The method of producing metalphthalocyanine

 

(57) Abstract:

The essence: gaining phthalocyanine metal (Cu, Ni, Zn) improved way. Reagent 1: phthalic anhydride. Reagent 2: urea. Reagent 3: copper sulphate or copper-zinc, or zinc-containing galvanic sludge. Process conditions: fusion reagents 1, 2 and 3 with pretreatment weight water in an amount of 10-30 wt.%, and to bind the ammonia released during the synthesis process, the exhaust gases are passed through a barbaterom with a water suspension of phthalic anhydride at 20-60oC. table 3.

The invention relates to the field of technology for metal complexes with phthalocyanine MPC where M is metal ion, RS phthalocyanine (C32H16N8)2-. These compounds are widely used as pigments, catalysts, lubricants, etc.

Analogues of the proposed method are methods for producing metal complexes of phthalocyanine by fusing a mixture of urea, phthalic anhydride, metal salt in the presence of a catalyst at a temperature in the region of 150-250o(1-7). A recognized catalyst is ammonium molybdate. This forms a technical phthalocyanine, further treatment

In the known solutions at the stage of obtaining technical product does not reflect modern requirements of environmental safety, the principles of waste products and reduce the cost of technology for the metal complex of phthalocyanine. In particular, there should be no waste purification of exhaust gases from hazardous ammonia, it does not solve the problem of using a cheaper source of reagents for the synthesis of MPC. To improve the mechanical and pigment properties of the product of synthesis in the melt is injected additives of organic solvents or compounds inorganic nature, containing a chloride or nitrate ions. Reset these ingredients synthesis in the allocation process of the MPC from the reaction mixture leads to environmental pollution.

A prototype of the proposed method can serve as a method of producing copper phthalocyanine described in (6). According to the prototype of the copper phthalocyanine is produced by fusing a mixture of phthalic anhydride (12.0 g), urea (22,5 g), copper acetate (6.0 g), ammonium molybdate (0.4 g) at 250oWith at least three hours. To improve product yield and quality in the reactive mixture is injected from 0.5 to 5% (calculated on the dry weight of the mixture) of chlorides and nitrates in the form of their ammonium salts and/or see above for analogues.

To overcome these shortcomings features formed during the synthesis of MPC gases to clean, skipping through the suspension of phthalic anhydride in water. The resulting mixture of products of interaction of gases with phthalic anhydride used for the synthesis of phthalocyanine. The result achieved a high degree of purification of the gas stream from the ammonia and return it as a product of interaction with phthalic anhydride in the composition of the reacting mixture. In addition, to obtain technical metalphthalocyanine proposed to use instead of industrially produced metal salts waste electroplating plants that contain compounds of transition metals. It was established experimentally that the introduction of water leads to a more uniform flow of process synthesis, decreases the likelihood of foaming of the reaction mixture and the cooled water of the final product is obtained in the form of a loose mass, irritated by mechanical grinding.

The set of essential features of the proposed method of obtaining MPC allows to achieve a positive technical result to dispose of waste the technological process of synthesis of MPC and metal-containing waste galvanic PR is x, to reduce the cost of the target product, to improve the mechanical properties.

Below are examples of the implementation of predlagemogo method of producing phthalocyanine complexes with different metals, including part of the waste electroplating plants.

Example 1. A mixture of the product of the interaction of gases with phthalic anhydride (15,8 g), urea (22,8 g), copper sulfate (6.0 g), water (10.0 g), ammonium molybdate (0.4 g) was melted in a reactor made of stainless steel (water in the amount of 20 wt. was added to the reactor before the beginning of melting) for three hours at a slow rise of temperature up to 250oC. the Exhaust gases from the reactor was passed through a barbaterom with absorbent material, consisting of a suspension of 23 g of phthalic anhydride and 55 g of water. The temperature of the environment in barbaterom was supported by the 20oC. At the outlet of the barbaterom controlled the content of ammonia in the gas by gas chromatography (with the accumulation of ammonia in the cryogenic trap) and ammonia analyzer touch type.

The composition of the exhaust gases are given in table 1.

According to visual observations in the composition of the exhaust gases included chromatographic indefinite particles (pairs) of phthalic anhydride and ammonium carbonate.

In othow the unbound state. Control of ammonia at the outlet of the barbaterom using cryogenic traps allowed us to evaluate its contents in the exhaust gas at the level of 10-4volume%. This underlines the high collection efficiency of ammonia suspension of phthalic anhydride in water. The product of the interaction of ammonia and phthalic anhydride are well soluble in water and is distinguished from it by the method of crystallization. In the sediment is also a significant amount of unreacted phthalic anhydride (poorly soluble in water). This mixture of substances is returned to the reactor for the synthesis of copper phthalocyanine.

