Method for preparing palladium acetate

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of platinum metal salts, in particular, palladium salts, namely, palladium (II) acetate. Method for synthesis of palladium (II) acetate involves dissolving metallic palladium in concentrated nitric acid, filtering and evaporation of palladium nitrate solution, its treatment with glacial acetic acid, filtration of formed sediment and its treatment with acetic acid ethyl ester and glacial acetic acid for its conversion to palladium (II) acetate followed by heating the prepared suspension for 6 h. Method provides preparing palladium (II) acetate with high yield in monophase state and without impurities of insoluble polymeric palladium (II) acetate.

EFFECT: improved method of synthesis.

3 cl, 2 tbl, 21 ex

 

The invention relates to the field of chemistry of the platinum metals, in particular the synthesis of compounds of palladium, namely the synthesis of palladium(II)acetate, used as a catalyst, for example, to obtain a vinyl acetate or source of salt for other palladium salts, for example to obtain palladium acetylacetonate.

A known method of producing palladium(II) acetate by dissolving palladium oxide in acetic acid. The palladium oxide is produced from palladium hydroxide deposited from chloride solution of palladium hydroxide sodium. (Korea Patent No. 8904783, 1989). The disadvantage of this method is incomplete dissolution of palladium oxide in acetic acid, which requires additional filter operations. While palladium hydroxide obtained by precipitation with alkali, requires a special method of filtration.

A known method of producing palladium acetate by dissolving palladium mobiles in a mixture of glacial acetic acid and concentrated nitric acid in an inert atmosphere (Japan Patent No. 61047440, 1986). The disadvantage of this method is the need for the presence of an excess of palladium mobiles throughout the process, before crystallization of the product requires filtering solution from the mob. No mobiles leads to the formation of oxidative environment in solution (due to the presence of nitrogen is iSlate or oxygen compounds of nitrogen), what contributes to the formation of insoluble in acetic acid and organic solvents polymeric palladium(II) acetate [Pd3(CH3Soo)2]n.

A known method of producing palladium (II) acetate by the interaction of palladium nitrate with acetic acid. The palladium nitrate is produced by evaporation to wet salts diluted nitric acid solution of palladium (inorganic synthesis Manual /edited Gbauer. M.: Mir, 1985. V.5, s). This method is adopted for the prototype.

The disadvantage of this method is the product not in monophasic condition and its low output. Upon receipt of palladium acetate (II) from nitrate solutions of palladium inevitably the presence of nitric acid and products of its decomposition, which contributes to the dissolution of palladium (II) acetate and reduced product yield, as well as the formation of nitriloacetate palladium (II) [Pd3(CH3Soo)5NO2]that goes into polymeric form.

The technical result, which is aimed by the invention, is to increase the output of palladium (II) acetate and getting it in monophasic state [Pd3(CH3Soo)6].

The specified technical result is achieved by the fact that the nitric acid solution of palladium after evaporation, prior to the crystallization of salt nitrate, palladium (II), amrabat who live glacial acetic acid at a temperature (20-30)° With consumption (10-11) liters per 1 kg of palladium in solution within (1-2) h, the precipitate is filtered, treated him with a mixture of glacial acetic acid and ethyl ester of acetic acid at a temperature (60-90)°for (2-5) h consumption (2-4) l glacial acetic acid and (0,05-0,2 liters of ethyl acetate for 1 kg of precipitate and heating the resulting suspension at a temperature (120-140)°With not less than 6 hours

The essence of the method is that the synthesis of palladium (II) acetate carry through the stage of formation of the intermediate - nitriloacetate palladium (II), which is then transferred to the palladium (II) acetate at an elevated temperature in the acetic acid medium using the ethyl ester of acetic acid (acetate). The ethyl acetate allows you to recover nitric acid, present as impurity in nitriloacetate palladium (II) to nitrogen oxides, which are removed from the reaction zone, and the ethyl acetate is oxidized to acetic acid, which has a negative influence on the process, not help, as it is a reagent. The absence of nitric acid prevents further formation of polymeric palladium (II)acetate.

