Method of preparing iron(iii) formate in presence of hydrogen peroxide

FIELD: inorganic synthesis.

SUBSTANCE: invention relates to preparation of salts of transition metals with organic acids, in particular to formic acid ferric salt. Method is accomplished via oxidation of ferrous formate with hydrogen peroxide in presence of formic acid and in absence of any dorm of iron as reducer in order to prevent reduction of ferric salt into original ferrous salt. As reducer, ferrous formate is used preliminarily recrystallized and dried or filtered off from reaction mixture suspension. Process is carried out in upright bead mill in two steps. In the first step, ferrous formate powder or precipitate is combined, stepwise or in one go, with 85% formic acid or mixture of filtrate with wash water formed during isolation of desired product to form pasty slurry ensuring stable functioning of bead mill. Second-step operation is effected in bead mill functioning mode involving forced cooling through side surfaces of reactor and continuous introduction of 12.5-25% hydrogen peroxide solution at a rate of 3.25-4.24 g H2O2 per 1 kg starting charge until degree of Fe(II) salt conversion achieves 85-90%. Supply velocity is then lowered until complete conversion is reached. Resulting product slurry is separated from beads and filtered. Filter cake is washed with 85% formic acid and recrystallized in saturated ferric formate solution containing 20-30% of formic acid. Wash liquid is combined with filtrate and used in the first step as described above.

EFFECT: increased yield of target product and simplified its isolation step.

1 tbl, 8 ex

 

The invention relates to the technology of ferric salts and low molecular weight fatty acids and can be used in various fields of industrial and laboratory chemicals, scientific research and analytical testing of various objects.

A known method of producing formate, iron (II) by the interaction of iron sulfate (II) and sodium formate, which indicated that the product is poorly soluble in water and resistant to oxidation in air (U.S. Pat. US No. 2688032 from 31.08.1954). These properties of the product and ensure the implementation specified in the patent exchange process.

On the other hand, there is no reason to assume that a similar type of exchange process may be implemented to obtain formate, iron (III). Moreover, there is no information about the solubility of salts of trivalent iron, which plays a primary role in shifting the equilibrium of the exchange process in the desired direction.

Closest to the claimed is a method of obtaining basic formate and acetate India (A.S. USSR №454198), according to which the metal is subjected to interaction with acid in the presence of hydrogen peroxide in the periodic heating to 80-100°and subsequent isolation of the product by evaporation of the solution.

The disadvantages of this method are

1. Complete uncertainty,how will hydrogen peroxide in suspension formate, ferrous iron, in particular, will there be a preferential oxidation of Fe2+in Fe3+or will dominate the catalysis of homolytic and heterolytic decomposition of the peroxide with the formation of oxygen as a product of oxidation under the influence of salts of trivalent iron, etc. anyway, iron and indium as the metal not the same and to make any conclusions by analogy hardly justified.

2. Temperature 80-100°for most heterolytic reactions of hydrogen peroxide is too high. On the contrary, these temperatures should help homolytic and induced collapse of this oxidant.

3. In the system with no indium rich solid phase salt in the reaction mixture, which is to highlight the product has to be was evaporated. In the case of formate, iron (II) solid phase due to the poor solubility of this salt should be. You can expect that it will and in the presence in the reaction mixture of formate, iron (III). While not obvious, such as solid phase will affect the stability and effectiveness of hydrogen peroxide as oxidant.

4. Salt of iron (III) can oxidize the metal with the formation of salts of iron (II). Therefore, it is not obvious that in the presence of hydrogen peroxide product will be the salt of iron (III), but not the salt of divalent iron.

5. From the group of salt-product by evaporation - long-lasting and energy-intensive operation that should be avoided.

The objective of the proposed solution is to find such conditions oxidation of a suspension of formate, iron (II) hydrogen peroxide, which would provide almost quantitative conversion of the salt of divalent iron salt is ferric, thus renounce evaporation as required surgery for the selection of the target product.

