SU1620126A1 - Method of preparing polyphthalocyanine catalyst for oxidizing mercaptans - Google Patents

Abstract

This invention relates to catalytic chemistry, in particular, to the preparation of a hydrogen-phthalocyanine catalyst for the oxidation of mercaptans. Purpose - to increase the yield of the catalyst and simplify the process. cleaning and drying Urea is pre-impregnated with an aqueous solution of ammonium molybdate containing water (5.0–8.0% by weight of urea). A cobalt metal salt is added, followed by pyromellite. New dianhydride, urea, copper and nickel when heated, followed by purification and drying Table 2. U5 CO

Description

The invention relates to methods for producing catalysts for the oxidation of mercaptans, in particular to a method for producing a polyphthalocyanine catalyst for demercaptanizing liquefied gases, gasolines and kerosene.

The purpose of the invention is to increase the yield of the catalyst and simplify the process by pre-soaking the urea with an aqueous solution of ammonium molybdate containing 5-8% by weight of water by weight of the urea followed by the introduction of the metal salt and pyromellitic dianhydride.

Example 1. A solution of 0.25 g of ammonium molybdate in 2.5 g of water (the amount of water is 5.0% by weight of urea) and 50 g (0.835 mol) of urea are introduced into the reactor. After 60 minutes of exposure, 4.2 g (0.015 mol) of cobalt sulfate seven seven grams of cobalt sulfate and K) are urea impregnated with an aqueous solution of ammonium molybdate and K) g (0.046 mol) of pyromellite dianhydride in this sequence. 185 ° C for 3 hours, then cooled to 100 ° C and treated with 200 ml of boiling water for 1.5 hours. The solid phase is settled at 85 ° C and the solution is decanted with 160 ml of solution above precipitate. While stirring, 25 g of 93 wt.% Sulfuric acid is added to the remaining mass. The acidic suspension is heated at 60 ° C and stirred for 2 hours. After completing the acid treatment, 300 ml of boiling water is added to the acidic mass, after 15 minutes of stirring, the cobalt polyphthalocyanine is settled at 85 ° C and the acidic solution is decanted as completely as possible. the operation of washing polyphthalocyanine cobalt from sulfuric acid is repeated until neutral

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water. The neutral suspension is evaporated at 100 ° C to form a paste, which is dried at 125 ° C to constant weight. 9.0 g (87.4% of the theoretical amount) of cobalt polyphthalocyanine with carboxyl functional groups and an average degree of polymerization 7 are obtained.

Example 2. A cobalt polyphthalocyanine was prepared under conditions analogous to example 1, using a solution of 0.25 g of ammonium molybdate in 3.0 g of water for urea impregnation (the amount of water is 6% by weight of urea). The yield of cobalt polyphthalocyanine is 9.15 g (88.4% of the theoretical amount).

Example 3. A cobalt polyphthalocyanine was prepared under conditions analogous to example 1, using a solution of 0.25 g of ammonium molybdate in 4.0 g of water (the amount of water was 8.0% by weight of urea) for impregnating urea. The yield of cobalt polyphthalocyanine is 8.9 g (86.4% of the theoretical amount).

Example 4. Under conditions analogous to Example I, cobalt polyphthalocyanine is prepared using a solution of 0.25 g of ammonium molybdate in 4.2 g of water for urea impregnation (the amount of water is 8.4% by weight of urea). The yield of cobalt polyphthalocyanine is 8.63 g (83.7% of the theoretical amount).

EXAMPLE 5 Under conditions analogous to Example 1, cobalt polyphthalocyanine is obtained using a solution of 0.25 g of ammonium molybdate in 28 g of water for urea impregnation (the amount of water is 56% by weight of urea). The yield of cobalt polyphthalocyanine with carboxyl functional groups and an average degree of polymerization 5 is 5.6 g (54% of the theoretical amount).

When water is used in an amount of less than 5.0% by weight, based on the weight of urea, the yield of polyphthalocyanine cobalt is reduced.

EXAMPLE 6 Under conditions analogous to Example 1, cobalt polyphthalocyanine is prepared using a solution of 0.25 g of ammonium molybdate in 2 g of water for urea impregnation (the amount of water is 4.0% by weight of urea). The yield of cobalt polyphthalocyanine is 7.80 g (75.7% of the theoretical amount).

