RU2313393C1 - Method of preparing heterogeneous phthalocyanine catalyst for oxidation of sulfur-containing compounds - Google Patents

Abstract

FIELD: oxidation catalysts.

SUBSTANCE: invention concerns preparation of heterogeneous phthalocyanine catalyst for use in liquid-phase oxidation of sulfur-containing compounds and provides a method, which involves preparing nonwoven polypropylene carrier by treating it with boiling alkaline solution of sodium peroxycarbonate, 3.2-4.6 g/L, at pH 9-10 followed by treatment cobalt phthalocyanine-disulfonate, 3.2-4.6 g/L, and final treatment, which consists in washing preliminarily treated carrier with sodium hydroxide solution in concentration 0.1-0.5 g/L.

EFFECT: increased catalytic activity up to 92% and simplified catalyst preparation procedure.

2 cl, 1 tbl, 5 ex

Description

Technical field

The invention relates to the chemical industry, namely to the production of phthalocyanine catalysts that are used in the oil refining, petrochemical, gas, chemical, leather and pulp and paper industries for liquid-phase oxidation of sulfur-containing compounds.

State of the art

Various methods are known for the preparation of heterogeneous phthalocyanine catalysts for the oxidation of sulfur-containing compounds.

So, it is known [USSR Author's Certificate No. 1041142, cl. B01J 37/04, 1980] a method for preparing a catalyst. It is carried out by mixing a thermoplastic polymer with a water-insoluble phthalocyanine complex, which is used cobalt phthalocyanine or its tetrachloro and tetrachloromethyl derivative, followed by heating, stirring and molding.

Also known [USSR Author's Certificate No. 978913, 1982] is a method of preparing a catalyst for the oxidation of sulfur-containing compounds. It is carried out by mixing a thermoplastic polymer used in the form of its solution in an organic solvent - benzene or its chlorine derivative at a solution temperature of 80-160 ° C and a concentration of 137-310 g / l, with cobalt phthalocyanine or its tetrachloro and tetrachloromethyl derivatives, holding with stirring for 30-40 minutes and subsequent molding while distilling off the solvent.

However, a common disadvantage of these methods is the insufficiently high activity of the resulting catalysts. So, the oxidation state of mercaptide sulfur in the presence of the catalysts obtained by these methods is 55-86%.

Closest to the invention in terms of essential features is a method of preparing a catalyst according to US patent No. 3396123, CL. 208-244, published. 1971. It consists in the first preparation of the carrier — activated carbon — by melting it into high-pressure polyethylene and grinding. Then, the prepared carrier is treated in an aqueous solution of cobalt sulfo-phthalocyanine, which is used as cobalt disulfophthalocyanine. The carrier thus treated is subjected to final processing by drying.

However, this method has the following disadvantages:

- insufficiently high catalytic activity of the catalyst (not higher than 80%);

- the complexity of the method, due to the need to use special energy-intensive equipment for the operation of pre-fusion of activated carbon into high-pressure polyethylene and grinding operations.

Thus, there is no known method of preparing a heterogeneous phthalocyanine catalyst for the oxidation of sulfur-containing compounds, which allows to increase the catalytic activity of the catalyst and simplify the method of its preparation.

SUMMARY OF THE INVENTION

The inventive task was to find a method for preparing a heterogeneous phthalocyanine catalyst for the oxidation of sulfur-containing compounds, including preparing a carrier, treating it in an aqueous solution of cobalt phthalocyanine sulfo-phthalocyanine and final processing, which would increase the catalytic activity of the target product and simplify the method of its preparation.

The problem is solved by a method for preparing a heterogeneous phthalocyanine catalyst for the oxidation of sulfur-containing compounds, including preparing a carrier, treating it in an aqueous solution of cobalt phthalocyanine sulfo-phthalocyanine and final processing, in which non-woven polypropylene is used as a carrier, the carrier is prepared by treating it in a boiling alkaline solution of sodium peroxycarbonate , as the sulfo derivative of cobalt phthalocyanine, phthalocyanine disulfonic acid is used cobalt at a concentration of 3.2-4.6 g / l, and the final treatment is carried out by washing the treated carrier in a solution of sodium hydroxide at a concentration of 0.1-0.5 g / l.