This objective is achieved in that the process is conducted in the absence of iron as a reductant in any form, as the reductant used is obtained by any method previously recrystallized and dried or shoutfactory of the suspension of the reaction mixture formate, iron (II), and the process is carried out in a bead mill, vertical type in two stages: at the first powder or shoutfactory precipitate formate, iron (II) fractional input if necessary, the selection of the optimum number or one dose if previously found optimal amount of 85%formic acid or obtained by the Department of formate, iron (III), the filtrate is mixed with wash with formic acid in the mode of episodic mixing turned into quite moving and leggierissimo pasta grayish-greenish color, and the second include paramesh the existence in permanent operation, serves cooling through the side and bottom surfaces of the reactor and start a continuous dosage of 12.5-25%-aqueous solution peroxide hydrogen with a speed of 3.25 4,24 g H2O2in min per 1 kg initial load and up to 85-90% of the degree of consumption of formate, iron (II), is close to a constant, and in the final stages with decreasing, and in this mode, bring the process to practically complete conversion of the salt of iron (II) salt of iron (III), after which the dosage of peroxide solution, stirring and cooling stops, the suspension of the product of a brick-red-brown color is separated from the beads and direct the filtered; the precipitate is washed on the filter with 85%formic acid and sent to recrystallization from 20-30% formic acid in the saturated formate, iron (III) at room temperature the solution, and the wash liquid is combined with the filtrate and used for preparation of solution for the recrystallization of the product for transfer of powder or sludge formate, iron (II) in the slurry, paste or accumulate for subsequent consolidation and allocation of additional quantities of formate, iron (III).

Characteristics of the raw materials used

Formate, iron (II) was prepared as follows:

1. Through direct interaction powdered iron and its alloys (steel, iron) from 4.5-10 mol/kg in the Noah formic acid at 45-65° In the presence of stimulating supplements of iodine in the number 0,016-0,164 mol/kg liquid phase and the bubbling of the air.

2. Through direct interaction powdered iron and its alloys (steel, iron) in any mass ratio between them at room temperature in the presence of iodine(bromine)containing stimulating additives and continuously fed into the reaction zone of hydrogen peroxide as oxidant.

3. By direct interaction of powdered iron and its alloys with 23-46%formic acid in bead mill at 55-75°in the presence of Fe2O3or Fe3O4as an additional oxidant and a major supplier of cations for the target salt product.

4. By direct interaction of powdered iron and its alloys in any mass ratio between them with formic acid in a solution of organic solvent and water in a mass sootnoshenii solvent: formic acid: water 100:(85÷100):(15÷0) in the presence of 0.03-0.10 mol/(kg of liquid phase) of iodine as stimulating supplements, and Fe2About3and (or) Fe2O4as an additional oxidant and primary provider cation for the target salt product.

5. By the exchange interaction between the iron sulfate (II) and sodium formate mode US patent No. 2688032.

Use the Ali: shoutfactory precipitate formate, iron (II), received 1-5 - ways, and recrystallized and dried product.

Formic acid according to GOST 5848-73.

Hydrogen peroxide according to GOST 10929-76.

Distilled water on THE 6709-72.

The process of the claimed method in a bead mill next. First selected as the reductant formate, iron (II) translate into quite fluid and leggierissimo paddle mixer pasta-suspension. For this purpose, the powder is recrystallized and dried formate, iron (II) or shoutfactory precipitate this connection moisten with formic acid or a filtrate (a mixture of filtrate and wash acid)obtained by the selection of the final product, i.e. formate, iron (III). The amount of liquid phase wetting depends on, is there a powder formate, iron (II) or shoutfactory sediment. In the first case, it is the largest, second tends to a minimum. This number is determined experimentally by the method of fractional enter the liquid phase and episodic mixing after each entry. In those cases, when it is known, all of the liquid phase can be introduced in one step.

