SU1745333A1 - Method of producing manganese containing catalyst for oxidation of paraffin - Google Patents

Abstract

Use: production of synthetic fatty acids. SUMMARY OF THE INVENTION: Sludge water is neutralized with soda ash at 95-110 ° C to pH 8.5-9.2. The resulting reaction mixture is treated with oxidate at 95–200 ° C in a mass ratio of oxidate: reaction mixture (0.3-0.5): 1. Stir for 20 minutes and settle for 5 minutes. Separate the upper fat layer. 2 tab.

Description

The invention relates to the production of synthetic fatty acids (FFA), in particular to a method for processing slurry water and the production of a regenerated oxidation catalyst;

Slurry water contains predominantly carboxylic acids mono Ct-Swee dicarboxylic. manganese and sodium compounds. Its discharge to biological wastewater treatment plants is limited due to manganese compounds. Therefore necessary. purification of sludge water both from an environmental point of view and economically, due to a shortage of manganese. -v

A known method for the preparation of a manganese-containing catalyst for the oxidation of paraffinic hydrocarbons, according to which the sludge waters of the production of synthetic fatty acids are treated with sodium carbonate, the resulting manganese carbonate is separated, which is further treated at 40-80 ° C and stirred with neutralized oxidate until a homogenized suspension is formed.

The disadvantage of this method is the increased consumption of soda ash, associated with obtaining neutralized oxidate, low activity of manganese catalyst, so at 40-80 ° C manganese carbonate is converted into manganese soaps by only 40-50%, and manganese carbonate itself is not an oxidation catalyst and, moreover, not dissolved in paraffin, precipitates directly in the oxidation column.

The closest in technical essence and the achieved result is the method of obtaining a homogeneous catalyst by treating slurry waters of the production of FFA with sodium or potassium carbonate. The resulting manganese carbonate is separated, treated with a mixture of carboxylic acids or oxidized paraffin at 100–200 ° C, and sodium or potassium salts of fatty acids are added, for example, from

te

4J

4 SP

with

CJ

with

whether formed during the treatment of sludge water with sodium carbonate or potassium. Moreover, as a mixture of carboxylic acids using the fraction of Cs-Sat fatty acids.

The disadvantages of this method are the technological difficulties in separating the manganese carbonate slurry caused by the constant compaction of the latter until the formation of a non-flowing sludge, the increased consumption of soda ash to neutralize the sludge water, which is 150% of the theoretically necessary.

The purpose of the invention is to simplify the process and reduce the consumption of soda ash.

This goal is achieved by the method of preparing a manganese-containing catalyst for oxidizing paraffin, which includes treating sludge water produced by SFA with soda ash at 95–110 ° C to obtain a reaction mixture containing manganese carbonate and low molecular weight carboxylic acid sodium salts with an oxidate in a mass ratio oxidate: a mixture of 0.3-0.5: 1 and the fat layer containing the catalyst is separated.

Carrying out neutralization at 95–110 ° C reduces soda consumption, and at a temperature below 95 ° C, the consumption of soda increases, and a rise in temperature above 110 ° C does not reduce the consumption of soda.

The subsequent treatment of the mixture containing manganese and sodium carbonates, salts of carboxylic acids Cs and higher, sodium bicarbonate and other impurities with an oxidate in the ratio of 1: 0.3-0.5 ensures its separation into 2 layers - fat and water. At the same time, under the influence of the fatty acid sodium soaps formed, manganese carbonate, as such, and in the form of manganese soaps, and Cs salts of carboxylic acids, is transferred to the fatty layer. It is this ratio that provides the most complete extraction of manganese and salts of carboxylic acids Cs and higher from the vodka phase and a clear separation of the layers, which provides simplification in their separation. At a ratio of 0.3: 1, a water-fat emulsion is formed, which is not separated, and at a ratio above 0.5-1, the mass fraction of manganese in the fat layer decreases and the oxidate is unreasonably consumed. The fatty layer after separation is used as a catalyst for the oxidation of paraffinic hydrocarbons.

The method is carried out as follows.

Sludge water is neutralized with soda ash at 95–110 ° C to pH 8.59, 2 to form a reaction mixture containing manganese and sodium carbonates and salts of carboxylic acids. Then the reaction mixture is treated with oxidate at 95-200 ° C and stirred for 20 minutes and

defend at least 5 minutes An upper fat layer containing 1.5-2.5% manganese and 1-2% sodium is separated. It is used as a catalyst as the main or after additional processing at 120 ° C in

for 30-60 minutes The bottom layer - clarified slurry water is used to prepare a solution of soda ash in the production of FFA or sent to consumers for the preparation of, for example, a concrete solution.