In the course of the research it was established that for the first stage of the process - obtain the intermediate compounds of nitriloacetate palladium (II) deposition of acetic acid from nitrate RA the creators of palladium optimal conditions are:

- consumption of glacial acetic acid (10-11) liters per 1 kg of palladium nitrate in the solution;

- temperature deposition process (20-30)°C;

the content of palladium nitrate in the solution is not less than 500 g/l;

the concentration of free nitric acid not more than 200 g/l;

- duration precipitation (1-2) hours.

Increase the flow of glacial acetic acid in the process of deposition of nitriloacetate palladium (II) from nitric acid solution of palladium over 11 liters per 1 kg of palladium is inefficient because it leads to the dissolution of the formed nitriloacetate palladium (II) and reduced output. The consumption of acetic acid is less than 10 liters per 1 kg of palladium decreases the output nitriloacetate palladium (II).

The temperature of deposition of nitriloacetate palladium (II) from nitric acid solution of palladium above 30°leads to the formation of polymeric palladium (II)acetate, decreasing the deposition temperature of nitriloacetate palladium (II) below 20°leads to a reduction in output.

The palladium content in a nitric acid solution of less than 500 g/l of nitric acid, more than 200 g/l leads to a reduction in product yield.

The duration of deposition of nitriloacetate palladium (II) from nitric acid solution of palladium is less than 1 h leads to lower output. The increase in the duration of deposition of about 2 hours is impractical because not increases the yield of the product is, but it increases the total duration of the process.

It is established that for the second stage of the process - removing impurity nitric acid from nitriloacetate palladium (II) and translating it into a palladium (II) acetate optimal conditions are:

- consumption of ethyl acetate and glacial acetic acid (0,05-0,2) l (2-4) l, respectively, at 1 kg original nitriloacetate palladium (II);

- temperature treatment with a mixture of ethyl acetate and glacial acetic acid (60-90)°C;

- treatment at a temperature (60-90)° - (2-5) h;

- the temperature of the translation process of nitriloacetate palladium (II) acetate, palladium (II) (120-140)°C;

- treatment at a temperature (120-140)°With not less than 6 hours

Consumption of added ethyl acetate less than 0.05 liters per 1 kg of nitriloacetate palladium (II) leads to incomplete removal of impurity nitric acid, which, in the future, with increasing temperature leads to the formation of insoluble polymeric palladium (II)acetate. The increased consumption of added ethyl acetate 0.2 liters per 1 kg of nitriloacetate palladium (II) leads to a reduction in product yield. Consumption glacial acetic acid (less than 2 liters per 1 kg of the original salt) leads to incomplete transition nitriloacetate palladium (II) acetate, palladium (II) and education under the further heating of the polymeric palladium (II)acetate. Increase the flow of glacial acetic acid (more than 4 liters per 1 kg of the original salt) is impractical as increases the volume of the solution and the greater the solubility of the product, i.e. the reduction of the output.

Temperature processing nitriloacetate palladium (II) a mixture of glacial acetic acid and ethyl ester of acetic acid less than 60°leads to the reduction reaction activity of ethyl acetate and nitric acid, which leads to incomplete removal of nitric acid and education in further heating of the polymeric palladium (II)acetate. Temperatures over 90°leads to strong evaporation of ethyl acetate and the product with an impurity phase nitriloacetate palladium (II).

The duration of treatment of nitriloacetate palladium (II) in a mixture of ethyl acetate and glacial acetic acid less than 2 h leads to incomplete removal of impurity nitric acid, which, in the future, with increasing temperature leads to the formation of polymeric palladium (II)acetate. The increase in processing time more than 5 hours is impractical because it increases the total duration of the process.

The temperature of the secondary treatment of the reaction mixture less than 120°yields a product with an admixture of nitriloacetate palladium (II). A temperature increase of more than 140°leads to boiling of the reaction mixture.

The duration of the secondary thermal treatment of the reaction mixture less than 6 h leads to incomplete transition nitriloacetic is and palladium (II) acetate, palladium (II). The increase in time warming up increases the duration of the process.