After this paste is a suspension of the reducing agent prepared (which indicates the completion of the first stage), include mechanical mixing of the contents of the reactor in mode is e permanent job enter the cooling of the reactor through its lateral and bottom surfaces and commence continuous dosage of an aqueous solution of hydrogen peroxide with controlled velocity: first, with close to a constant, at the completion of phase with decreasing. The process is conducted at very close to room temperature until almost complete spending just downloaded reductant. Upon reaching this point the dosage of hydrogen peroxide, stirring and cooling stops, the suspension of the salt of iron (III) (product) is separated from the glass beads and served on the filtering. The precipitate on the filter is washed with a solution of formic acid and sent to recrystallization from a saturated formate, iron (III) solution of formic acid. The wash liquid is combined with the filtrate and used to soak the source of reducing agent for the preparation of the starting solution for the recrystallization of the product or simply accumulate for subsequent consolidation and allocation of additional quantities of formate, iron (III) as the target product.

Example 1

In ball mill vertical type with glass enclosure and a mechanical stirrer (1440 rpm) blade type, the shaft and the blade which is made of Teflon, load 100 g of glass beads, 45 g of powder formate, iron (II) and 5 g of 85%m is RAVENOL acid. Scroll the mixer manually for a more or less uniform distribution of the loaded mass in the reaction zone of the apparatus. After 5 minutes of entering the second portion of formic acid in an amount of 5 g and again manually scroll a mechanical stirrer. The operation of the fractional input formic acid 5 g every 5 min and the scrolling shaft mixer manually spend 2 more times. All this is performed at room temperature. In the end, put the powder formate, iron (II) becomes fluid and leggierissimo agitator slurry paste grayish-greenish color. At this preparatory stage is completed.

The reactor vessel is placed in a cooling water bath, include mechanical mixing and continuous supply of 12.5%aqueous hydrogen peroxide solution with the mass rate of 3.84 g of N2O2/(min·kg load). The time taken for the beginning of the process. We control the quality by changing the color transitions in the reaction zone and the method of sampling for the conversion of salts of iron (II) salt of iron (III). First place entry peroxide appears red-brown spot, which quickly eroded at the edges, due to mixing of the reaction mass. Then flushes all of the weight, the color gradually becomes brick red and then in a brick-brown-red and all the time deepens. By the end 48 min USP is pointed to react more than 85% of the original salt of iron (II). The mass flow rate of peroxide reduce first 2 times, and then after 5 min 3 times. For 15 minutes this mode, the degree of conversion of the downloaded formate, iron (II) salt of iron (III) lead to almost 100%. The temperature of the reaction mixture at this point was 33°C.

Stop a continuous supply of hydrogen peroxide in the reaction zone, switch off mechanical stirring and remove forced cooling of the reactor. The latter is disconnected from the lid with automatic feed oxidant and placed on it the reflux-condenser, a stuffing box, a loading opening and a slot sampler. The reaction mixture was separated from the beads by filtration through a mesh filter instead of a partition, and then filtered. Sediment brick-brown washed on the filter with 85%formic acid in order to complete the transformations of the basic formate, iron (III) in medium salt of trivalent iron, after which he sent to recrystallization from a saturated formate, iron (III) solution of formic acid with the content of the last 20%. The recrystallized salt is filtered and dried without any restrictions contact with air. End up with 57 g of powder brick-brown, the analysis corresponding to the formula Fe(OS(O)H)3.

Flush water volume is inaut with the primary filtrate and accumulate to further enhance and highlight additional servings of iron (III). This mixture can be used in the main process for the initial wetting of the powder formate, iron (II) and a paste for oxidation by hydrogen peroxide.

Examples No. 2-8

Laboratory setting, bead mill reactor, the boot order of the reagents, the stages of the process, the sequence of operations, as well as in the separation of the reaction mixture from the beads and the selection of the target product are similar to those described in example 1. Different ways of obtaining the source of formate, iron (II), the degree of its purification and drying, the composition and amount of liquid phase that is added in the first stage, with the aim of turning the original solid phase reductant in leggierissimo in terms of bead mill pasta-suspension, the nature of the entry of such liquid phase, the input speed of the oxidant (in terms of 100%N2O2and the nature of its changes in the final stages of the process. The results obtained are given in table. Legend: SST - dry recrystallized formate, iron (II); WITH N... - their precipitate formate, iron (II) filtering the reaction mixture (slurry)obtained by the method described in the section characteristics of the feedstock with the corresponding number; MK - 85%formic acid; SFC - a mixture of filtrate and wash formic acid; α - the degree of p is euromania of formate, iron (II).

