RU2464093C1 - Method of producing catalyst for protium-deuterium isotopic exchange - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a catalyst for protium-deuterium isotopic exchange. Described is a method of producing a catalyst for protium-deuterium isotopic exchange, involving obtaining metal nanoparticles in a reverse micellar solution consisting of a metal salt solution, a surfactant which is sodium bis(2-ethylhexyl)sulphosuccinate, and a nonpolar solvent, isooctane, followed by deposition on a support, wherein reduction of the metal salt takes place upon reaction with quercetin; the support used is Sibunit and the metal salt used is RhCl₃ or RuOHCl₃ and reverse micellar solutions of rhodium or ruthenium are prepared with molar ratio of the aqueous metal salt solution to the surfactant ranging from 1:1 to 10:1; a water-alcohol solution is then added in amount of 5-50 wt %, a quercetin solution is added in amount of 0.5-5 wt % and ammonia solution is added in amount of 10-30 wt %.

EFFECT: catalyst for protium-deuterium isotopic exchange, having high catalytic activity, is obtained.

2 cl, 4 tbl, 4 ex

Description

The invention relates to the field of heterogeneous catalysis, in particular to a method for producing a catalyst for isotopic exchange of protium-deuterium.

A known method of producing a catalyst by ion exchange, in which a carrier of a refractory oxide containing a hydrogen cation is treated with a solution containing metal cations. Immediately after treatment, the oxide is washed with water to separate chemically unbound metal cations. Then the oxide is dried, and part of the metal cations is reduced by heating the refractory oxide to elemental metal by separation from bound water, which is associated with metal cations (German Pat. No. 1542012, class B01Y 37/30 from 10.21.76). This catalyst is used only for ion exchange.

A known method of producing a catalyst for isotopic exchange between water and hydrogen, where the catalyst includes a hydrophobic porous matrix dispersed in it with platinum and at least another metal selected from the group of chromium or titanium (US Pat. EP No. 1486457, CL. B01D 59 / 00, B01Y 37 / 00-37 / 02 of 06/06/2003). However, this catalyst is used only for isotopic exchange between water and hydrogen.

The closest in technical essence and the achieved result is a method of producing a catalyst Pt ^mitz / Al ₂ O ₃ for isotopic exchange of protium and deuterium and ^op conversion of protium. Pt nanoparticles are formed during radiation-chemical reduction of platinum ions in reverse micellar systems

H ₂ [PtCl ₆ ] / H ₂ O / acetone / bis (2 ethylhexyl) sodium sulfosuccinate / isooctane. Nanoparticles were obtained from three different initial reverse micellar solutions, differing in the values of solubilization coefficient ω = 1,5, 3 and 5 (“Promising materials”, pp. 288-293, 2010).

However, the catalyst has a low catalytic activity.

The technical result of the invention is to obtain a catalyst for isotope exchange of protium-deuterium, which has high catalytic activity and is designed to operate in the temperature range of 77-400 K.

This technical result is achieved by obtaining a catalyst for the isotope exchange of protium-deuterium, including the production of metal nanoparticles in a reverse micellar solution consisting of a solution of a metal salt, a surfactant, which is sodium bis (2-ethylhexyl) sulfosuccinate, and a non-polar solvent, isooctane, followed by coating on the carrier, and the metal salt is reduced by reaction with quercetin, Sibunit is used as the carrier, and RhCl ₃ or RuOHCl _{3 is} used as the metal salt, and tnomicellar solutions of rhodium or ruthenium in the ratio of molar amounts of an aqueous solution of a metal salt to a molar amount of a surfactant in the range from 1: 1 to 10: 1, then an aqueous-alcoholic solution in the amount of 5-50 wt.%, a quercetin solution in the amount of 0.5 -5 wt.% And ammonia solution in an amount of 10-30 wt.%.

Isopropanol is used as the alcohol in the aqueous-alcoholic solution.

Example No. 1

A reverse micellar solution of the rhodium salt RhCl _{3 was} prepared with a molar ratio of an aqueous solution of a metal salt to a molar amount of sodium 1: 1 bis (2-ethylhexyl) sulfosuccinate. Then add a water-alcohol solution in an amount of 3.4 · 10 ^-3 g (5 wt.%), A solution of quercetin 3.4 · 10 ^-4 g (0.5 wt.%) And an ammonia solution in an amount of 2.0 · 10 ^-2 g (30 wt.%).

Weighed 1 g of Sibunit carrier and placed in 10 ml of the obtained reverse micellar solution.

