The method of producing carboxylate ruthenium (iii)

 

(57) Abstract:

Describes how to obtain the solution of the carboxylate of ruthenium (III), which includes the interaction of the oxide of ruthenium (IV) with hydrazine powered by a reducing agent in the presence of carboxylic acids and includes the first stage of recovery of ruthenium (IV) ruthenium (III) the specified reducing agent in the presence of carboxylic acid and the second stage of aging at elevated temperature of the ruthenium (III) over a long period of time from 8 to 24 hours Technical result - obtaining high purity of the desired products in high yield. 5 C.p. f-crystals.

The invention relates to improvements in the field of compounds of precious metals, and more specifically to improvements in the field of ruthenium compounds and methods for their preparation. In particular the invention relates to a method of producing carboxylate ruthenium (III).

Acetate, ruthenium (III) is a term which in the present description used to refer to [Ru3O(SLA)6(H2O)n(AcOH)3-n]OAc, where n= 0-3, and the product of its desolvatation, i.e., [Ru3O(SLA)6]OAc, and products, including mainly acetate, ruthenium (III), possibly in a mixture with a small stake connection, which although is commercially available, however, is not a product of mass production or chemical consumer products. It can be used as source material for other ruthenium compounds and the intended field of application are the catalysts and catalyst precursors.

Well-known ways of getting acetate, ruthenium (III) include the interaction RuCl3xH2O or with acetic acid/acetic anhydride or sodium acetate in ethanol, but the drawback of such methods is rather low yield of the product and its contamination of other ruthenium materials such as [Ru2(OAc)4Cl] , as well as chloride and/or sodium ions. Another option is the interaction of the oxide of ruthenium (VIII) with a mixture of acetic acid and a reducing agent, such as acetaldehyde or ethanol. This latter reaction is associated with a particular risk due to the hazardous nature of the oxide of ruthenium (VIII), although the implementation of this method would be expected outputs high-purity product. There is a need to develop other methods acceptable for use in large-scale production of high-purity is i.i.d. product, containing impurities such as halide, which can be attributed to corrosion of the installation and/or reaction system, as well as unwanted metal impurities, which may be due to the loss of selectivity of catalytic processes. Another unwanted impurity is sulfur, which is well known as a catalytic poison.

The present invention is to eliminate the above disadvantages.

The task is achieved by the described method to obtain a solution of the carboxylate of ruthenium (III), which includes the interaction of the oxide of ruthenium (IV) with hydrazine powered by a reducing agent in the presence of carboxylic acid and which includes a first stage recovery of ruthenium (IV) ruthenium (III) the specified reducing agent in the presence of carboxylic acid and the second stage of aging at elevated temperature of the ruthenium (III) over a long period of time from 8 to 24 hours

In a preferred embodiment, the carboxylate is an acetate, and carbolic acid is an acetic acid.

The invention describes a method of producing acetate solution of ruthenium (III) with high yield, which includes the interaction of the lots.

This method is carried out in two stages, the first of which is the recovery of ruthenium (IV) to ruthenium (III) with hydrazine powered reductant in the presence of acetic acid, followed by aging at elevated temperatures, preferably at the boiling temperature for a long period, for example 8-24 hours as explicitating reagent can be used glacial acetic acid, however, the preferred aqueous solution of acetic acid, prepared by diluting glacial acetic acid a small amount of water, making it easy to prepare a solution of acetate of ruthenium (III) with the preferred content of acetic acid.

The recommended amount of hydrazine powered solvent - hydrazine - make 95-115% of the stoichiometric required. The stoichiometry of this reaction requires 1 mol of hydrazine to 4 mol of ruthenium as hydrazine acts as a reducing agent with 4 electrons. In a preferred embodiment, the amount of hydrazine should be as close to stoichiometric, which allows to avoid significant over - or nedoustanovlennoy ruthenium (IV) materials. In this process hydrazine converted into gaseous nitrogen, Catholicosate and in the form of a pure liquid or in the form of hydrazine powered salt, in solid form or in the form of a solution. Hydrazine powered by the reducing agent can serve as a substituted hydrazine, such as methylhydrazine, and in this case, the stoichiometry must be different. However, it is likely that in this case of the substituted hydrazine would be formed undesirable side products, such as methylamine, which would contaminate the finished product. For some applications such admixture may be negligible.