The positive effect of the proposed solution is as follows:

1. As the oxidant used is available hydrogen peroxide in a fairly large range of concentrations.

2. The process is conducted at room temperature and does not require any specific organizations cooling. This predetermines a fairly simple instrumentation of this process.

3. At room temperatures formate, iron (III) is poorly soluble in water and in solutions of formic acid and mainly accumulate in the solid phase, which greatly facilitates its selection.

4. The product is easily purified by conventional recrystallization.

5. The product in your environment (i.e. in the absence of iron and other reductants) and close to the room temperature stable and does not require any specific additional measures in this plan.

6. Despite the fact that most of the used reducing agent is in the solid phase, the process goes pretty quickly.

The method of producing formate, iron (III) in the presence of hydrogen peroxide as oxidant, wherein the process is conducted in the absence of iron as a reductant in any form, as the reductant used is obtained by any method previously recrystallized the first and the dried or shoutfactory of the suspension of the reaction mixture formate, iron (II), and the process is carried out in a bead mill, vertical type in two stages: at the first powder or shoutfactory precipitate formate, iron (II) fractional input if necessary, the selection of the optimum number or one dose if previously found optimal amount of 85%formic acid or obtained by the Department of formate, iron (III) in the mixture of filtrate with a wash of formic acid in the mode of episodic mixing turned into quite flexible and easy stir pasta-suspension grayish-greenish color, and the second include mixing in permanent operation, serves cooling through the side and bottom surface of the reactor and start a continuous dosage of 12.5-25%-aqueous solution of hydrogen peroxide with a speed of 3.25 4,24 g H2O2in min per 1 kg initial load and up to 85-90%of the consumption of formate, iron (II) with close to a constant, and in the final stages with decreasing, and in this mode, bring the process to practically complete conversion of the salt of iron (II) salt of iron (III), after which the dosage of peroxide solution, stirring and cooling stops, the suspension of the product of a brick-red-brown color is separated from the beads and direct the filtered; the precipitate is washed on the filter with 85%formic acid and e.g. the keys on recrystallization from 20-30%of formic acid in the saturated formate, iron (III) at room temperature the solution, and the wash liquid is combined with the filtrate and used for preparation of solution for the recrystallization of the product for transfer of powder or sludge formate, iron (II) in the slurry, paste or accumulate for subsequent consolidation and allocation of additional quantities of formate, iron (III).



 

Same patents:

FIELD: inorganic synthesis.

SUBSTANCE: invention relates to preparation of salts of transition metals with organic acids, in particular to formic acid ferric salt. Method is accomplished in bead mill provided with mechanical blade-type stirrer in aqueous formic acid solution (5-10 mole/kg). Iron is used in the form of steel sidewall across the height of reactor and also as particles of reduced iron stirred with stirrer together with glass beads, and/or as broken steel cuttings, and/or yet as split cast iron in any weight proportions. Method is accomplished by continuously introducing 10-20% hydrogen peroxide solution at a rate of 0.015-0,030 mole peroxide/min per 1 kg liquid phase (salt slurry) in presence of stimulating additive, in particular iodine, bromine, alkali metal or ferrous iodides or bromides in amounts (on conversion to halogens) 0.1-0.15 vole per 1 kg reaction mixture. When 1,2-1,5 mole/kg of ferrous salt is accumulated in reaction mixture, stirring and addition of hydrogen peroxide solution are stopped, product slurry is separated from unreacted iron and/or its alloys as well as from glass beads and filtered. Filtrate is recycled into process and precipitate is recrystallized from saturated iron formate solution of aqueous formic acid solution (1-2 mole/kg).

EFFECT: simplified finished product isolation stage, reduced total process time, and reduced power consumption.

