SU1693000A1 - Method for obtaining tetrasulfoacid of cobalt phtalocyanine - Google Patents

Abstract

The invention relates to cobalt-organic substances and, in particular, to the preparation of tetrasulfonic acid phthalocyanine cobalt, a catalyst for the oxidation of sulfur-containing substances in electrocatalytic processes. The purpose of the invention is to increase the yield of the target product, simplifying the process of improving its environmental friendliness. The process is carried out by fusing cobalt phthalocyanine with sulfamic acid at a molar ratio of 1: (4-4.5) and a temperature of 220-230 ° C. These conditions increase the content of the basic substance in the product from 50 to 98% with an increase in the yield of the target product from 56 to 98% and carrying out the process in one stage without the formation of wastewater. about fe

Description

The invention relates to an improved method for producing cobalt phthalocyanine tetrasulfonic acid of the formula

which is a catalyst for the oxidation of sulfur-containing compounds in electrocatalytic processes, and can be used in the petrochemical industry.

The aim of the invention is to increase yield, simplify the process and increase its environmental friendliness.

Example 1. In a horizontal reactor with a screw mixer load

5.76 g (0.01 mol) of cobalt phthalocyanine and 2.9 g (0.03 mol) of sulfamic acid (1: 3 molar ratio, respectively). The temperature of the reaction mixture was increased to 230 ° C and maintained at this temperature for 60 minutes. After cooling, the plan is unloaded. 8.51 g of cobalt phthalocyanine trisulfonic acid are obtained. Yield 96% of theoretical. There is no sewage.

Found,%: C42.68; .H 1.7; N, 12.4; S 14.5. C32H16N8S3O12C0 (mol. M. 815).

Calculated,%: C42.85; H1.78; N, 12.5; S 14.28. The composition of the technical product,%:

1693000A1

Tetrasulfonic acid 1.4

Trisulfonic acid96

Disulfonic acid 0.4

Monosulfonic acid 1.1

Phthalocyanine Co1.1

Example 2. In a horizontal reactor with a screw mixer load

5.76 g (0.01 mol) of cobalt phthalocyanine and 3.88 g (0.04 mol) of sulfamic acid (1: 4 molar ratio, respectively). The temperature is increased to 230 ° C and maintained at this temperature for 60 minutes. After cooling, the melt is discharged. Received 8.85 g of tetrasulfoki'slot phthalocyanine: cobalt. Yield 98% of theoretical. There is no sewage.

Found,%: C43; H 1.8; N, 12.5; S 14.26. C32H16N8S4O12CO (mol. M. 896).

Calculated,%: C42.85; H 1.78; N, 12.5; S14.28. The composition of the technical product,%:

Tetrasulfonic acid98

Trisulfonic acid 0.8

Disulfonic acid 0.5

Monosulfonic acid 0.2

Phthalocyanine Co0.5

Example 3. In a horizontal reactor with a screw mixer load

5.76 g (0.01 mol) of cobalt phthalocyanine and 4.37 g (0.045 mol) of sulfamic acid (in a molar ratio of 1: 4.5).

The temperature was raised to 230 ° C and held at this temperature for 60 minutes. After cooling, the melt is discharged. Received 8.85 g of cobalt phthalocyanine tetrasulfonic acid. Yield 98% of theoretical, j No wastewater.

i Found,%: C 42.7; H 1.76; N, 12.45; S 14.4. C32H16N8S2O12CO (mol. M. 736).

Calculated,%: C42.85; H 1.78; N, 12.5; S 14.25.

The composition of the technical product,%:

Tetrasulfonic acid98.5

Trisulfonic acid 0.8

Disulfonic acid 0.3

Monosulfonic acid0.1

Cobalt Phthalocyanine 0.3

Example 4. In a horizontal reactor with a screw mixer load

5.76 g (0.01 mol) of cobalt phthalocyanine and 4.85 g (0.05 mol) of sulfamic acid (in a molar ratio of 1: 5, respectively). The temperature was raised to 230 ° C and held at this temperature for 60 minutes. After cooling, the melt is discharged. Received 8.85 g of cobalt phthalocyanine tetrasulfonic acid. Yield 98% of theoretical. There is no sewage.

Found,%: C 42.6; H 1.9; N, 12.3; S, 14.3. C32H16N8S4O12C0 (mol. 896).

Calculated,%: C42.85; H 1.78; N, 12.5; S1428.

The composition of the technical product,%: Tetrasulfonic acid98

Trisulfonic acid1

Disulfonic acid 0.7

Monosulfonic acid 0.2

Cobalt Phthalocyanine 0.1

Example 5 (for the average ratio). 5.76 g (0.01 mol) of cobalt phthalocyanine and 4.136 (0.0425 mol) of sulfamic acid (molar ratio 1: 4.25) are charged into a horizontal reactor with a screw mixer. The temperature of the reaction mixture was increased to 230 ° C and maintained at this temperature for 60 minutes. After cooling, the melt is discharged. 8.85 g of cobalt phthalocyanine tetrasulfonic acid are obtained. Yield 98% of theoretical. There is no sewage.

Found,%: C 42.83; H 1.75; N, 12.4; S 14.3. C32H16N8S3O12CO

Calculated,%: C42.85; H 1.78; N, 12.5; S 14.28.

