Method of production of the ferric formiate (iii)

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°ะก 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

 

The invention relates to the technology of ferric salt and formic acid and can be used in various sectors of the chemical and allied industries, laboratory practice, analytical control, as well as in scientific research in various fields.

A known method of producing formate, iron (III) by reacting the nitrate iron (III) with formic acid in an alcohol solution. The resulting red product is slightly soluble in alcohol and precipitated in the solid phase. In water it dissolves better and can attach up to two water molecules. The color becomes more yellow. In aqueous solutions of formate, iron (III) is hydrolyzed with the formation of the basic formate, iron (III) and further until hydroxide iron (III) (Kirk-Othmer Encyclopedia of Chemical Technology, 2000, vol.14, p.435).

The disadvantage of this method is that the nitrate iron (III) natural connection is not and requires its prior. The same applies to formic acid.

Closest to the claimed method is receiving basic acetate of iron (III) (application No. 2004108558/04(009022) from 20.09.05), whereby the metal in the form of iron shells and (or) powder recovered iron interacts with acetic acid in a reactor with intensive mechanical stirring at 17-2° With intense bubbling air in the absence or in the presence of stimulating additives acetic anhydride prior to the accumulation of a certain quantity of a product in suspension, followed by the separation of this suspension of heavy particles of unreacted iron, filtering basic acetate of iron (III) and returning the filtrate to boot to re-process.

The disadvantages of this method are:

1. He may not be fully implemented for the interaction of iron with formic acid for the reason that the anhydride of formic acid in nature does not exist.

2. Despite the fact that formic acid is stronger than acetic, there is no certainty that it will interact with the metal easier and faster acetic acid and will not require specific methods of encouraging this interaction.

3. Required to process the liquid phase in the form of formic acid is much less convenient in operation, primarily due to the higher volatility of such acid.

4. There is no reason to believe that the suspension of the basic acetate of iron (III) in acetic acid and the suspension of formate, iron (III) in formic acid will be similar to one another and will have approximately the same technological characteristics.

The objective of the proposed solution is p is to get thinner and ranges of concentrations of formic acid and iodine in it, in which the main product of the transformation would be formate, iron (III), and the process proceeded with a good solution for technologically acceptable time.

This object is achieved in that the solvent of the liquid phase take dimethylformamide, in which dissolve 0.03 to 0.11 mol/kg of iodine and 4.5-10 mol/kg of formic acid, the liquid phase is introduced into intensive contact with powdered iron in a mass ratio of 3:1, and the process starting at room temperature and are under intensive mechanical mixing iron powder and the bubbling of air with a flow rate of 0.6-1.2 l/min per 1 kg of the liquid phase containment of the spontaneously rising temperature in the range of 50-80°through the use of forced cooling to accumulation in the reaction mixture 1-1,2 mol/kg formate, iron (III), after which stirring is stopped, give a few minutes for sedimentation of heavy particles of unreacted iron, red-brown suspension of the reaction mixture is carefully drained and sent for filtration, the precipitate filtered salt is dried, and the resulting filtrate is directed to repeat the process.

Characteristics of the raw materials used.

The reactive iron in THE 6-09-2227-81

Iodine crystal according to GOST 4159-79

Formic acid according to GOST 5848-73

N,N-dimethylformamide according to GOST 20289-74

Carrying out the process of the inventive method the following. In a reactor with intensive mechanical mixing, including the benthic zone, introducing a pre-prepared solution of iodine and formic acid in dimethylformamide or separately calculated quantity of solvent, formic acid and iodine, and then the powder recovered iron. Include mechanical stirring, served on the bubbling of the air and the time taken for the beginning of the process. Observe the change of the temperature of the reaction mixture. As soon as it begins to grow impose forced cooling of the reactor and stabilized temperature in the range of 50-80°C. Continue the process in this mode to accumulate in the reaction mixture of the target product in the amount of 1-1,2 mol/kg of the Control lead method of sampling during the process, and the determination of salts of iron (III) and (II).

Upon reaching the specified time, the stirring stopped, remove forced cooling and give a few minutes for sedimentation of heavy particles of iron. Then through the side drain pipe reactor gently poured the reaction mixture, which is a suspension mainly formate, iron (III) in the liquid phase system. Remote from the reactor the reaction mixture is sent to filtration, the filtrate is returned to repeat the process, and the residue is dried or optionally recrystallized.