1 tbl, 11 ex

FIELD: chemical industry; methods of production of the salts of iron and the organic acids.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the salts of iron and the organic acids, in particular, to production of the salt of the ferrous iron and the formic acid. The method is realized by the direct interaction of the acid with the iron, its alloys and the ferric oxides. The crumber with the beads and the backflow condenser is loaded with the organic solvent, the formic acid and the water in the mass ratio of 100:(85÷100): (15÷0). As the organic solvent they use ethylcellosolve, butyl acetate, butyl and amyl alcohols, ethylene glycol. The mass ratio of the beads and the liquid phase is 1:1. Ferric oxideFe2O3 orFe3O4 and the iodine are loaded in the amount of 0.40-0.56 or 0/21-0.42 and 0.03-0.1 mole/kg of the liquid phase accordingly. The iron is introduced in the form of the steel shell along the whole height of the reactor and additionally in form of the reduced iron, the fractions of the broken cast iron with dimensions of up to 5 mm and the steel chips in any ratio among themselves at total amount of 20 % from the mass of the liquid phase. The process is conducted at the temperature of 35-55°С practically till the complete consumption of the ferric oxide. The gained suspension is separated from the beads and the metal particles of the greater dimensions and subjected to centrifuging or sedimentation. The clarified liquid phase is returned to the repeated process, and the solid phase is dissolved at stirring action and warming up to 85-95°С in the water solution of the formic acid saturated by the ferric formiate (II) up to 1-2 mole/kg. The present solid impurities are removed at the hot filtration process and the filtrate is cooled and the salt crystals are separated. The technical result of the invention is simplification of the technology of the production process with utilization of the accessible raw.

EFFECT: the invention ensures simplification of the technology of the production process with utilization of the accessible raw.

3 cl, 17 ex

FIELD: chemical industry; methods of production of the salts of iron and the organic acids.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the salts of the metals of the organic acids, in particular, to production of the salt of the ferrous iron and the formic acid. The method is realized by the direct interaction of the formic acid water solution with the iron and/or its alloys and the ferric oxidesFe2O3 and Fe3O4 in the bead crumber of the vertical type along the whole its height with the steel shell, with the heat supply and equipped with the mechanical stirrer and the backflow condenser-refrigerator. The apparatus is loaded with 23-46 % water solution of the formic acid as the liquid phase in the mass ratio with the glass beads as 1:1.25 and then introduce the oxide - Fe3O4 orFe2O3 in amount of 0.27-0.49 or 0.48-0.64 mole/kg of the liquid phase accordingly, and besides in amount of 18 % from the mass of the liquid phase they add the powder of the reduced iron and-or the crushed cast iron, and-or the crushed steel chips in any mass ratios. Switch on the mechanical stirring and heating and keep the temperature in the reaction zone within the limits of 55-75°С. The process is terminated, when practically the whole loaded oxide is completely consumed. The suspension of the salt is separated from the non-reacted iron, its alloy and the beads and dilute with the water up to the contents of the formic acid within the limits of 1-2 mole/kg. The gained mass at stirring action is slowly heated up to temperature of 85-95°С, controlling transformation of the solid phase into the solution. The gained solution is subjected to the hot filtration, evaporation, cooling and separation of the salt crystals. The filtrate and the earlier the gained distillate are sent back to the repeated process. The technical result of the invention is simplification of the technology of the production process with utilization of the accessible raw.

EFFECT: the invention ensures simplification of the technology of the production process with utilization of the accessible raw.

10 ex

FIELD: production of salts of organic acids, salt of ferrous iron and formic acid in particular.

SUBSTANCE: proposed method consists in loading preliminarily prepared aqueous solution of formic acid at concentration of 4.5-10 mole/kg into reactor provided with bladed mixer, back-flow condenser-cooler and air bubbler. Then, powder of reduced iron and/or broken iron and/or steel chips at any mass ratio in total amount of 20.0-30.6% of mass of liquid phase and stimulating iodine additive in the amount of 0.016-0.164 mole/kg of liquid phase are introduced. Reactor may be provided with steel or cast iron ferrule over entire height. At mechanical mixing, consumption of air for bubbling is maintained between 1.2 and 2.0 l/(min·kg of liquid phase). Working temperature range is 45-65°C which is maintained by external cooling. Process is discontinued when content of iron salts (II) in reaction mixture reaches 1.8-2.0 mole/kg. Suspension of salt in liquid phase is separated from unreacted iron particles and is filtered afterwards. Filtrate is directed for repeated process and salt sediment is re-crystallized from aqueous solution saturated with iron formate by formic acid at concentration of 1-2 mole/kg at heating to temperature of 95°C followed by natural cooling.