Technical phthalocyanine copper in the reactor (10 g) was a fragile substance in dark blue.

Identified by the absorption bands of the solution in chloronaphthalene with maximum long-wave absorption band at 680 nm and side maxima at 652 and 614 nm. The content of the target product in the technical IFAS, found presidenial samples from sulfuric acid, 70%

Example 2. In a reactor made of stainless steel (with a capacity of 0.3 l) was melted mixture of the product of the interaction admixtures exhaust gases with phthalic anhydride (45,3 g), urea (56.7 g), copper-containing galvanic sludge (6.0 g), water (is 40% copper 29 wt. in terms of dry matter, calcium -1,0% insolubles - 11,0% other compounds (sulphates, chlorides) of 18.5%

The maximum ammonia after passing the exhaust gas barbaterom with a suspension of phthalic anhydride (57,0 g) in water (137 g) does not exceed 10-3% vol. (according to chromatographic analysis for ammonia).

The temperature of the environment in barbaterom 20oC. the Amount of copper phthalocyanine, perezajennogo of sulfuric acid, accounted for 75% of the total mass of the reaction products. Absorption spectrum of the obtained substances in chloronaphthalene similar absorption spectrum of copper.

Example 3. A mixture of the product of the interaction leakagerough gas with phthalic anhydride (45,3 g), urea (56.7 g), zinc-containing galvanic sludge (6.0 g), water (12.0 g), ammonium molybdate (0.4 g) was melted in a reactor of stainless steel for three hours in a slow rise of temperature up to 250oC. the Mixture of the reagents contained 10 wt.%. water.

The composition of the electroplating sludge (% wt.): residual moisture 32,0, zinc 9,4, copper 0,3, calcium 16.5, and other connections 42,0.

The exhaust of the reaction gases was passed through the barbaterom with a suspension of phthalic anhydride (57.6 g) in water (137,0 g) at a temperature of 60oC.

The temperature of the environment in barbaterom above 60oWith impractical due to increased entrainment of water vapor, which is confirmed by the data analysis.

Phthalocyanine zinc identified by the absorption bands of its solution in chloronaphthalene 681, 649, 611 nm. The content of the target product in the water, found presidenial samples from sulfuric acid, was 63%

Example 4. A mixture of the product of the interaction leakagerough gas with phthalic anhydride (45,3 g), urea (56.7 g), water (45,0 g), ammonium molybdate (0.4 g) and Nickel-containing galvanic sludge (6.0 g) was melted in the reactor for three hours with a gradual rise of temperature up to 250oC. the Mixture of the reagents contained 30 wt.%. water.

The composition of the electroplating sludge (% wt.): Nickel 9,1; zinc 1,3; copper 0,2; calcium 3,0, residual moisture 50, an organic part 19,9 (the composition of the organic impurities from the plant owner sludge not specified) other compounds (chlorides, sulfates, etc.,) 17,6.

Exhaust gases were passed through the barbaterom with a suspension of phthalic anhydride in water at 40oC. the gas Composition before and after barbaterom presented in table 3.

Phthalocyanine Nickel identified on the main maximum of the absorption band solution pitaniem samples from sulfuric acid, 60%

It was established experimentally that the essential feature is the presence of water in the barbaterom, as in this case, the highest efficiency of purification of exhaust gases from ammonia compared with only clean water or only dry phthalic anhydride.

It should be noted that the composition of exhaust gases in the conditions of the experiments and the specifics of the process of synthesis of phthalocyanine with the use of urea is not reproduced and the exhaust gases contain also a large number of particles (up to 20% by weight of the initial load) phthalic anhydride (So pl. 130, 8mmoWith So Kip. 284,5oC), water vapor, which, falling in the scope of barbaterom, condense there.

It should be noted that a necessary condition for highly efficient purification of ammonia is the education phase, water-phthalic anhydride, but the degree of purification does not practically depend on the ratio of water-phthalic anhydride. However, from a technical and economic considerations the amount of water in the barbaterom should be limited, because the product of the interaction of ammonia with phthalic anhydride it is soluble in water and more practical to work in this case, the concentrated solution. Optimal Ghania of metallophthalocyanines by fusing a mixture of phthalic anhydride, urea, metal salt and ammonium molybdate, characterized in that the reaction mixture before injection of the injected water in an amount 10 to 30 wt. and to bind the ammonia released during the synthesis process, the exhaust gases are passed through a bubbler with a water suspension of phthalic anhydride at 20 - 60oC.

2. The method according to p. 1, characterized in that as the metal salt used containing transition metals waste electroplating plants.

3. The method according to p. 1, 2, characterized in that the reaction mixture as phthalic anhydride using the product of its interaction with ammonia in barbaterom.

 

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