SU1446111A1 - Method of producing barium octafluorozirconate - Google Patents

Abstract

The invention relates to methods for producing a barium fluorocirconate composition and allows for increasing the yield of the target product and simplifying the process. 10 g of ammonium hexafluorocirconate are dissolved in 50 ml of water with a temperature of 50-85 seconds, 4.1-6.0 ml of 44% hydrofluoric acid are added, and 120 ml of a saturated solution of barium nitrate containing 21.67 g of Ba are poured. (NO.j) 2. The white crystalline precipitate formed is filtered, washed and dried at 190 ° C to constant weight. The product yield was 98.6-99.7%. 1 zi f-ly. € (L "and i4i) Od

Description

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The invention relates to methods for producing barium octafluorozirconate composition, which can be used as a component of the batch for optical glassmaking and replace used mixtures of simple zirconium fluoride and barium.

The purpose of the invention is to increase the yield of the target product and simplify the process by eliminating the operation of high-temperature three-phase synthesis.

Example 1. 10 g (NH, dissolved in 50 ml of water, A is added, 1 ml (Ijl from the stoichiometrically necessary) 44% aqueous solution of hydrofluoric acid, 120 ml of a saturated solution of barium nitrate containing 21, 67 are added. g of Ba (NOj). A white crystalline precipitate formed is filtered through a blue filter paper and washed with approximately 100 ml of three portions of distilled water. Then the precipitate at 190 ° C to constant weight. %

Example 2 South (NH4) ZrF6 is dissolved in 50 ml of water (temperature in a thermostat 70 C) j 5.6 m is added (an excess of 1.5 HF, 120 ml of a saturated solution of barium nitrate containing 21.67 g of sugar are added (Schz g) .The precipitate formed is treated in the same manner as in Example 1. 21.40 g Ba, r 2 gPr is obtained. The yield is 99.7%. Example H. South (NH4) iZrF is dissolved in 50 ml of water (temperature in a thermostat 55 ° C), 6.0 ml (an excess of 1.6) of 44% HF is added, 120 ml of a saturated solution of barium nitrate containing 21.67 g of Ba (NO, j) are poured in. The precipitate formed is treated in the same way as and in example 1. 21.35 g of Ba iZrFg is obtained, yield 99.5%.

Example 4. South (NH4) iZrF was dissolved in 50 ml of water, temperature in a thermostat 70 ° C), 3.7 ml (stoichiometrically required amount) of 44% HF was added, 120 ml of a saturated solution of barium nitrate containing 21 were added, 67 g of Ba (NO.j). The precipitate formed is treated in the same way as in Example 5. 18.30 g with BaZrF admixture is obtained (according to X-ray data, 12-15%). Yield 85.3%. .

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Example 5. South (. Dissolved in 50 ml of water (temperature in a thermostat is 70 ° C), 6.3 ml (1.7 from stoichiometrically required) of 44% HF are added, 120 ml of a saturated solution of barium nitrate containing 21.67 g of Ba (COZ) 2. The precipitate formed is processed in the same way as in Example 1. 19.08 g with BaF impurity (according to X-ray data not more than 5.6%) are obtained. Yield 88.9%.

Example 6. South (NH) 2ZrF is dissolved in 50 ml of water (temperature in a thermostat), 5.6 ml (excess 1.5) of 44% HF is added, 100 ml of a saturated solution of barium chloride containing 17.27 is poured g BaCl. The precipitate formed is worked up in the same manner as in Example 1. 21.40 g of BajZrFg are obtained. The yield is 99.7%.

Example 7. South (NH4) ZrF is dissolved in 50 ml of water (thermostat temperature 50 ° C), 5.6 ml (excess 1.5) of 44% HF is added, 1 20 ml of an expensive barium nitrate solution are added, containing 21.67 g of Ba (N03) 2. The precipitate formed is worked up in the same manner as in Example 1 to give 21.35 g. The yield is 99.5%.