EFFECT: enhanced efficiency.

1 tbl, 9 ex

FIELD: chemical industry; methods of production of the ferric formiate (III).

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the ferric formiate (III). The invention is dealt with the organic salts of the transition metals, in particular to production of the salt of the ferric iron and the formic acid. The method is realized by the direct interaction of the regenerated iron powder with the formic acid at presence of the molecular iodine and oxygen of the air as the oxidizing agents. The process is running in the medium of dimethylformamide as the dissolvent for preparation of the necessary liquid phase with the concentrations of the formic acid and iodine of 4.5-10 and 0.03-0.11 mole/kg accordingly. The mass ratio of the liquid phase and the powder of the regenerated iron is 3:1. The process starts at the room temperature and is conducted in the conditions of the forced cooling at the temperature of 50-80°С at the rate of the air consumption for the bubbling of 0.6-1.2 l\minute per 1 kg of the liquid phase. The process is terminated at accumulation of the ferric formiate (III) in the suspension up to 1-1.2 mole/kg. The suspension is separated from the particles of the non-reacted iron and then filtered. The filtrate is recycled to the repeated process, and the ferric formiate (III) (salt) is dried and either is used as required, or additionally is purified by the recrystallization. The technical result of the invention is simplification of the method with improvement of the economic indicators and the increased purity of the final product.

EFFECT: the invention ensures simplification of the method with improvement of the economic indicators and the increased purity of the final product.

8 ex

FIELD: inorganic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing metal complex compounds, in particular, to iron complex (chelate) as its concentrated solution. Method is carried out by interaction of iron salt in an aqueous medium with a chelate-forming agent wherein N,N,N',N'-ethylenediaminetetraacetic acid is used as a chelating agent and citric acid that are added simultaneously or successively. The process is carried out at temperature 70-90°C and in the process of mixing iron salt or after mixing with chelate-forming agent an aqueous solution of ammonia or ammonium citrate is added for providing pH value of the end product 2.0-2.3. The complex-forming agent can comprise succinic acid additionally. Method provides preparing iron chelate as a concentrated solution with the content of iron 60-100 g/l. Invention can be used in agriculture for root and leaf feeding of plants.

EFFECT: improved preparing method.

4 cl, 6 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: 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: inorganic synthesis.

SUBSTANCE: invention relates to preparation of salts of transition metals with organic acids, in particular to formic acid ferric salt. Method is accomplished in bead mill provided with mechanical blade-type stirrer in aqueous formic acid solution (5-10 mole/kg). Iron is used in the form of steel sidewall across the height of reactor and also as particles of reduced iron stirred with stirrer together with glass beads, and/or as broken steel cuttings, and/or yet as split cast iron in any weight proportions. Method is accomplished by continuously introducing 10-20% hydrogen peroxide solution at a rate of 0.015-0,030 mole peroxide/min per 1 kg liquid phase (salt slurry) in presence of stimulating additive, in particular iodine, bromine, alkali metal or ferrous iodides or bromides in amounts (on conversion to halogens) 0.1-0.15 vole per 1 kg reaction mixture. When 1,2-1,5 mole/kg of ferrous salt is accumulated in reaction mixture, stirring and addition of hydrogen peroxide solution are stopped, product slurry is separated from unreacted iron and/or its alloys as well as from glass beads and filtered. Filtrate is recycled into process and precipitate is recrystallized from saturated iron formate solution of aqueous formic acid solution (1-2 mole/kg).

EFFECT: simplified finished product isolation stage, reduced total process time, and reduced power consumption.

