RU2152823C1 - Method of preparing catalyst for liquid-phase oxidation of sulfur compounds - Google Patents

Abstract

FIELD: oxidation catalysts. SUBSTANCE: high-efficiency catalysts for oxidative purification of hydrocarbon distillates, diesel fuel, waste waters, and gas emissions from sulfur compounds are prepared on basis of polysubstituted cobalt phthalocyanine. For that, cobalt phthalocyanine is sulfurized with chlorosulfonic acid while simultaneously treating reaction mixture with hydroxylamine sulfate and potassium bromide. EFFECT: reduced expenses due to utilization of accessible and inexpensive starting materials, simplified preparation technology, and improved catalytic characteristics. 1 tbl, 3 ex

Description

 The invention relates to methods for the preparation of highly effective catalysts based on polysubstituted cobalt phthalocyanine for the oxidative purification of hydrocarbon distillates, diesel fuel, wastewater and gas emissions from sulfur compounds and can be used in gas, oil refining, petrochemical, leather, chemical, pulp and paper and other industries.

Known (ed. St. USSR N 1640862, B.I. N 21, 1994) a method for preparing a catalyst based on a phthalocyanine compound, namely cobalt tetrachlorophthalocyanine. According to this method, cobalt tetra-4-chlorophthalocyanine is sulfonated with 10% oleum at 111-115 ^o C in the presence of boric acid at a mass ratio of cobalt tetra-4-chlorophthalocyanine: oleum: boric acid, respectively 1: (37.05-46 , 31): (0.208-0.65), followed by cooling the mass to 15 ^o C. Then the sulfomass is treated with an oxidizing agent - a freshly prepared solution of nitrosylsulfuric acid in monohydrate at the rate of 0.739 weight. parts of sodium nitrite per 1 weight. part of tetra-4-chlorophthalocyanine cobalt, incubated for two hours and diluted with water to isolate the precipitate of the target product. The sediment is decanted to a residual acidity of wash water ≤ 1%. The suspension of the catalyst is filtered off, washed on the filter with water to a neutral medium, dried and ground.

 Also known (Pat. RF N 1786719, 1995) is also a method of preparing a catalyst for liquid-phase oxidation of sulfur compounds, which differs from the above only by isolating the target product, which is carried out by diluting sulfomass with water to a residual acidity of 50-70% and then working out with 2-5% sodium chloride solution.

 The disadvantages of these methods are: complexity, the complexity and duration of the process, a large amount of wastewater.

Closest to the invention in technical essence and the achieved result is a method of preparing a catalyst for liquid-phase oxidation of sulfur compounds (US Pat. RF N 2100077 - B. I. N 36, 1997). According to this method, cobalt tetra-4-chlorophthalocyanine is sulfonated in 19% oleum in the presence of boric acid at 113 ^° C. Then, an oxidizing agent, sodium nitrite, in a weight ratio of cobalt tetra-4-chlorophthalocyanine: sodium nitrite, equal to 1: is added to the cooled sulfomass. (0,097-0,584), make an exposure, and then carry out the isolation of the target product by known methods, namely, reprecipitation on ice or chilled water, washing the precipitate by decantation, filtration, drying, grinding.

 The disadvantages of this method are the relative complexity and complexity due to the stage of preparation of a 19% oleum, as well as the duration of the process, the presence of a large amount of acidic wastewater, the use of deficient tetra-4-chlorophthalocyanine cobalt, which is produced as an intermediate from monosodium, as the initial phthalocyanine compound. salts of 4-fluorophthalic acid, the production of which, in turn, is limited and located outside the Russian Federation.

 The inventive task was to create a simplified method for producing a catalyst for liquid-phase oxidation of sulfur compounds, which would reduce the duration of the process, reduce the amount of acidic wastewater, eliminate scarce and expensive raw materials while maintaining high catalytic characteristics of the target product.

 The essence of the invention lies in the fact that in the method of preparing a catalyst for liquid-phase oxidation of sulfur compounds, including sulfonation of a phthalocyanine compound and isolation of the target product, cobalt phthalocyanine is sulfonated with chlorosulfonic acid and, during sulfonation, the reaction mixture is treated with hydroxylamine sulfate and potassium bromide.