When replacing the cobalt salt with a nickel or copper salt, a polyphthalocyanine nickel or a polyphthalocyanine copper are obtained.

Example 7. A solution of 0.25 g of ammonium molybdate in 3 g of water (the amount of water is 6% by weight of urea), then 50 g of urea are introduced into the reactor. After 60 minutes of exposure, 2.5 g (0.015 mol) of copper chloride dihydrate and 10 g (0.046 mol) of pyromellite dianhydride are added to urea impregnated with an aqueous solution of ammonium molybdate and 10 g (0.046 mol) of pyromellite dianhydride

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respectability. For 60 min, the components are heated to 190 ° C and the reaction mass is maintained at 190 ° C for 3 h, then cooled to 110 ° C and, processing as in Example 1, 8.85 g (85.8%

from theoretical amount of polyphthalocyanine, copper with an average degree of polymerization 7.

Example 8. Under conditions analogous to example 7, polyphthalocyanine nickel is obtained,

0 using 4.36 g (0.15 mol) of nickel sulphide nitrate. By treating the reaction mass as in Example 1, 9.5 g (92.1% of the theoretical amount) of polyphthalocyanine nickel with an average degree of polymerization 7 are obtained.

Keeping the reaction mass at 210 ° C for 3 h and not conducting acid hydrolysis, polyphthalocyanines of metals with imide functional groups are obtained.

Example 9. A solution of 0.25 g of ammonium molybdate in 3 g of water (the amount of water is 6 wt.% By weight of urea) is added to the reactor, then 50 g of urea and, after 60 minutes of exposure, the urea soaked in an aqueous solution of ammonium molybdate is 4 , 2 g (0.015 mol) of cobalt sulphate and 10 g (0.046 mol) of pyromellitic dianhydride in the indicated sequence. For 60 minutes, the components are heated to 2 ° C and hold the reaction mass for 3 hours at 210 ° C, then it is cooled to 110 ° C and treated with 200 ml of boiling water for 1.5 hours. The solid phase is settled at 85 ° C and decant 160 ml of solution. 200 ml of a 1.5 wt.% Solution of sulfuric acid are added to the remaining mass, the suspension is heated with stirring to 85 ° C and maintained at 85 ° C for 15 minutes, then the stirring is stopped, the solid phase is settled at 85 ° C and the acidic solution of the precipitate is decanted as completely as possible. The remaining acid is washed with water by decantation until neutral wash water. The neutral suspension is evaporated at 100 ° C to form a paste, which is dried at 135 ° C to constant weight. 8.6 g (89.3% of the theoretical amount) of cobalt polyphthalocyanine with imide functional groups and an average degree of polymerization 8 are obtained.

Example 10. Under conditions analogous to example 9, polyphthalocyanine nickel is obtained,

5Q using 4.36 g (0.015 mol) of nickel sulphide nitrate. The yield of nickel polyphthalocyanine is 8.7 g (90.7% of the theoretical amount).

Example 11. Under conditions analogous to example 11, polyphthalocyanine is obtained.

5 copper, using 2.5 g (0.015 mol) of copper chloride dihydrate. The yield of copper polyphthalocyanine is 8.50 g (87.6% of the theoretical amount).

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A change in the sequence of the loading of the metal salt and airomellitic dianhydride leads to a decrease in the yield of polyphthalocyanines of metals by 13-16.5%.

Example 12. Under conditions analogous to example 1, cobalt polyphthalocyanine is obtained by loading urea, impregnated with ammonium molybdate urea water, first pyromellitic dianhydride, then seven-cobalt sulfate. The yield of cobalt polyphthalocyanine with carboxyl functional groups and an average degree of polymerization 7 is 74.5% of the theoretical amount (7.70 g).

Example 13. Under conditions analogous to experiment 9, cobalt polyphthalocyanine is obtained by loading urea impregnated with an aqueous solution of ammonium molybdate, first pyromellitic dianhydride, then cobalt sulfide. The yield of cobalt polyphthalocyanine with imide functional groups and an average degree of polymerization 7 is 72.8% of the theoretical amount (7.0 g).