The composition of the technical product,%:

Tetrasulfonic acid 98 Trisulfonic acid 0.8 Disulfonic acid 0.4 Monosulfonic acid 0.3 Phthalocyanine Co 0.5 Example 6 (for the minimum value

temperature). In a horizontal reactor with a screw mixer load

5.76 g (0.01 mol) of cobalt phthalocyanine and 3.88 g (0.04 mol) of sulfamic acid (1: 4 molar ratio, respectively). The temperature is increased to 220 ° C and maintained at this temperature for 60 minutes. After cooling, the melt is discharged. Received 8.85 g of cobalt phthalocyanine tetrasulfonic acid. Yield 98% of theoretical. There is no sewage.

Found,%: C 42.83; H 1.76; N, 12.3; S 14.31.

C32H16N8S4O12CO

Calculated,%: C 42.85; H 1.78; N, 12.5; S 14.28.

The composition of the technical product,%:

Tetrasulfonic acid 98.3 T rice sulfonic acid 0.7 Disulfonic acid 0.5 Monosulfonic acid 0.3 Phthalocyanine Co 0.2 Example 7 (for medium

temperature), 5.76 g (0.012 mol) of cobalt phthalocyanine and 3.88 g (0.04 mol) of sulfamic acid (molar ratio 1: 4, respectively) are loaded into a horizontal reactor with a screw mixer. The temperature was raised to 225 ° C and maintained at this temperature for 60 minutes. After cooling, the melt is discharged. Received 8.85 g of cobalt phthalocyanine tetrasulfonic acid. Yield 98% of theoretical. There is no sewage.

Found,%: C 42.82; H 1.79; N, 12.5;

S 14.4.

C32H16N8S4O12CO

Calculated,%: C 42.85; H 1.78; N, 12.5;

S 14.28.

The composition of the technical product,%:

T etrasul acid 98 Trisulfonic acid 0.5 Disulfonic acid 0.8 Monosulfonic acid 0.2 Phthalocyanine Co 0.5

Example 8 (going beyond the lower temperature limit). 5.76 g (0.01 mol) of cobalt phthalocyanine and 3.88 g (0.04 mol) of sulfamic acid (molar ratio 1: 4, respectively) are charged into a horizontal reactor with a screw mixer. The temperature was raised to 210 ° C and maintained at this temperature for 60 minutes. After cooling, the melt is discharged. Received 8.8 g of tetrasulfonic acid phthalocyanine cobalt. Yield 97.44% of theoretical. There is no sewage.

Found. %; C, 42.83; H 1.77; N, 12.3; S 14.5.

C32H16N8S4O12CO

Calculated,%: C 42.85; H 1.78; N, 12.5; S 14.28.

The composition of the technical product,%:

Tetrasulfonic acid97

Trisulfonic acid1

Disulfonic acid 0.8

Monosulfonic acid 0.6

Cobalt Phthalocyanine 0.6

Example 9 (going beyond the upper temperature limit). 5.76 g (0.01 mol) of cobalt phthalocyanine and 3.88 g (0.04 mol) of sulfamic acid (molar ratio 1: 4, respectively) are charged into a horizontal reactor with a screw mixer. The temperature was raised to 240 ° C and maintained at this temperature for 60 minutes. After cooling, the melt is discharged. Received 8.85 g of cobalt phthalocyanine tetrasulfonic acid. Yield 98% of theoretical. There is no sewage.

Found,%: C 42.83: H 1.75; N, 12.4; S 14.3.

C32H16N8S4O12CO

Calculated,%: C 42.85: H 1.78; N, 12.5; S 14.28.

The composition of the technical product,%:

Tetrasul Acid 98 Trisulfonic acid 0.6 Disulfonic acid 0.6 Monosulfonic acid . 0.5 Phthalocyanine Co 0.3

Changes in temperature and the ratio of the starting components (cobalt phthalocyanine and sulfamic acid) within the indicated intervals do not significantly affect the yield and composition of the technical product. An increase in the ratio of components and an increase in the temperature of synthesis is not advisable, since it leads to an overspending of the products without changing the yield and purity of the final product — cobalt tetrasulfonic acid.

The structure of the synthesized compound is confirmed by elemental analysis, the results of electronic and IR spectra. The absorption spectrum of the synthesized compound in dimethylformamide is shown. characterized by the presence of two electronic transitions Λι = 608 nm and Ar = 674 nm. which corresponds to cobalt tetrasulfonic acid phthalocyanine.

IR spectrum of the synthesized compound, cm '¹;1050-1120;1250-1150; 1400-1300, allow us to identify it as a spectrum of cobalt phthalocyanine tetrasulfonic acid.

To determine the qualitative composition of the obtained samples, the latter after each synthesis are purified according to the following procedure. The substance resulting from the synthesis is dissolved in ammonia, the insoluble precipitate is filtered off. The ammonia solution is passed through a chromatography column with silica gel brand L 100/250. Chromatography zones are isolated and identified by electronic and infrared spectra.

The proposed method for producing cobalt phthalocyanine tetrasulfonic acid has several advantages over the known one: the content of the main component in the technical product increases significantly to 98% compared to 50% in the known product, the yield of the final cobalt phthalocyanine tetrasulfonic acid product increases to 98% compared to 56% in the known , the technological scheme of production is simplified (the process is carried out in one stage). In addition, the method is environmentally friendly, as acidic effluents are not formed.

Claims (1)

SUMMARY OF THE INVENTION A method for producing cobalt phthalocyanine tetrasulfonic acid of the formula by the interaction of cobalt phthalocyanine and a sulfonating agent, characterized in that, in order to increase the yield, simplify the process and improve its environmental friendliness, sulfamic acid is used as a sulfonating agent and the process is fused at a molar ratio reagents 1: (4-4.5) at 220-230 ° C,