The decrease in the intensity of the peaks corresponding to rhodium nanoparticles in a solution with the Sibunit carrier immersed in it was used to determine the adsorption of rhodium nanoparticles. The fact of the formation of nanostructured rhodium particles was recorded by the presence of characteristic peaks in the optical absorption spectra, as well as by atomic force microscopy. Samples of the carrier with precipitated rhodium nanoparticles were removed from the reverse micellar solution and dried in air for 24 hours. The dried samples were washed sequentially with isooctane (once), aqueous-alcoholic solution (once) and distilled water (three times). The prepared catalyst samples with precipitated rhodium nanoparticles were heated in vacuum to 550 K for four hours. At a pressure of 0.5 Torr and a temperature of 77 K, the catalytic activity of the Rh / Sibunit catalyst with respect to the protium-deuterium isotopic exchange is 4.66 · 10 ¹⁴ molecules / (cm ² · s), which is ~ 2 times higher than the activity of the Pt ^mic catalyst / Al ₂ O ₃ selected as a prototype. Data on the activity of this sample of the catalyst Rh / Sibunit prepared according to example 1, in the temperature range 77-400 K are presented in table 1.

Example No. 2

A reverse micellar solution of the rhodium salt RhCb was prepared with a molar ratio of an aqueous solution of a metal salt to a molar amount of sodium bis (2-ethylhexyl) sulfosuccinate 10: 1. Then add a water-alcohol solution in an amount of 3.4 · 10 ^-2 g (50 wt.%), A solution of quercetin 3.4 · 10 ^-3 g (5 wt.%) And an ammonia solution in an amount of 6.8 · 10 ^{- 3} g (10 wt.%).

Weighed 1 g of Sibunit carrier and placed in 10 ml of the obtained reverse micellar solution.

The decrease in the intensity of the peaks corresponding to rhodium nanoparticles in a solution with the Sibunit carrier immersed in it was used to determine the adsorption of rhodium nanoparticles. The fact of the formation of nanostructured rhodium particles was recorded by the presence of characteristic peaks in the optical absorption spectra, as well as by atomic force microscopy. Samples of the carrier with precipitated rhodium nanoparticles were removed from the reverse micellar solution and dried in air for 24 hours. The dried samples were washed sequentially with isooctane (once), aqueous-alcoholic solution (once) and distilled water (three times). The prepared catalyst samples with precipitated rhodium nanoparticles were heated in vacuum to 550 K for four hours. At a pressure of 0.5 Torr and a temperature of 77 K, the catalytic activity of the Rh / Sibunit catalyst with respect to the protium-deuterium isotopic exchange reaction was 4.90 · 10 ¹⁴ molecules / (cm ² · s), which is ~ 2 times higher than the activity of the Pt catalyst ^Mitz / Al ₂ O ₃ selected as a prototype.

Data on the activity of this sample of the catalyst Rh / Sibunit prepared according to example 2, in the temperature range 77-400 K are presented in table 2.

Example No. 3

A reverse micellar solution of the ruthenium salt RuOHCl _{3 was} prepared with a molar ratio of an aqueous solution of a metal salt to a molar amount of sodium bis (2-ethylhexyl) sulfosuccinate 1: 1. Then add a water-alcohol solution in an amount of 3.4 · 10 ^-3 g (5 wt.%), A solution of quercetin 3.4 · 10 ^-4 g (0.5 wt.%) And an ammonia solution in an amount of 2.0 · 10 ^-2 g (30 wt.%).

Weighed 1 g of Sibunit carrier and placed in 10 ml of the obtained reverse micellar solution.

The decrease in the intensity of the peaks corresponding to ruthenium nanoparticles in a solution with the Sibunit carrier immersed in it was used to determine the adsorption of rhodium nanoparticles. The fact of the formation of nanostructured rhodium particles was recorded by the presence of characteristic peaks in the optical absorption spectra, as well as by atomic force microscopy. Carrier samples coated with rhodium nanoparticles were removed from a reverse micellar solution and dried in air for 24 hours. The dried samples were washed sequentially with isooctane (once), aqueous-alcoholic solution (once) and distilled water (three times). The prepared catalyst samples with precipitated rhodium nanoparticles were heated in vacuum to 550 K for four hours. At a pressure of 0.5 Torr and a temperature of 77 K, the catalytic activity of the Ru / Sibunit catalyst with respect to the protium-deuterium isotope exchange reaction was 4.98 × 10 ¹⁴ molecules / (cm ² · s), which is ~ 2 times higher than the activity of the Pt catalyst ^Mitz / Al ₂ O ₃ selected as a prototype.

Data on the activity of this sample of the Ru / Sibunit catalyst prepared according to example 3 in the temperature range 77-400 K are presented in table 3.

Example No. 4

A reverse micellar solution of the ruthenium salt RuOHl _{3 was} prepared with a molar ratio of an aqueous solution of a metal salt to a molar amount of 10: 1 sodium bis (2-ethylhexyl) sulfosuccinate. Then add a water-alcohol solution in an amount of 3.4 · 10 ^-2 g (50 wt.%), A solution of quercetin 3.4 · 10 ^-3 g (5 wt.%) And an ammonia solution in an amount of 6.8 · 10 ^{- 3} g (10 wt.%).