The essential distinguishing features of the invention is that non-woven polypropylene is used as a carrier, the carrier is prepared by treating it in a boiling alkaline solution of sodium peroxycarbonate, and cobalt phthalocyanine disulfonic acid at a concentration of 3.2-4.6 g / l is used as a co-phthalocyanine sulfon derivative and the final processing is carried out by washing the treated carrier in a solution of sodium hydroxide at a concentration of 0.1-0.5 g / L.

The sodium peroxycarbonate solution is used at a pH of 9-10 and a concentration of 33-35 g / l.

The invention allows:

- increase the catalytic activity of the target product to 90-92%;

to simplify the method of preparation of the catalyst.

Information confirming the reproducibility of the invention

To implement the method, you can use the following reagents:

Cobalt Phthalocyaninate Disulfonic Acid TU 6-09-32-41-84

Sodium hydroxide GOST 130109

Sodium peroxycarbonate TU 2144-284-05763441-99

As a carrier, you can use non-woven polypropylene PGDS-B with a density of 500 g / m ² .

The method is implemented as follows.

Non-woven polypropylene material with a size of 10 × 10 cm is placed in 300 ml of an alkaline solution of sodium peroxycarbonate with a concentration of 33-35 g / l at a pH of 9-10, heated to boiling and incubated for 2 hours.

The material is removed, washed with distilled water and placed in an aqueous solution of cobalt phthalocyanine disulfonic acid at a concentration of 3.2-4.6 g / L. The material is kept in this solution for about 12 hours, then removed and washed in a solution of sodium hydroxide at a concentration of 0.1-0.5 g / l to remove excess cobalt phthalocyaninate disulfonic acid.

Catalytic activity was evaluated by the degree of oxidation of mercaptide sulfur in a solution of sodium butyl mercaptide, containing, wt.%: Sodium hydroxide - 15; sodium butyl mercaptide - 1.8; water is the rest. The oxidation is carried out in a batch glass reactor with a diameter of 30 mm and a height of 350 mm, equipped with a reflux condenser and outlets for oxygen supply and sampling. The tests were carried out at room temperature, atmospheric pressure, oxygen supply rate of 1800 h ^-1 for 1 h. The mercaptide sulfur content in the oxidized solution was determined potentiometrically according to GOST 22985-78.

The catalytic activity of the samples obtained under various conditions of the claimed method in the oxidation of mercaptide sulfur in a solution of sodium butyl mercaptide is shown in the table.

Table The catalytic activity of samples prepared under various conditions No. Concentration and pH of sodium peroxycarbonate solution, g / l The concentration of an aqueous solution of cobalt phthalocyaninate disulfonic acid, g / l The concentration of an aqueous solution of sodium hydroxide, g / l The degree of oxidation of mercaptide sulfur in a solution of sodium butyl mercaptide,% one 33 g / l pH = 9 3.2 0.5 90.23 2 33 g / l pH = 10 3.9 0.4 90.62 3 34 g / l pH = 9 4.2 0.3 91.32 four 34 g / l pH = 10 4.4 0.2 91.76 5 35 g / l pH = 10 4.6 0.1 92

Claims (2)

1. A method of preparing a heterogeneous phthalocyanine catalyst for the oxidation of sulfur-containing compounds, comprising preparing a carrier, treating it in an aqueous solution of cobalt phthalocyanine sulfo-phthalocyanine and final processing, characterized in that non-woven polypropylene is used as a carrier, the carrier is prepared by treating it in a boiling alkaline peroxycarbonate solution sodium, cobalt phthalocyanine disulfonic acid is used as a cobalt phthalocyanine sulfonic derivative concentrations of 3.2-4.6 g / l, and the final treatment is carried out by washing the treated carrier in a solution of sodium hydroxide at a concentration of 0.1-0.5 g / l. 2. The method according to claim 1, characterized in that the alkaline solution of sodium peroxycarbonate has a pH of 9-10 and a concentration of 33-35 g / L.