.

The rate of air flow of 110 l/h duration of the experiment for 1 hour.

At the end of the experience contents GPIB in the reaction mass oxidation, determined by the method iodometric titration of 14.5 wt.%. The selectivity of the formation of the hydroperoxide to 91.1 mol.%.

Example 6

The oxidation of ethylbenzene with oxygen is carried out on nepreryvnolitoy laboratory bench installation, made of metal at a temperature, pressure, air flow and duration, as in example 1. The content of the catalyst-initiator additives in the reaction mass oxidation 0,n ethylbenzene sent to representatves laboratory distillation column, which when reduced pressure is separated into an upper product return ethylbenzene. The resulting ethylbenzene enters the diaphragm mixer, which is washed from acidic impurities (organic acids) 5 wt.% NaOH solution. While getting the aqueous phase containing 0.5 wt.% hydrogen peroxide, 0.2 wt.% Gidropress ethylbenzene, 0.01 wt.% ethylbenzene, of 0.95 wt.% NaOH, 0.4 wt.% Na2CO3and 7.4 wt.% sodium benzoate. The resulting aqueous alkaline solution is partially sent to the oxidation reactor for use as a catalyst and initiator receiving hydroperoxide.

The rate of air flow of 110 l/h duration of the experiment for 1 hour.

At the end of the experience contents GPIB in the reaction mass oxidation, determined by the method iodometric titration 14.64 percent wt.%. The selectivity of the formation of hydroperoxide 91,46 mol.%.

Example 7

The oxidation of ethylbenzene with oxygen is carried out in the conditions of example 1. The content of the catalyst-initiator additives in the reaction mass oxidation of 0.003 wt. % based on the sodium. The catalyst and the initiator additive was prepared as follows.

The mixture of condensate flow obtained analogously to example 1,is sent to the oxidation reactor for use as initiating supplements.

The rate of air flow of 110 l/h duration of the experiment 1 h

At the end of the experience contents GPIB in the reaction mass oxidation, determined by the method iodometric titration 14,54 wt.%. The selectivity of the formation of hydroperoxide 91,2 mol.%.

As seen from the above examples, using as a catalyst-initiator additive flows generated during the washing and/or neutralization of the reaction products from acidic impurities and/or condensed part of the flow of exhaust air from the stage of oxidation of ethylbenzene can improve the selectivity of the formation of gidroperekisi ethylbenzene and reduce the consumption of alkali used as the catalyst.

1. The way to get gidroperekisi ethylbenzene liquid-phase catalytic oxidation of ethylbenzene with oxygen at elevated temperature in the presence of a catalyst and initiator additives, characterized in that as the catalyst and the initiator of the additive used and the condensed part of the flow of exhaust air from the stage of oxidation of ethyl benzene, treated with sodium hydroxide, and/or flow generated during the washing and/or neutralization of the reaction products from acidic impurities.

ion mass.

 

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