Examples of the method:

As the initial product for experiments No. 1-10 (table 1) to obtain a palladium(II) acetate was prepared solution of palladium nitrate by dissolving palladium metal in nitric acid and evaporation. The content of palladium in the solution - 605 g/l, free of nitric acid - 189 g/l For experiments No. 11-16 (table 1) was prepared solution with different concentrations of palladium and free of nitric acid.

Example 1

In a certain amount of cooked nitric acid solution of palladium was added to the estimated volume of glacial acetic acid and stirred. The formed precipitate nitriloacetate palladium (II) was separated by filtration, were unloaded on a baking tray and dried in a drying Cabinet at 40°C for 24 hours. The residue was weighed, and analyzed for the content of palladium and determine the phase composition. The mother liquor is sent to regeneration. These experiments are shown in table 1.

The precipitate of nitriloacetate palladium (II) for carrying out the second stage of the process (translation in the palladium (II)acetate) was obtained according to the modes of experience No. 2 (table 1), as the optimal option for the first stage of the process. Sludge treatment of nitriloacetate palladium (II) in a mixture of acetic acid and ethyl acetate was carried out in the mouth the operating evaporator with heating and trapping and cooling of exhaust fumes. To a certain sample of sediment nitriloacetate palladium (II) was added to the estimated volume of glacial acetic acid and ethyl acetate. The reaction mixture is warmed up, drove ethyl acetate (condensed ethyl acetate can be used repeatedly), then raise the temperature of and even warmed up. The slurry was cooled to room temperature, the precipitate was separated by filtration and dried at 120°C for 3 hours the precipitate of palladium (II) acetate were weighed, and analyzed for the content of palladium and determine the phase composition. These experiments are shown in table 2 (experiments No. 1-20).

The mother liquor after separation of the precipitate can be re-used for the translation process of nitriloacetate palladium (II) acetate, palladium (II).

Example 2

The precipitate of nitriloacetate palladium (II)obtained according to the experiences No. 2 (table 1), was treated according to the modes of experience No. 8 (table 2), as the optimal option for the second stage of the process, but thermal processing at (120-140)°carried out without separation of the precipitate from the mother liquor. After increasing the temperature to 120°With the reaction, the suspension is passed to a complete evaporation of acetic acid and obtain a dry salt. This has increased the product yield, but increased the duration of the process (table 2, experience No. 21 ).

As seen from the above examples, the use of the proposed method allows the returns of the palladium (II) acetate with high yield in monophase state and to exclude the appearance of impurities insoluble polymeric palladium (II)acetate.

1. The method of producing palladium acetate, including the dissolution of metallic palladium in concentrated nitric acid, evaporation of the resulting solution and the processing of acetic acid, characterized in that the nitric acid solution of palladium after evaporation prior to the crystallization of salt nitrate, palladium (II) is treated with glacial acetic acid at a temperature of 20-30°C with a flow rate of 10-11 liters per 1 kg of palladium in the solution for 1 to 2 h, the precipitate is filtered, treated him with a mixture of glacial acetic acid and ethyl ester of acetic acid at a temperature of 60-90°With a flow rate of 2-4 l of glacial acetic acid and 0.05-0.2 l of ethyl ester of acetic acid per 1 kg of sediment for 2 to 5 h and heating the resulting suspension at a temperature of 120-140°With not less than 6 hours

2. The method according to claim 1, characterized in that the process of evaporation of nitric acid solution of palladium carried out until the content of palladium is not less than 500 g/l and free nitric acid not more than 200 g/L.

3. The method according to claim 1, characterized in that the heating of the suspension at 120-140°With lead to get dry salts.



 

Same patents:

FIELD: organic chemistry of complex compounds.

SUBSTANCE: invention relates to novel derivatives of metalloporphyrazine of the formula (I) that can be used as dyes, catalysts in different processes. Invention provides preparing compounds possessing with coloring properties.

EFFECT: valuable properties of complexes.