The cobalt, nickel, and copper polyphthalocyanines obtained by the proposed method were tested for catalytic activity in the oxidation of mercaptans with air oxygen to disulfides according to the method used to determine the catalytic activity of cobalt polyphthalocyanine produced according to TU 38.40152-85; The catalytic activity of the polyphthalocyanines of copper, nickel and cobalt obtained by a known method was determined by the same method for comparison.

The procedure for determining the activity of polyphthalocyanine catalysts for the oxidation of mercaptans to disulfides is as follows.

In a 500 cm spherical flat-bottomed flask, 50 ml of a solution obtained by dissolving 0.1 g of a metal polyphthalocyanine in 100 g of a 10 wt.% Aqueous solution of sodium hydroxide and 200 ml of a reference isooctane with p-butyl mercaptan dissolved in it is placed. The rubber tube of the flask is connected to a water seal, which is the simplest counter of bubbles connected to the atmosphere. The contents of the flask were shaken on a shaking machine at room temperature (15-30 ° C), fixing the time from the breakthrough through the counter of the first bubble until the interval between the breakthroughs of the bubbles through the counter becomes more than 60 s; shaking is then stopped and after separation of the alkaline and hydrocarbon phase by sludge, the content of n-butyl mercaptan in the isooctane is determined. There is no need to neutralize the alkaline solution of the catalyst, since it does not contain butyl mercaptan (in the form of sodium butyl mercaptide). Initial con

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The concentration of n-butylmercaptan is determined in a separate sample which is prepared by adding to 200 ml of isooctane the exact volume of n-butylmercaptan taken to determine the activity of the catalyst. The initial and final concentrations of n-butylmercaptan in isooctane are determined according to GOST in the form of mercaptan sulfur SH.

The initial concentration of mercaptan sulfur in isooctane must be at least 0.5 wt.% (500 ppm). The final concentration of mercaptan sulfur in isooctane is determined by catalyst activity, which is estimated by the time (in minutes and seconds) for which at least 97 wt.% Mercaptan sulfur is oxidized to disulfide.

The results of determining the activity of the catalyst in the oxidation of n-butylmercaptan according to this method are shown in Table 1 and 2.

From the table. 1 and 2, the results of determining the activity of catalysts show that the catalytic activity of copper, nickel and cobalt polyphthalocyanine obtained according to the proposed method is slightly higher than the catalytic activity of copper, nickel and cobalt polyphthalocyanine obtained according to the prototype method.

Thus, the invention permits the production of polyphthalocyanine catalysts for the oxidation of mercaptans in high yield, greatly simplifying the process technology. The stage of preparation of the pyromellitic dihydrogen – anthracene complex, including the steps of dissolving pyromellitic dianhydride in acetone, adding a solution of anthracene in acetone to the resulting solution, filtering, drying, and grinding the resulting complex, was excluded from the technology. There is no need to prepare a mixture of pyromellitic dianhydride and anthracene complex with urea, a metal salt and ammonium molybdate, as well as a stage of purification of the catalyst from anthracene, including the extraction of anthracene with acetone, acetone distillation, filtration and drying of anthracene.

When producing polyphthalocyanine catalysts according to the proposed method, the yields of metal polyphthalocyanines are practically independent of the metal used and higher than the yields of the corresponding metal polyphthalocyanines obtained by a known method. Thus, the yield of copper polyphthalocyanine is 85.8% of the theoretical amount, cobalt polyphthalocyanine 88.6%, nickel polyphthalocyanine 92.1%, i.e., 3–12% higher than the yield of the corresponding catalysts according to a known method.

Claims (1)

Invention Formula A method for preparing a polyphthalocyanine catalyst for the oxidation of mercaptans by the interaction of pyromellitic dianhydride, urea, salt, metal-cobalt, copper or nickel, and ammonium molybdate when heated, followed by cleaning and drying, characterized in that, in order to increase the catalyst yield and simplify the process, before heating the urea is pre-impregnated with an aqueous solution of ammonium molybdate containing water in an amount of 5.0-8.0% by weight of urea, and a metal salt is introduced then pyromellitic dianhydride. Polyphthalocyanine C: with carboxyl groups with imide groups Ni polyphthalocyanine: with carboxyl groups with imide groups Nolithalocyanine So: with carboxyl Table 1 540,542 533 526 four four 5 6 Table 2