Method of production of iron formate (ii)

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

 

The invention relates to technology acquisition and allocation ferrous iron salt and formic acid in aqueous media and can be used in various fields of industrial and laboratory chemicals, analytical methods of monitoring and research in different directions.

A known method of producing formate, iron (II) by the interaction of sulphate of iron (II) with sodium formate in aqueous solution in an inert environment. The resulting product is slightly soluble in water and resistant to oxidation in air (U.S. Pat. US No. 2688032, publ. 1952, serial No. 311733).

The disadvantages of this method is the use as reagents soluble salts of iron (II) and sodium formate, which must be obtained by numerous chains of consecutive reactions, as well as creating and maintaining an inert environment.

Closest to the claimed is a method of obtaining acetate iron (II) (application No. 2004108557/04 (009022) op. 20.09.05), according to which first lead to the oxidation of iron powder oxygen in the mode of bubbling in the acetic acid medium in the presence of acetic anhydride under intensive mechanical stirring until the accumulation of 0.75 to 0.96 mol/kg of the salt of iron (III), and then the air is replaced with nitrogen, increase the content of acetic anhydride in the reaction mixture and the temperature in this mode are OK slania iron salt of iron (III) until complete consumption of the latter with the accumulation of salts of iron (II).

The disadvantages of this method is:

1. Obtaining salts of iron (II) in fact, only in the second stage by oxidation of iron salt of iron (III). This is predetermined by the fact that salt is iron (III) is more stable in normal conditions, i.e. in contact with air in solution, in suspension and soaked in the reaction mixture of sludge in the process of filtering and drying in comparison with the salt of iron (II). It is not necessary that this situation will continue when replacing the anion of acetic acid to formic.

2. The use environment of nitrogen in the second stage of the process, which is inconvenient and complicated instrumentation process.

3. Conducting the process in a virtually anhydrous medium, achieved by entering into the reaction mixture of acetic anhydride for removing the reaction water and stimulate redox process in General.

4. The absence of anhydride of formic acid as such makes it almost impossible for the reproduction of the model when replacing acetic acid formic.

The purpose of this solution is to get formate, iron (II) in the process where the raw materials are iron, formic acid and oxygen, the process to be held in one stage and in the aquatic environment.

Task d is attained, however, that the liquid phase of the load in the form of a 4.5-10 mol/kg of an aqueous solution of formic acid is administered in an intensive and updated with a high frequency of contact with iron and its alloys in the form of a steel or cast-iron shell over the entire height of the reactor or (and later) from 20,0-30,6% by weight of the liquid phase powder recovered iron, or pieces of broken cast iron and / or steel wool in any mass ratio between them in the presence of stimulating supplements of iodine at 0,016-0,164 mol/kg liquid phase and air sparging consumption of 1.2-2.0 l/(min·kg liquid phase), and the process starting at room temperature, is carried out in the temperature range of 45-65°in the deterrence of spontaneous growth in the use of external forced cooling and stop when you reach a content of iron salts in the reaction mixture of 1.8-2.0 mol/kg, after which a suspension of the salt in the liquid phase of the final reaction mixture is separated from the heavy particles of iron and its alloys(a) and sent to the filtration, the filtrate is returned to repeat the process, and the residue dissolved in stirring and heating of the saturated formate, iron (II) aqueous solution with a content of formic acid 1-2 mol/kg, the resulting solution was clear from nerastvorim solid impurities by hot filtration and leave on the crystallization of salt in the natural is to promote cooling, which further separated by filtration and dried.

Characteristics of the raw materials used.

Iron restored reactive on THE 6-09-2227-81

Steel 3 on CMTU 1-84-67

Steel 45 GOST 1050-74

The grey cast iron grey 15-32 according to GOST 1412-70

Iodine crystal according to GOST 4159-79

Formic acid according to GOST 5848-73

The process of the inventive method the following. In the reactor with glass enclosure in the absence or iron (steel) cowling over the entire height, as well as with high-speed paddle stirrer, well mimic the profile of the bottom and separated from it by not more than 0.3 mm, with a reflux-condenser and a bubbler for air load pre-cooked (or component-wise) aqueous solution of formic acid with a concentration of 4.5 to 10 mol/kg, injected powder recovered iron individually, or together with the fractions of broken cast iron and (or) steel wool in any mass ratio between them, but the estimated total number and stimulating Supplement of iodine at 0,016-0,164 mol/kg liquid phase. When the download is complete, the reactor is put into place in the installation serves for cooling water at a reflux-condenser, include mechanical mixing and establish a flow of air sparging. This point is considered at the beginning of the process. Watch edit the observed temperature. As soon as the latter begins to rise, impose forced cooling through the liquid bath and stabilize temperature in the range of 45-65°C. In this mode, continue the process until the accumulation of iron salts in the reaction mixture of 1.8-2.0 mol/kg Control lead method of sampling the reaction mixture and the determination of the salt content of iron (II) and (III).

Upon reaching the specified salt content in the reaction mixture, the process stops (stop stirring and sparging air, remove the reverse cooling condenser and through a liquid bath). The reaction mixture is separated from the heavy particles of unreacted iron and is sent to the filtering. The filtrate is returned to repeat the process. And the residue is dissolved under heating in saturated iron formate aqueous solution of formic acid with a concentration of 1-2 mol/kg followed by hot filtration and crystallization of the product under natural cooling.