5 dwg, 4 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the formula (I): . These compounds can be used as dyes, catalysts in different processes and the material in sensitive members of gas transducers. Invention provides synthesis of compounds showing dyeing properties.

EFFECT: valuable properties of compounds.

5 dwg, 4 ex

FIELD: organic chemistry, polymers.

SUBSTANCE: invention relates to low-branched high-molecular polyvinyl acetate, methods for its preparing and to polyvinyl alcohol prepared on its base. Invention describes low-branched high-molecular polyvinyl acetate prepared by aqueous-emulsion polymerization of vinyl acetate in the presence of emulsifier and initiating agent wherein complexes of alkylcobalt (III) with tridentate ligands of the general formula (I) are used as an initiating agent taken in the amount 0.04-0.2 mas. p., and the polymerization process is carried out at temperature 10-40°C. Polyvinyl acetate prepared by this method has molecular mass 850000 Da, not less, and degree of branching 0.39-0.7. Polyvinyl alcohol with the polymerization degree 6000 Da, not less, and the saponification degree 98-99.9% that is able for making high-module fibers is prepared by saponification of indicated low-branched polyvinyl acetate.

EFFECT: improved preparing method, valuable properties of product.

3 cl, 3 tbl, 10 ex

FIELD: organometallic polymerization catalysts.

SUBSTANCE: invention relates to alkylcobalt(III) complexes with tridentate Schiff's bases wherein alkyl ligand contains functional group, notably hydroxyl, carboxyl, or amino group, in accordance with general formula:

(I),

in which W represents two-moiety unsaturated hydrocarbon bridge group expressed by formula =C(H)=C(CH3)- (propene-1,2-diyl) or o-C6H4 (o-phenylene); X is OH, NH2 or COONa; Y monovalent anion: Cl-, Br-, NO3- or ClO4-; and Z polymethylene bridge group (CH2)n, wherein n=3-11 when X = OH or NH2 and n=2-11 when X = COONa. The complex are used as initiators of emulsion polymerization and copolymerization of diene and vinyl monomers to produce reactive bifunctional oligomers and polymers with terminal functions, which oligomers and polymers are suitable for further conjugation with corresponding reagents.

EFFECT: extended choice of specific polymerization catalysts.

3 tbl, 30 ex

FIELD: chemistry of metalloorganic compounds.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazines of the general formula (I):

wherein M means Cu, Co. These compounds can be used as dyes, catalysts of different processes and material for sensitive members of gas pickups.

EFFECT: valuable properties of complexes.

4 fig, 1 dwg, 5 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the general formula (I): wherein M means Cu, Co. These compounds can be used as dyes, catalysts in different processes and materials of sensitive members of gas sensor.

EFFECT: valuable properties of compounds.

2 cl, 6 sch, 1 dwg, 5 ex

The invention relates to new derivatives of metalloporphyrins that can primeneniia as pigments, catalysts, materials sensitive elements gases

The invention relates to new substituted the phthalocyanine, which may find application as a dye, catalyst for various redox processes

The invention relates to ORGANOMETALLIC compounds, to compositions containing them and their use

The invention relates to petrochemistry, specifically to the production dialkyldithiocarbamate accelerators of vulcanization of rubbers

FIELD: chemical industry; methods of neutralization of the water combustible solutions of the acetic acids at the computerized batching-packing machine.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method neutralization of the acetic acid and its solutions at leakages and accidents. The method of neutralization of the water combustible solutions of the acetic acids at the computerized batching-packing production line provides for the treatment of the surface, on which there is a leakage of the acetic acid, with the powdery anhydrous sodium carbonate. The treatment of the spilled acetic acid is exercised till formation of the paste and the paste is left on the surface for a while. At the second and the subsequent leakage of the acetic acid on the tray and at formation of the liquid phase the place of the spill is treated with a sodium carbonate till formation of the paste with the purpose for binding the liquid phase. In the case the acetic acid spills on the surfaces located outside of the tray, the neutralization of the acetic acid is exercised by water till gaining the 25-30 % solution. The surface treatment with the powder of the sodium carbonate at the first spill is exercised at the following components ratio (in mass %): Na2CO3:CH3C00H = 1.6÷4.0:1. The invention ensures reduction of the wastes of the production process, allows to reduce emissionof CO2 and allows to diminish toxicity of the production process.