1 tbl, 11 ex

FIELD: chemical industry; methods of production of the salts of iron and the organic acids.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the salts of iron and the organic acids, in particular, to production of the salt of the ferrous iron and the formic acid. The method is realized by the direct interaction of the acid with the iron, its alloys and the ferric oxides. The crumber with the beads and the backflow condenser is loaded with the organic solvent, the formic acid and the water in the mass ratio of 100:(85÷100): (15÷0). As the organic solvent they use ethylcellosolve, butyl acetate, butyl and amyl alcohols, ethylene glycol. The mass ratio of the beads and the liquid phase is 1:1. Ferric oxideFe2O3 orFe3O4 and the iodine are loaded in the amount of 0.40-0.56 or 0/21-0.42 and 0.03-0.1 mole/kg of the liquid phase accordingly. The iron is introduced in the form of the steel shell along the whole height of the reactor and additionally in form of the reduced iron, the fractions of the broken cast iron with dimensions of up to 5 mm and the steel chips in any ratio among themselves at total amount of 20 % from the mass of the liquid phase. The process is conducted at the temperature of 35-55°С practically till the complete consumption of the ferric oxide. The gained suspension is separated from the beads and the metal particles of the greater dimensions and subjected to centrifuging or sedimentation. The clarified liquid phase is returned to the repeated process, and the solid phase is dissolved at stirring action and warming up to 85-95°С in the water solution of the formic acid saturated by the ferric formiate (II) up to 1-2 mole/kg. The present solid impurities are removed at the hot filtration process and the filtrate is cooled and the salt crystals are separated. The technical result of the invention is simplification of the technology of the production process with utilization of the accessible raw.

EFFECT: the invention ensures simplification of the technology of the production process with utilization of the accessible raw.

3 cl, 17 ex

FIELD: chemical industry; methods of production of the salts of iron and the organic acids.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the salts of the metals of the organic acids, in particular, to production of the salt of the ferrous iron and the formic acid. The method is realized by the direct interaction of the formic acid water solution with the iron and/or its alloys and the ferric oxidesFe2O3 and Fe3O4 in the bead crumber of the vertical type along the whole its height with the steel shell, with the heat supply and equipped with the mechanical stirrer and the backflow condenser-refrigerator. The apparatus is loaded with 23-46 % water solution of the formic acid as the liquid phase in the mass ratio with the glass beads as 1:1.25 and then introduce the oxide - Fe3O4 orFe2O3 in amount of 0.27-0.49 or 0.48-0.64 mole/kg of the liquid phase accordingly, and besides in amount of 18 % from the mass of the liquid phase they add the powder of the reduced iron and-or the crushed cast iron, and-or the crushed steel chips in any mass ratios. Switch on the mechanical stirring and heating and keep the temperature in the reaction zone within the limits of 55-75°С. The process is terminated, when practically the whole loaded oxide is completely consumed. The suspension of the salt is separated from the non-reacted iron, its alloy and the beads and dilute with the water up to the contents of the formic acid within the limits of 1-2 mole/kg. The gained mass at stirring action is slowly heated up to temperature of 85-95°С, controlling transformation of the solid phase into the solution. The gained solution is subjected to the hot filtration, evaporation, cooling and separation of the salt crystals. The filtrate and the earlier the gained distillate are sent back to the repeated process. The technical result of the invention is simplification of the technology of the production process with utilization of the accessible raw.

EFFECT: the invention ensures simplification of the technology of the production process with utilization of the accessible raw.

10 ex

FIELD: production of salts of organic acids, salt of ferrous iron and formic acid in particular.

SUBSTANCE: proposed method consists in loading preliminarily prepared aqueous solution of formic acid at concentration of 4.5-10 mole/kg into reactor provided with bladed mixer, back-flow condenser-cooler and air bubbler. Then, powder of reduced iron and/or broken iron and/or steel chips at any mass ratio in total amount of 20.0-30.6% of mass of liquid phase and stimulating iodine additive in the amount of 0.016-0.164 mole/kg of liquid phase are introduced. Reactor may be provided with steel or cast iron ferrule over entire height. At mechanical mixing, consumption of air for bubbling is maintained between 1.2 and 2.0 l/(min·kg of liquid phase). Working temperature range is 45-65°C which is maintained by external cooling. Process is discontinued when content of iron salts (II) in reaction mixture reaches 1.8-2.0 mole/kg. Suspension of salt in liquid phase is separated from unreacted iron particles and is filtered afterwards. Filtrate is directed for repeated process and salt sediment is re-crystallized from aqueous solution saturated with iron formate by formic acid at concentration of 1-2 mole/kg at heating to temperature of 95°C followed by natural cooling.