PRI me R 1. 100 g of slurry water with an acid number of 89 mg KOH / g and a mass fraction of manganese 1% neutralized at 95 ° C with a 24.9% solution of soda ash in

the amount of 51.96 g, i.e. more calculated

by 25%, stirred for 20 minutes,

50 grams of acidate acid is added

. 75 mg KOH / g, mixed with the same

temperature for 5 min. Then

5 minutes and separated. 55.5 g of the upper fat layer (mass fraction of manganese in it 1.76%, sodium 1.2%, acid number 20.7 mg KOH / r) and lower 141.2 g (mass fraction of manganese 0.014%, sodium are obtained

3.5%, acid number 4.2 mg KOH / g). The recovery rate of manganese is 98%. The upper layer containing the catalyst is treated at 120 ° C for 60 minutes. The resulting catalyst is used to oxidize paraffin.

Example 2.100 g of sludge water of the same composition as in Example 1 is neutralized at 100 ° C with 24.9% soda ash in the amount of 51.96 g, i.e. by 20%

more calculated, stirred for 20 minutes, 40 g of oxidate are added, stirred at the same temperature for 5 minutes. After which they are defended and separated. Get 44,4 g of upper fat

- a layer (mass fraction of manganese 2.18%, sodium 1.8%, acid number 18 mg KOH / r) and lower layer 141 g (mass fraction manganese 0.0212%, sodium 2.9%, acid number 4.0 mg KOH / g).

The degree of regeneration of manganese 97%.

Example (known). Sludge water with indicators, as in Example 1, in an amount of 100 g is neutralized at 85 ° C with a 24.9% solution of soda ash in an amount of 62.35 g (the excess is 50%). The reaction mixture is allowed to settle for 3 hours, while 9.1 g of a manganese carbonate suspension with a manganese content of 10.8% and sludge water with an acid content of C $ and above 18 mg KOH / g are isolated.

To the manganese carbonate, 34 g of the oxidate and 20 g of the solution of sodium salts of low molecular weight acids are added and immediately fed into an oxidation column, where 1 kg of a mixture of paraffin and unwashed is preloaded. The temperature is raised to 120 ° C. The mixture is acidified to an acid number of 70 at 120 ° C for 20 hours. The carbonyl oxidate number is 6.0 mg KOH / g.

Examples of the method are presented in table 1.

Example 8 is made under prototype conditions.

It can be seen from the above data that at a neutralizing temperature of slurry water of 95-110 ° C and processing it with oxidate at a ratio of 1: 0.3-0.5, the consumption of alkali is reduced to 15-25% and the content of organic acids Cs and above decreases. in slurry water to 0.2-4.2 mg KOH / g. When the neutralization temperature decreases to 85 ° C, the consumption of alkali sharply increases, and an increase above 110 ° C does not lead to an increase in the positive effect. Outside the specified ratios of slurry water and oxidate, it follows that when they decrease, a stable emulsion is formed and the separation does not occur, and as this ratio increases, the concentration of manganese in the fat layer decreases and the oxide unnecessarily consumes.

The proposed method is simplified by eliminating the separation of manganese carbonate, since it is this stage that causes technological difficulties in that the manganese carbonate suspension is constantly compacted.

up to non-flowing sediment. In addition, the method allows to reduce the consumption of soda and neutralize the sludge water at a 15-25% excess, while in the prototype this excess is 50%. The method also makes it possible to extract Cs fatty acids and higher from the aqueous layer, thereby reducing their content in sludge water to 0.2-4 g mg / KOH / g.

Obtained in examples 1-3, the catalyst is tested in the oxidation of paraffin.

Characteristics of the obtained oxidate are presented in table 2. Thus, the proposed method makes it possible to simplify the technology for producing a manganese catalyst from slime wastewater produced by FFA, reduce the consumption of alkali for neutralization and sufficiently completely extract Svyvyshe acids from the slurry water. The catalyst obtained by the proposed method is not inferior in activity known, as well as traditionally used in the oxidation of paraffin manganese dioxide.

Claims (1)

Invention Formula A method of preparing a manganese-containing catalyst for oxidizing paraffin, including treating sludge water to produce synthetic fatty acids with soda ash to obtain a reaction mixture containing manganese carbonate and low molecular weight carboxylic acid sodium salts, with an oxidate treatment that is different in order to simplify the process and reduce soda ash consumption, treatment of sludge water is carried out at 95-110 ° C, the reaction mixture is treated with oxidate in a mass ratio of oxidate: reaction The mixture is 0.3-0.5: 1 and the fat layer containing the catalyst is separated. 55.5 1.76 th, 4 2.18 32.5 2.92 Not stratified 43, Q 2.25 Not stratified 65.1 1.49 00 1745333 10 Table2