Example 1

In placed in a protective casing of a thick-walled glass reactor internal diameter 71,3 mm and a height of 117 mm with high-speed (1440 rpm) paddle stirrer, well mimic the profile of the bottom and separated from it by 0.3 mm, with a reflux-condenser and a bubbler air load 180 g of an aqueous solution of formic acid with a concentration of 6.1 Molech, 1.27 g of iodine and 55,08 g of powder recovered iron. Serves cooling water in the cooler-condenser, to include mechanical mixing and establish a flow of air sparging 1.5 l/(min·kg liquid phase). The temperature at this time was 24°C. After 31 minutes it had risen to 39°C. the Reactor is placed in a cooling liquid bath and stabilize the temperature at 45°C. After 110 min of stirring at this temperature the salt content of the suspension was 1,80 mol/kg. stop Stirring and allow 3 minutes for sedimentation of heavy particles of unreacted iron. A suspension of the salt in the liquid phase of the system gently poured so that the particles of iron with the remnants of the reaction mixture remained in the dead zone of the reactor. Uploaded 184 g of suspension. It is directed to the filtering. The filtrate is returned to repeat the process.

The residue is dissolved in 300 g of saturated formate, iron (II) solution of formic acid with a concentration of 1.54 mol/kg with stirring and heated to 93°C for 95 minutes the resulting mass is immediately filtered at about the same temperature. The obtained filtrate is left for natural cooling and crystallization of salts within 12 hours Vykristallizovalsya salt is filtered and dried. Output 49,4,

Examples No. 2-9

Used reactor, the amount of liquid phase and consistently the th operations similar to those described in example 1. Different separate loading of water and formic acid, the presence of shells along the entire height of the reactor, the nature of the material of the shell, the concentrations of formic acid and iodine in the liquid phase of the initial reaction mixture, by using in addition to the iron powder fractions of broken cast iron and broken steel shavings and their mass ratio, dosage of shredded ferrous materials, the operating temperature of the process, the characteristic time of the termination process, the mass of the solution on the recrystallization and the concentration of formic acid in it. The results obtained are summarized in table.

Table
Load characteristics and processExample No.
23456789
Shellnononocast ironcast ironcast ironsteelsteel
The concentration of acid in the liquid phase, mol/kg7,98,310,04,5of 5.4the 5.76,16,3
The concentration of iodine in W is dcoi phase, mol/kg0,0530,0710,0160,1640,0480,0480,073of 0.081
Download:
reduced iron, g0010,0000036,004,59
broken cast iron, g55,08020,1325,2710,4835,42020,11
broken steel shavings, g055,0820,1725,3935,6310,87020,47
in sum, % of liquid phase30,630,622,428,125,625,720,025,1
Temperature, °when the process starts2321192523242018
within the operating range51584557495 6365
Air consumption, l/(min·kg liquid phase)1,21,71,41,51,61,22,01,9
The process duration, min89751838410597103111
The concentration of iron salts in the reaction mixture at the time of termination1,901,95to 1.862,001,871,931,841,97
The quantity taken for the recrystallization solution, g350330340283290290300300
The concentration of formic acid in the recrystallization, mol/kg1,001,401,272,001,841,841,751,75
The yield of dried formate, iron (II) after recrystallization, g52,853,150,255,154,353,2of 54.856,2

The positive effect of the proposed solution consists of the following is relevant.

1. There is no need to use organic solvents and inert environment.

2. In the preparation of the liquid phase can be used aqueous solutions of formic acid instead of virtually anhydrous acid.

3. When cleaning the product by recrystallization uses only components of the reaction mixture of the basic process.

4. The process occurs at low operating temperatures, which may be supported through the use of exothermic heat stages.

5. As raw materials may be used wastes iron and steel. Produced from them carbon inhibitor of the process is not and can be easily removed by recrystallization.

6. The process can be repeated many times without intermediate cleaning of the reactor and discharge dead zones, which significantly reduces the loss of the reaction mixture and favors the release of the product and waste reduction-pollution.

The method of producing formate, iron (II) by direct interaction of powdered iron with acid in the presence of oxygen as oxidant under conditions of intensive mechanical mixing, characterized in that the liquid phase of the load in the form of a 4.5-10 mol/kg of an aqueous solution of formic acid is administered in an intensive and updated with a high frequency of contact with iron is(or its alloys in the form of a steel or cast-iron shell over the entire height of the reactor or(and later) from 20,0-30,6% by weight of the liquid phase powder recovered iron or pieces of broken cast iron and / or) steel wool in any the mass ratio between them in the presence of stimulating supplements of iodine at 0,016-0,164 mol/kg liquid phase and the bubbling of air with a flow rate of 1.2-2.0 l/min-kg liquid phase, and the process starting at room temperature and are in the temperature range of 45-65°in the deterrence of spontaneous growth in the use of external forced cooling and stop when you reach a content of iron salts in the reaction mixture of 1.8-2.0 mol/kg, after which a suspension of the salt in the liquid phase of the final reaction mixture is separated from the heavy particles of iron and its alloys(a) and sent to the filtration, the filtrate is returned to repeat the process, and the residue is dissolved with stirring and heating in saturated formate, iron (II) aqueous solution with a content of formic acid 1.2 to 2.0 mol/kg, the resulting solution was clear from nerastvorim solid impurities by hot filtration and leave on the crystallization of salt in natural cooling, which further separated by filtration and dried.



 

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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.

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4 cl, 6 ex

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2 ex

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2 ex

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2 ex

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3 cl, 2 tbl, 8 ex

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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.

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3 cl, 4 tbl, 4 ex

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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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