EFFECT: enhanced efficiency.

1 tbl, 9 ex

FIELD: chemical industry; methods of production of the ferric formiate (III).

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the ferric formiate (III). The invention is dealt with the organic salts of the transition metals, in particular to production of the salt of the ferric iron and the formic acid. The method is realized by the direct interaction of the regenerated iron powder with the formic acid at presence of the molecular iodine and oxygen of the air as the oxidizing agents. The process is running in the medium of dimethylformamide as the dissolvent for preparation of the necessary liquid phase with the concentrations of the formic acid and iodine of 4.5-10 and 0.03-0.11 mole/kg accordingly. The mass ratio of the liquid phase and the powder of the regenerated iron is 3:1. The process starts at the room temperature and is conducted in the conditions of the forced cooling at the temperature of 50-80°С at the rate of the air consumption for the bubbling of 0.6-1.2 l\minute per 1 kg of the liquid phase. The process is terminated at accumulation of the ferric formiate (III) in the suspension up to 1-1.2 mole/kg. The suspension is separated from the particles of the non-reacted iron and then filtered. The filtrate is recycled to the repeated process, and the ferric formiate (III) (salt) is dried and either is used as required, or additionally is purified by the recrystallization. The technical result of the invention is simplification of the method with improvement of the economic indicators and the increased purity of the final product.

EFFECT: the invention ensures simplification of the method with improvement of the economic indicators and the increased purity of the final product.

8 ex

FIELD: anti-conglomeration agents.

SUBSTANCE: invention relates to loose product based on potassium formate, which contains 0.1 to 1% water and 0.5-5% water-soluble conglomeration-preventing agent, such as potassium carbonate or potassium hydroxide, which possesses affinity for water and corresponds to equilibrium humidity below equilibrium 15% relative humidity (22°C) for potassium formate.

EFFECT: provided modifying and conglomeration preventing agents for potassium formate to allow it to achieve looseness under practical storage and processing conditions.

3 cl, 4 tbl, 4 ex

The invention relates to an improved method of separation of polyols, such as neopentyl glycol or atrial, and sodium formate or calcium, comprising adding to the mixture of the partial organic solvent, in which the polyhydric alcohol is dissolved, the crystallization of sodium formate or calcium, Department of formate sodium or calcium from the solution of a polyhydric alcohol in an organic solvent, for example, by filtration, recycling of organic solvent, cooling the solution and crystallization of a polyhydric alcohol, and as the organic solvent used solvent aromatic series such as toluene, after adding to the mixture of the partial substances organic solvent, the resulting mixture is heated to boiling point and produce at this temperature simultaneously: dehydration of the mixture by distillation with water recirculation separated from water, organic solvent, crystallization dissolved in an organic solvent, sodium formate or calcium and dissolution in an organic solvent, a polyhydric alcohol

The invention relates to a method for the simultaneous receipt of pentaerythritol and sodium formate used in the chemical, leather and paint and other industries

The invention relates to a technology for technical formate sodium from aqueous solution technical Chlorella, which is a waste product of chloroform
The invention relates to the production of sodium formiate and obtaining thus purified chloroform

FIELD: anti-conglomeration agents.

SUBSTANCE: invention relates to loose product based on potassium formate, which contains 0.1 to 1% water and 0.5-5% water-soluble conglomeration-preventing agent, such as potassium carbonate or potassium hydroxide, which possesses affinity for water and corresponds to equilibrium humidity below equilibrium 15% relative humidity (22°C) for potassium formate.

EFFECT: provided modifying and conglomeration preventing agents for potassium formate to allow it to achieve looseness under practical storage and processing conditions.

3 cl, 4 tbl, 4 ex

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