SU1680704A1 - Method for obtaining catalyst for demercaptanization of hydrocarbon raw material - Google Patents

Abstract

The invention relates to phthalocyanine complexes of metals, in particular the preparation of phthalocyanine and polyphthalocyanine complexes of cobalt — catalysts for the demercaptane hydrocarbon feedstock. -40% of the mass of the reaction mixture, at 1 / О С “As the ligand-forming agent, use is made of ft left anhydride, 3-nitrophthalic anhydride, pyromellitic dianhydride and a mixture of phthalic anhydride and pyromellitic dianhydride (1: 1.4 ratio) 0 These conditions increase the yield of the target product from 36% to 84%. The resulting catalysts increase the degree of demercaptanization from 98% to 99.99% of 1%.

Description

The invention relates to a method for producing a new catalyst for the demercaptanization of a hydrocarbon feedstock that is used in the production of petroleum distillates.

The aim of the invention is to increase the yield and quality of the target product.

Example 1 o Mixture composition: 50 g of urea (0.8 / M), 10 g of phthalic anhydride (0.067 M), 5 g of cobalt sulfate, 0.5 g of ammonium molybdate and 15 ml of sulfuric acid, d 1.84 ( 28% by weight of the reaction mixture) is placed in a reactor. The reactor is placed in an adjustable electric furnace, it is heated to 1/0 ° C and maintained at

This temperature is 1 h. Then the melt is poured with hot water and boiled for 3 hours. The resulting suspension is washed on the filter with hot water and dried at 100 ° C to constant weight. The resulting product, purified from water-soluble substances and salts, is poured 100 ml (d 1.84), stirred until complete dissolution and precipitated in 2 l of ice water. The precipitate is decanted, filtered and dried at 130 ° C to constant weight. 8.1 g cobalt phthalocyanine Yield 85% „

Example 2 o Mixture composition: 50 g of urea (0.87 M), south of 3-nitro-phthalic anhydride, 5 g of sulphate

about with

about vj

g

cobalt, 0.5 g of ammonium molybdate and 15 ml of sulfuric acid (d 1.84) are introduced into the reactor. The reactor is placed in an adjustable electric furnace, it is heated to 1/0 ° C and maintained at this temperature for 1 hour.

Then the melt is poured with hot water and boiled for 3 hours. The resulting suspension is washed on the filter with hot water and dried at 100 ° C until constant weight.

The resulting product, purified from water-soluble substances and salts, is poured onto 100 ml of sulfuric acid, 84 is stirred until complete dissolution, is precipitated in 2 liters of ice-water. The precipitated precipitate is decanted and dried at 130 ° C to constant weight. Cobalt phthalocyanine is obtained /, 8 g „Yield 81%.

 Example 3 Mixture composition: 50 g (0.87 M) urea, 10 g (0.046 M) pyromellitic dianhydride (GO-ALA), 5 g cobalt sulfate, 0.5 g ammonium molybdate and 15 ml (28 wt.% ) sulfuric acid (d 1.84) is introduced into the reactor about

The reactor is placed in an adjustable electric furnace, the mixture is heated to 170 ° C and maintained at this temperature for 1 hour.

Then the melt is poured with hot water and boiled for 2 hours. The resulting suspension is washed on the filter with hot water and dried at 100 ° C until constant weight is about

The resulting product, purified from water-soluble substances and salts, is poured over 100 ml of sulfuric acid (stirred until complete dissolution is poured into 2 liters of ice water. The precipitated precipitate is decanted, filtered and dried for 2 hours at 130 ° C to constant weight. 8.4 g polyphthalocyanine cobaltao Yield 81% „

Example 4o A mixture of composition: 50 g of urea (0.87 M), 5 g of PMDA (0.023 M), 5 g of phthalic anhydride (0.033 M), 5 g of cobalt sulfate, 0.5 g of ammonium molybdate and 15 ml of concentrated sulfuric acid, 84 (28% by weight of the reaction mixture) are introduced into the reactor

The reactor is placed in an adjustable electric furnace, the mixture is heated to 170 ° C and kept at this temperature for 1 hour.