I believe that the reaction of recovery can be described using the following equation:

3RuO2HN2O+3/4N2H4+ASon-->[Ru3O(SLA)6(H2O)3]OAc+(2+3)H2O+3/4N2< / BR>
It may be necessary to get this product in the form of a solution by cooling the reaction mixture and removal of all unreacted oxide of ruthenium (IV) by filtration or centrifugation. It is possible to allocate in the form of solids using a variety of media, obvious to a person skilled in the art, such as the concentration of a solution, spray drying or precipitation of the connection processing at low temperature or by addition of an appropriate solvent.

Describes also aceta is such as nitrogen (not higher than 200 ppm million), the halide (not exceeding 50 part./million). Preferably the solution contains not more than 50 ppm million of sulfur and not more than 100 ppm million of metallic impurities. In the most preferred embodiment, the concentration of acetic acid in the resulting solution is in the range of 40-80 wt.%, and the concentration of ruthenium is in the range of 4-8 wt.%.

Source material, hydrated oxide of ruthenium (IV), is a known compound, but for the implementation of the present invention it is desirable to prepare a recovery ruthenate (IV) sodium using alcohol. Ruthenate (IV) sodium is a known product.

The present invention also includes other ruthenium carboxylates that can be obtained similarly as receive acetate.

Hereinafter the invention is described on the example of the working of the experiment below.

Example. 43,88 g of hydrated oxide of ruthenium (IV) obtained by the method described above, was transferred to a 250-ml chemical beaker and thoroughly mixed with 42,3 g glacial acetic acid, and then the mass was transferred into a 250-ml round-bottom flask equipped with a rod stirrer with Teflon seal. This suspension was washed facilities what omashu pipettes for 10 min was slowly added 4,37 g of solution in water concentration 15,26 wt.%. The amount of hydrazine powered solution was 110% of the stoichiometric amount, defined on the basis of the calculated content of ruthenium in the reaction mixture. There was a rapid separation of the liquid gas bubbles and a gradual increase in the temperature for approximately 15oC. To return condensate to the flask was supplied with the refrigerator Liebig and the contents gently warmed up to the boiling point, after which boiling was continued for 21 h, and during this time the reaction mixture turned into a dark green solution. The stirring was stopped, the flask was allowed to cool and left to stand for 24 hours, the Contents were filtered through a paper circle of glass fiber with a diameter of 7 cm, receiving 141,0 g transparent dark green solution, which contained 5,59% wt. ruthenium in the form of compounds of ruthenium (III). This is consistent with the overall product yield of 98.5%. Such a solution of the product contained less than 50 ppm million halide and less than 100 ppm million of nitrogen.

1. The method of obtaining the solution of the carboxylate of ruthenium (III), which includes the interaction of the oxide of ruthenium (IV) with hydrazine powered by a reducing agent in the presence of carboxylic acids and includes the first stage of recovery of ruthenium (IV) Ruth temperature of the ruthenium (III) over a long period of time from 8 to 24 hours

2. The method according to p. 1, in which the reducing agent is hydrazine powered represents a substituted hydrazine.

3. The method according to p. 2, in which the substituted hydrazine is methylhydrazine.

4. The method according to any of the preceding paragraphs, in which the carboxylate is an acetate and the carboxylic acid is acetic acid.

5. The method according to any of the preceding paragraphs, where the specified reducing agent is contained in the amount of 95-115% of the stoichiometric amount.

6. The method according to p. 4 or 5, in which the concentration of ruthenium in the resulting solution is 4-8 weight. %, and the concentration of acetic acid - 40-80 weight. %.

 

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