EFFECT: the invention ensures reduction of the wastes of the production process, reduction of emissionof CO2 and reduction toxicity of the production process.

FIELD: chemical industry; methods of production of acetates.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of lead tetraacetate. The method provides for realization of interaction of the red-lead with anhydrous acetic acid at the temperatures of 30-40°C with the subsequent separation of the target product not later than 3-5 hours after the termination of reaction. In the capacity of the dehydrating reagent is used the by-product of the interaction - lead diacetate, which forms the hydrated complex with water. The invention ensures production of lead tetraacetate equal to 70-75 % from the theoretical value. The technical result of the invention is simplification of the production process, improvement of the economic features.

EFFECT: the invention ensures simplification of the production process, improvement of the economic features.

1 ex

FIELD: inorganic syntheses.

SUBSTANCE: method consists in that iron powder is oxidized in acetic acid/acetic anhydride (4%) medium with air oxygen bubbled through the medium, while maintaining iron-to-acetic acid molar ratio 5:1 and temperature 17-25°C. Reaction mixture is thoroughly stirred with blade stirrer at speed of rotation 720-1440 rpm until reaction mixture accumulates 0.75-0.96 mol/kg ferric salt. Thereafter, air is replaced by nitrogen and 4% acetic anhydride based on initially charged acetic acid is added, temperature is raised to 35-40°C, and iron is oxidized with ferric salt until full consumption of the latter. Resulting snow-white ferrous acetate suspension is separated from unreacted iron, filtered off, and dried. All above operations are carried out under a nitrogen atmosphere. Filtrate, which is saturated ferric acetate solution in acetic acid/acetic anhydride mixture, is recycled to reactor to be reprocessed or it is used according another destination.

EFFECT: simplified technology and improved economical characteristics of process due to use of inexpensive oxidant.

2 ex

FIELD: inorganic syntheses.

SUBSTANCE: ferric acetate is prepared by interaction of metallic iron with acetic acid in presence of an oxidant. Process is carried out at ambient temperature in acetic acid/acetic anhydride medium (weight ratio 5:1) under nitrogen atmosphere. Molar ratio acetic acid/iron/basic ferric acetate is maintained the following: 10:8:1. Reaction mixture is thoroughly stirred with high-speed blade stirrer or shaken at shaking frequency 2 Hz. When consumption of basic ferric acetate is completed, suspension of ferrous acetate is separated by filtration from unreacted iron powder. Precipitate is dried and filtrate returned into the process.

EFFECT: simplified process due to selection of optimal oxidant.

2 ex

FIELD: industrial inorganic synthesis.

SUBSTANCE: implementation of the method comprises contacting iron in the form of iron powder or iron sidewall adjacent to a body with glacial acetic acid and air oxygen at 17-25°C and vigorous stirring effected by high-speed blade-type mechanical stirrer. Initial acetic acid-to-iron molar ratio is (224÷274):100. Acetic anhydride additive is preferably introduced in amount of 2% based on the initial concentration of acetic acid. When concentration of ferric salt in the mixture reaches 2.70-3.51 mole/kg, stirring is stopped and heavy unreacted iron particles are allowed to settle/ Major mass of product suspension is filtered off and thus obtained basic ferric acetate precipitate is dried. Filtrate, which is saturated acetic acid solution of basic ferric acetate, is returned into reactor to be reprocessed. Yield of desired product achieves 99.2-99.3%.

EFFECT: simplified process and improved economical efficiency due to utilization of inexpensive raw material and accessible oxidant.

2 ex

FIELD: organic chemistry, medicine, dermatology.