Distinctive features of the invention are:
- use as a phthalocyanine compound - cobalt phthalocyanine;
- use as a sulfonating agent - chlorosulfonic acid;
- treatment of the reaction mass during sulfonation with hydroxylamine sulfate and potassium bromide.

The invention allows:
- use as an initial compound of the phthalocyanine series available and cheaper cobalt phthalocyanine;
- to simplify the technology by eliminating the stage of preparation of the 19% oleum;
- reduce the duration of obtaining the target product from 24-25 hours to 13-15 hours by eliminating the stage of preparation of the oleum and reducing the time of washing and isolation of the target product;
- reduce the consumption of sulfonating agent, and as a result, the volume of acidic wastewater;
- improve the catalytic characteristics (activity and stability) of the target product.

 Information confirming the possibility of carrying out the invention.

 To implement the method, the following substances are used: cobalt phthalocyanine - TU 6-07-1135-78; chlorosulfonic acid - GOST 2124-73; hydroxylamine sulfate - GOST 7298-79; potassium bromide - GOST 4160-74; aqueous ammonia solution - GOST 7298-79.

 The method is implemented as follows. Cobalt phthalocyanine is dissolved in chlorosulfonic acid, hydroxylamine sulfate (or potassium bromide) is added, heated, and soaked. The sulfomass is cooled, potassium bromide (or hydroxylamine sulfate) is added with stirring, it is heated again and aged, and then the desired product is isolated by known methods (reprecipitation on ice or chilled water, washing the precipitate by decantation, filtration, treatment with aqueous ammonia, evaporation, drying, grinding). The mass ratio of cobalt phthalocyanine: chlorosulfonic acid: hydroxylamine sulfate: potassium bromide is 1: (5.19-6.23): (0.74-0.78) :( 0.74-1.56).

Example 1. 6.8 g (11.9 mmol) of cobalt phthalocyanine and 5 g (30.5 mmol) of hydroxylamine sulfate are placed in 20 ml of chlorosulfonic acid. The reaction mass is heated to 145 ^o C and incubated for 2 hours. At the end of the exposure, the sulfomass is cooled to 50 ^° C. and 5 g (42 mmol) of potassium bromide are added, again heated to 145 ^° C. and held for 2 hours. At the end of the exposure, the reaction mass is poured onto ice, then the precipitate is washed by decantation, filtered. The resulting paste is placed in 25 ml of ammonia water, filtered, dried, and ground.

 Yield: 10.1 g.

Example 2. 6.4 g (11.2 mmol) of cobalt phthalocyanine and 10 g (84 mmol) of potassium bromide are placed in 20 ml of chlorosulfonic acid. The reaction mass is heated to 145 ^o C and maintained until the disappearance of brown bromine vapor (about 40 minutes), cooled to 60 ^o C and add 5 g (30.5 mmol) of hydroxylamine sulfate. Sulfomassa is heated to 145 ^o C and incubated for 2 hours. At the end of the exposure, the reaction mass is poured onto ice, then the precipitate is washed by decantation, filtered. The resulting paste is placed in 25 ml of ammonia water, evaporated, dried, and ground.

 Yield: 10.3 g.

Example 3. 3.4 g (6.0 mmol) of cobalt phthalocyanine and 3.5 g (29.4 mmol) of potassium bromide are placed in 12 ml of chlorosulfonic acid. The reaction mass is heated to 145 ^o C and maintained until the disappearance of brown bromine vapor (about 30 minutes), cooled to 60 ^o C and add 2.5 g (15.2 mmol) of hydroxylamine sulfate. Sulfomassa is heated to 145 ^o C and incubated for 2 hours. At the end of the exposure, the reaction mass is poured onto ice, then the precipitate is washed by decantation, filtered. The resulting paste is placed in 15 ml of ammonia water, evaporated, dried, and ground.

 Yield: 6.0 g.

 The test data of the obtained samples and the catalyst prepared in a known manner (prototype) for activity and stability in the oxidation reaction of sodium n-propyl mercaptide are shown in the table.

Claims (1)

 A method of preparing a catalyst for liquid-phase oxidation of sulfur compounds, including sulfonation of a phthalocyanine compound and isolation of the target product, characterized in that cobalt phthalocyanine is sulfonated with chlorosulfonic acid and, during sulfonation, the reaction mixture is treated with hydroxylamine sulfate and potassium bromide.

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