Then melt is poured with hot water and boiled for 2 hours.

The resulting suspension is washed on the filter with hot water and dried at 100 ° C to a constant weight.

The resulting product, purified from water-soluble substances and salts, is poured over 100 ml of sulfuric acid (84), stirred until complete dissolution and poured into 2 liters of ice water.

The precipitated precipitate is decanted, filtered and dried at up to constant weight. 8.1 g of cobalt polyphthalocyanine “Yield 78%” are obtained.

The dependence of the output of phthalocyanine cobalt on the content of sulfuric acid (d 1.84) in the initial mixture of the composition, g, phthalic anhydride 10, urea 50, ammonium molybdate 0.5, cobalt sulfate 5, is as follows:

Attitude towards Exit

reaction mixture, product,

weight0 %%

25 52 64 70 78 80 85 75 63 58 41

The dependence of the output of polyphthalocyanine cobalt on the content of sulfuric acid (d 1.84) in the initial mixture of the same composition is as follows:

Relation to the yield of the reaction mixture, product, weight0 %%

53

561

1064.

20/5

3081

4078

5041

As can be seen from the presented data, a high yield of catalyst is achieved when 10–40 concentrated sulfuric acid is introduced into the system. When less than 10% sulfuric acid is introduced into the reaction mixture, the effect is weak: the yield of the product increases slightly, the water contains many impurities, and to obtain high quality ( with a concentration of the main substance of at least 98%), reprecipitation from concentrated sulfuric acid is necessary, which will lead to a large amount of acidic effluents during industrial implementation

When the content in the initial mixture of sulfuric acid is more than 40%, a sharp decrease in yield is observed, a partial resinification of the reaction products occurs.

Table 2 shows the dependence of the yield of polyphthalocyanine cobalt on the ratio of ligand-forming agents

Example 5 The phthalocyanine catalysts obtained by this method were tested for catalytic activity in the oxidation reaction of n-butylmercaptan in isoctane with oxygen by the following method

In a 200 ml conical flask, a 1 N aqueous solution of sodium hydroxide containing 0.1 g / l of catalyst prepared by various methods and 40 ml of a solution of n-butylmercaptan in isooctane (0.15) is placed, the flask is closed at 23 ° C for 3 min. Next, a sample of the hydrocarbon is taken and the content of mercans of tan sulfur is determined by potentiometric titration.

The results of the quantitative determination of sulfur in the form of mercaptans in the hydrocarbon phase before and after the reaction are given in Table 2, Along with the model mixture, the catalyst tested

five

on the gasoline and diesel fi qi of the Karachygansk gas-condensate field, they were reported. Table 02 also contains information on the catalytic activity of known catalysts, and of the decomposition of hydrocarbons.

Thus, the use of this method ensures the production of highly active catalysts of both mono- and polymeric structure with high yield (from 36% by a known method to 84% by the offer), which allow increasing the degree of mercaptan conversion from 98% to 99.99 % „

Claims (2)

Formula invention 1 o Method for preparing hydrocarbon demercaptanization catalyst raw materials by reacting urea, cobalt salts, ligand-forming agents - polycarboxylic aromatic acid anhydride and ammonium molybdate when heated, differing from the fact that, in order to increase the yield and quality of the target product, the interaction is carried out in the presence of sulfuric acid, taken in an amount of 10 -40% by weight of the reaction mix 2. Method pop.1, characterized in that phthalic anhydride, 3-nitrophthalic acid is used as ligand-forming agent anhydride, pyromellitic dianhydride and a mixture of pyromellitic dianhydride and phthalic anhydride in a ratio of 1.0: 1.4 100% PVDA 8: 2 6: 4 1: 1 4: 6 Table 1 (Without catalyst) Merox Firn-Butilmer- In isooctane Kaptan 0.101 0.15 table 2