SUBSTANCE: invention relates to zinc and aliphatic halogen-carboxylic acid salts that can be used in treatment of benign neoplasms of skin and visible mucosa tissues. Invention proposes the following formula of zinc and aliphatic halogen-carboxylic acid salts: (1): wherein R means -CHal3, -CHHal2, -CH2Hal and (2): wherein R' means Alk, hydrogen atom (H); R'' means Hal; R' means Alk; R'' means H, Alk wherein in these formulae halogen atom can be represented by fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or iodine atom (J). Invention provides the development of original preparation used in treatment of benign neoplasms of skin and visible mucosa tissues with low toxicity, rapid effect, expressed therapeutic effect and eliciting good tolerance, absence of complications in treatment, healing without formation of scar tissue. The development of the preparation provides expanding assortment of agents used in treatment of such diseases.

EFFECT: enhanced and valuable properties of agents.

13 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing acetic acid salts, in particular, anhydrous ferrous (II) acetate. Method for preparing anhydrous ferrous (II) acetate involves interaction of metallic iron with acetic acid in the presence of oxidizing agents of ferric oxide Fe2O3 or Fe3O4 and molecular iodine in the mole ratio acetic acid : acetic anhydride : iron oxide = 100:(6-20):(2-2.5), respectively, and in the mole ratio iron oxide : iodine = 100:6.3. The process is carried out at temperature 80°C in the beaded mill of vertical type with high-rotation blade mixer and reflux condenser in the mass ratio of glass beads and liquid phase in the charge = 1:1. The process is carried out with periodic taking off samples of the end product solid phase by filtering and the following recover filtrate and feeding with acetic acid and iron oxide. For compensation of components loss of liquid phase in filtering there are recovered into reactor to the repeated process that is carried out for four times at a time. All procedures of the basic process and filtration are carried out in nitrogen medium. Preferably, method involves using hematite, γ-oxide, iron minium, magnetite or Fe3O4 x 4 H2O as the iron oxide source. Invention provides possibility for preparing anhydrous ferrous (II) acetate and simplifying method due to excluding the evaporation stage in isolation of salt.

EFFECT: improved preparing method.

3 cl, 2 tbl, 8 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing copper (II) acetate monohydrate that represents organic carboxylic acid salt. Copper (II) acetate monohydrate is prepared by crystallization from solution obtained by mixing acetic acid, alkaline metal acetates or ammonium with copper-containing spent solution used in etching printing boards. Method provides reducing cost of the proposed method for preparing copper (II) acetate monohydrate, retaining purity of product with simultaneous utilization of toxic waste in electronic engineering manufacture - the spent solution in etching printing boards. Also, invention provides reducing material consumptions in preparing copper (II) acetate monohydrate, expanding assortment of materials used for its preparing and utilization of toxic waste in electronic engineering manufacture. Product obtained by the proposed method can be used as pigment, fungicide and copper microfertilizer in agriculture, as catalyst in processes of polymerization, as a stabilizing agent of artificial fibers, for preparing galvanic solutions and preparing other copper compounds.

EFFECT: improved preparing method.

14 cl, 5 ex

The invention relates to the production of salts of acetic acid
The invention relates to waste disposal and the simultaneous achievement of commercial products and can be used in other industries where liquid wastes with a content of acetic acid

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing copper (II) acetate monohydrate that represents organic carboxylic acid salt. Copper (II) acetate monohydrate is prepared by crystallization from solution obtained by mixing acetic acid, alkaline metal acetates or ammonium with copper-containing spent solution used in etching printing boards. Method provides reducing cost of the proposed method for preparing copper (II) acetate monohydrate, retaining purity of product with simultaneous utilization of toxic waste in electronic engineering manufacture - the spent solution in etching printing boards. Also, invention provides reducing material consumptions in preparing copper (II) acetate monohydrate, expanding assortment of materials used for its preparing and utilization of toxic waste in electronic engineering manufacture. Product obtained by the proposed method can be used as pigment, fungicide and copper microfertilizer in agriculture, as catalyst in processes of polymerization, as a stabilizing agent of artificial fibers, for preparing galvanic solutions and preparing other copper compounds.

EFFECT: improved preparing method.

14 cl, 5 ex

Up!