Weighed 1 g of Sibunit carrier and placed in 10 ml of the obtained reverse micellar solution.

The decrease in the intensity of the peaks corresponding to ruthenium nanoparticles in a solution with the Sibunit carrier immersed in it was used to determine the adsorption of rhodium nanoparticles. The fact of the formation of nanostructured rhodium particles was recorded by the presence of characteristic peaks in the optical absorption spectra, as well as by atomic force microscopy. Carrier samples coated with rhodium nanoparticles were removed from a reverse micellar solution and dried in air for 24 hours. The dried samples were washed sequentially with isooctane (once), aqueous-alcoholic solution (once) and distilled water (three times). The prepared catalyst samples with precipitated rhodium nanoparticles were heated in vacuum to 550 K for four hours. At a pressure of 0.5 Torr and a temperature of 77 K, the catalytic activity of the Ru / Sibunit catalyst with respect to the protium-deuterium isotopic exchange reaction was 4.94 · 10 ¹⁴ molecules / (cm ² · s), which is ~ 2 times higher than the activity of the Pt catalyst ^Mitz / Al ₂ O ₃ selected as a prototype.

The results of measurements of the specific catalytic activity of the Ru / Sibunit catalyst sample prepared according to Example 4 in the temperature range 77-400 K are presented in Table 4.

Table 1 The values of the specific catalytic activity of Rh / Sibunit, the preparation of which is considered in example 1, in relation to the reaction of isotope exchange of protium-deuterium (the ratio of an aqueous solution of RhCl ₃ to sodium bis (2-ethylhexyl) sulfosuccinate is 1: 1) K _beats · 10 ^-14 molecules / (cm ² · s) at T, K 77 110 133 153 163 173 193 227 243 295 320 370 400 4.66 4,52 4.35 6.63 8.16 15.22 15.18 16.54 34.75 62.98 73.11 90.33 100.06

table 2 The values of the specific catalytic activity of Rh / Sibunit, the preparation of which is considered, in example 2, with respect to the reaction of isotope exchange of protium-deuterium (the ratio of an aqueous solution of RhCl ₃ to sodium bis (2-ethylhexyl) sulfosuccinate is 10: 1) K _beats · 10 ^-14 molecules / (cm ² · s) at T, K 77 110 133 153 163 173 193 227 243 295 320 370 400 4.90 4.34 4.23 6.86 8.12 14.75 15.97 16.25 36.75 66.22 72.86 96.22 103.74

Table 3 The values of the specific catalytic activity of Ru / Sibunit, the preparation of which is considered in Example 3, in relation to the isotope exchange reaction of protium-deuterium (the ratio of an aqueous-alcoholic solution of RuOHCl ₃ to sodium bis (2-ethylhexyl) sulfosuccinate is 1: 1) K _beats · 10 ^-14 molecules / (cm ² · s) at T, K 77 110 133 153 163 173 193 227 243 295 320 370 400 4.98 4.34 4.75 6.36 9.15 15,52 15.26 16.32 33.27 63.27 63.65 100.59 112.36

Table 4 The values of the specific catalytic activity of Ru / Sibunit, the preparation of which is considered in Example 4, with respect to the isotope exchange reaction of protium-deuterium (the ratio of an aqueous-alcoholic solution of RuOHCl ₃ to sodium bis (2-ethylhexyl) sulfosuccinate is 10: 1) K _beats · 10 ^-14 molecules / (cm ² · s) at T, K 77 110 133 153 163 173 193 227 243 295 320 370 400 4.94 4.64 4.23 5.45 8.85 15.23 17.52 19.16 40.02 62.55 68.89 84.35 102,03

The presented data show the absence of significant differences in the values of catalytic activity with respect to the molar amount of an aqueous-alcoholic solution of rhodium or ruthenium salt with the addition of ammonia to the molar amount of surfactant in the range from 1: 1 to 10: 1.

Claims (2)

1. A method of producing a catalyst for isotope exchange of protium-deuterium, including the production of metal nanoparticles in a reverse micellar solution consisting of a solution of a metal salt, a surfactant, which is sodium bis (2-ethylhexyl) sulfosuccinate, and a non-polar solvent, isooctane, followed by coating on a carrier characterized in that the reduction of the metal salt occurs upon interaction with quercetin, Sibunit is used as a carrier, and RhCl ₃ or RuOHCl _{3 is} used as a metal salt, and reverse micellar solutions are prepared rhodium or ruthenium creatures in the ratio of molar amounts of an aqueous solution of a metal salt to a molar amount of a surfactant in the range from 1: 1 to 10: 1, then an aqueous-alcoholic solution in the amount of 5-50 wt.%, a solution of quercetin in an amount of 0.5- 5 wt.% And ammonia solution in an amount of 10-30 wt.%. 2. The method of producing a catalyst for the isotope exchange of protium-deuterium according to claim 1, characterized in that isopropanol is used as the alcohol in the aqueous-alcohol solution.