An example is 1

Located in a protective steel casing glass reactor internal diameter 74,8 mm and a height of 137 mm, equipped with a reflux-condenser, high-speed paddle stirrer (1440 rpm), spaced from the bottom of the reactor is not more than 0.3 mm, the bubbler for air sampler and a loading opening, injected sequentially 120 g of dimethylformamide, of 55.5 g of formic acid and 4.5 g of crystalline iodine. End up with 180 g of the liquid phase concentrations of formic acid and iodine, respectively, 6,7 and 0,098 mol/kg. Then injected 60 g of the powder recovered iron include mechanical mixing and flow of water in a reflux-condenser. The temperature of the reaction mixture at this point was 17°C. offers air sparging with a flow rate of 0.8 l/min per 1 kg of the liquid phase. The time taken for the beginning of the process.

After 23 minutes the temperature rose to 32°C. Introducing a cooling liquid bath and stabilize the temperature at 54°C. during the process, take samples of the reaction mixture, which analyze the content of salts of iron (II) and (III). The content of the latter throughout the process was dominant and reached 1.05 mol/kg every 115 minutes after the start of the process. Stirring is stopped, remove the cooling bath and after 3 min of settling suspension is poured salt of iron (III) W is dcoi the final phase of the reaction mixture through the drain pipe at a distance of 15.8 mm from the lowest point of the bottom of the reactor. Obtain 184 g of the suspension (the dead zone of the reactor occupied by the particles of unreacted iron and the reaction mass prior experience, which eliminates loss of the reaction mixture for this reason). The last is directed to filtration, the filtrate, representing a solution of formic acid, iodine, iodide, iron (II) formate, iron (III)analyze the content of the above components and sent for subsequent loading process. And the residue of formate, iron (III) is dried. Received 34.3 g of product. If necessary, the resulting salt is additionally purified by recrystallization.

Example No. 2-8

Instrumentation, mass ratio of the liquid phase and iron and basic sequence of operations similar to that described in example 1. Differ in that the liquid phase of loading prepared in advance, as well as concentrations of formic acid and iodine in the liquid phase, the working temperature and flow of air sparging. The results obtained are summarized in the table.

Load characteristics and processExample No.
2345678
The concentration in the liquid phase, mol/kg: formic acid1093 8,45,14,51010
iodine0,030,050,070,090,110,100,07
The temperature in the reaction zone, °With: first19162122191817
at the time of filing of forced cooling33312830312527
working in the process50566469688073
The flow of air sparging, l/min per 1 kg of the liquid phase0,81,21,00,90,90,60,6
The process duration, min15910510395976782
The salt content of iron (III) in the final reaction mixture, in mol/kg1,001,091,141,121,031,201,17
Unloaded the suspension of the reaction mixture, g83 185190186183185184
The output of formate, iron (III), g31,635,938,237,131,9to 38.337,4

The positive effect of the proposed solution is as follows.

1. The proposed method is simple and uses as a provider of cation salts of iron, which is more affordable in comparison with nitrate iron (III). And as the oxidant is air, which is the natural composition.

2. Simple and instrumentation, in which there is no boiler-supervising positions. But the poor solubility of the target product used in the liquid phase greatly facilitates its selection.

3. When using reagents reactive frequency product obtained is sufficiently pure and in many cases does not require additional purification.

4. Formate, iron (III) stable to the effects of the atmosphere, and in organic media are not susceptible to hydrolysis in basic formate, iron (III) and next. So there is no need to use any protective measures in these directions.

The method of producing formate, iron (III) interaction powdered restored iron with acid in the presence of oxygen as the oxidant by eff is active sparging the reactor with a high speed blade mixer, reflux-condenser and a bubbler, characterized in that the solvent of the liquid phase take dimethylformamide, in which dissolve 0.03 to 0.11 mol/kg of iodine and 4.5-10 mol/kg of formic acid, the liquid phase is introduced into intensive contact with the powder recovered iron mass ratio of 3:1, and the process starting at room temperature and are under intensive mechanical mixing iron powder and the bubbling of air with a flow rate of 0.6-1.2 l/min per 1 kg of the liquid phase containment of the spontaneously rising temperature in the range of 50-80° through the use of forced cooling to accumulate in the reaction mixture 1-1,2 mol/kg formate, iron (III), after which stirring is stopped, give a few minutes for sedimentation of heavy particles of unreacted iron, red-brown suspension of formate, iron (III) carefully drained and sent for filtration, the precipitate filtered salt is dried, and the resulting filtrate is returned to repeat the process.



 

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