Example 8. South (NH4) iZrF was dissolved in 50 ml of water (thermostat temperature 85 ° C), 5.2 ml (excess 1.4) of 44% HF was added, 120 ml of a saturated solution of barium nitrate containing 21.67 g of Ba (N05). The precipitate formed is worked up in the same manner as in Example I. 21.16 g are obtained. The yield is 98.6%.

Example 9. South (NHj-z i Ft is dissolved in 50 ml of water (thermostat temperature 45 ° C), 5.6 ml (an excess of 1.5) is added with 44% HF, 120 ml of a saturated barium nitrate solution are poured containing 21.67 g of Ba (NOj). The precipitate formed is treated in the same way as in Example 1. 17.69 g of precipitate is obtained, 82.1%.

Example 10. 10 g of (NH) 4ZrF was dissolved in 50 ml of water (temperature in a thermostat), 5.6 ml (1.5) of 44% HF was added and 120 ml of a saturated solution of nitrate was poured. Bari S, containing 21.67 g of Ba (NO) i. The resulting precipitate is treated in the same manner as in Example 1. 20.3 g of BajZrF.g are obtained, mixed with

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BaZrF and BaFj (according to X-ray data, 5-10%). Yield 94.6%.

Example P. South NH4ZrF5 is dissolved in 150 ml of water (thermostat temperature 70 ° C), 9.8 ml (excess 1.5) is added with 44% HF and 150 ml of a saturated solution of barium nitrate containing 25.5 are poured r Ba (B) 2. The precipitate formed is processed in the same manner as in Example 1. 18.54 g of Ba, 7, rFj are obtained. The yield is 99.6%.

Example 12. 10 g of (NH) 3ZrF-, dissolved in 100 ml of water (temperature in a thermostat 70 C), 2.4 ml (excess Ij5) of 44% HF are added and 100 ml of a saturated solution of barium nitrate containing 18.79 g. Ba (NOj) j. The precipitate formed is worked up in the same manner as in Example 1. 18.54 g are obtained. The yield is 99.6%.

Regardless of the composition of ammonium fluorozirconate with the addition of a well-defined excess (1.1-1.6 times the stoichiometrically required amount) HF (examples 1, 2, 3, 11, 12) and at a certain temperature (50-85 ° C ) (examples 6, 7, 8) is formed with a yield of 98.6-99.7%; at lower amounts, a mixture of BaZrF is formed, and at large amounts a mixture of BajZrFj and BaF (examples 4 and 5). The effect of the synthesis temperature appears as follows: with an optimal excess of HF, a decrease in temperature below 50 ° C leads to a decrease in yield (example 9 ), and the increase in temperature - to. partial decomposition (example 10).

Thus, the implementation of the invention allows, in comparison with the known method, which involves the solid-phase interaction of zirconium tetrafluoride and barium difluoride at 400-860 ° C for 48 hours, to increase the yield of the desired product from 76.1%.

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to 98.6-99.7% and simplify the process by eliminating the solid-phase synthesis operation and the associated need to use high temperatures and prolonged exposure of the reaction mixture.

In addition, according to the proposed method, soluble zirconium and barium salts are used as starting reagents, which can be relatively easily purified to the required degree of purity using relatively simple methods. The use of Ba (III) in the synthesis process makes it possible to make the technology waste-free.

The relatively low synthesis temperatures (50-85 ° C) allow the synthesis to be carried out in polyethylene vessels, which simplifies the process of obtaining the desired product.

Formula of invention

Claims (2)

1. A method for the preparation of Ba, 2ZrFg barium octafluorocyanate, includes (the interaction of fluorine-containing zirconium compounds with a barium compound, characterized in that, in order to increase the yield of the target product and simplify the process by eliminating the operation of high-temperature solid-phase synthesis, aqueous solutions of ammonium fluorocirconate and barium salts are used as starting compounds, and the process is carried out at 50-85 ° C in the presence of hydrofluoric acid, which is introduced into the initial solution in an amount stoichiometrically necessary 1.1-1.6 times, 2. The method according to claim 1, characterized in that the compounds of ammonium hexafluorozirconate are used as compounds of zirconium and barium and barium nitrate.