Method of production of formic acid formates

FIELD: chemistry.

SUBSTANCE: preparation of liquid flow I, containing formic acid, and liquid flow II, containing alkali metal formate, is carried out; liquid flows I and II are supplied to rectification column in such way that for liquid flow II place for feeding into rectifying column is chosen higher than place of feeding liquid flow I, or the same place as for liquid flow I, liquid flows I and II are mixed in rectification column, removing water from upper part of rectification column, and lower flow, containing formic acid formate is removed from rectification column, lower flow being separated in form of melt, which contains less than 0.5 wt % of water.

EFFECT: improved method of production of formic acid formates.

10 cl, 4 ex

 

The invention relates to a method for arabinoxylan formate and arabinoxylan formate obtained in this way, for canning and/or acidification of vegetable and/or animal material for processing biological waste, and as an additive in animal feed or as growth promoters.

Muraveinike the formate have antimicrobial activity and are used, for example, for canning, as well as acidification of plant and animal materials, such as grasses, agricultural products or meat, for processing biological waste or as an additive in animal feed.

Arabinoxylane the formate are compounds and mixtures which contain formate anions (NCOO-), cations (Mx+) and formic acid (HCOOH). They may be present together in the form of solids or liquids, and may optionally contain other components such as other salts, additives or solvents, for example water. In General muraveinike the formate can be represented by the formula

where M stands for a monovalent or polyvalent inorganic or organic cation, x is a positive integer and indicates the charge of the cation, and shows the molar fraction of Murav the Noah acid, based on the formate anion. The molar proportion of formic acid, based on the formate anion, is usually from 0.01 to 100, preferably from 0.05 to 20, particularly preferably from 0.5 to 5 and in particular from 0.9 to 3.1.

The nature of the inorganic or organic cation Mx+in principle immaterial provided that the said cation is stable under conditions in which acid formate should be handled. This includes, for example, the stability of the remedial action formate anion. Possible inorganic cations are monovalent and/or polyvalent metal cations 1-14 groups of the Periodic system of elements, such as lithium (Li+), sodium (Na+), potassium (K+), cesium (Cs+), magnesium (Mg2+), calcium (CA2+), strontium (Sr2+) and barium (BA2+), preferably sodium (Na+), potassium (K+), cesium (Cs+) and calcium (CA2+). Possible organic cations are unsubstituted ammonium (NH4+and ammonium, substituted by one or more carbon-containing radicals, which also may not necessarily be related to each other, for example matrimony, dimethylamine, ammonium, ethylamine, diethylamine, triethylamine, pyrrolidine, N-methylpyrrolidine, piperidine, N-methylpiperidine or pyridine.

Operadagen is ASCII organic radical is unsubstituted or substituted aliphatic, aromatic or alifaticheskimi radical having from 1 to 30 volumes of carbon. This radical can contain one or more heteroatoms, such as oxygen, nitrogen, sulfur or phosphorus, for example-O-, -S-, -NR-, -CO-, -N=, -PR - and/or-PR2and/or be substituted by one or more functional groups, which contain, for example, oxygen, nitrogen, sulfur and/or halogen, for example fluorine, chlorine, bromine, iodine and/or cyano (radical R in this case is similar to the carbon-containing organic radical). Carbon-containing organic radical may be monovalent or multivalent, such as divalent or trivalent.

There are many ways to get arabinoxylan formate. In these ways, usually prepared liquid flow I, containing formic acid, and the liquid flow II containing formate metal, and the above-mentioned liquid streams I and II are mixed to obtain the product stream containing muravlensky formate, which is then optionally processed.

This method is disclosed, for example, in DE-A 10237379. According to this method streams containing formic acid and formate metal, unite preferably in the column, which is usually manipulated in such a way that part of the supplied solvent, usually water, is removed. This process can be obtained from the lower ring, containing mu is vinocity formate and having a water content of from 0.5 to 30 wt.%, in particular, having a water content usually less than or equal to 1 wt.%.

On the contrary, despite the expected advantages in further processing of the product stream containing the acid formate, a specialist in this field should not assume that it is possible to obtain a product stream having a water content that is noticeably lower than with the known methods, directly from the column in which the mixed streams containing formic acid and containing formate metal.

Thus was developed the method of obtaining arabinoxylan formate, which serves

- liquid flow I, containing formic acid and

- liquid flow II containing formate metal,

liquid flows I and II served in the distillation column so that the liquid flow II choose a seat located above the inlet liquid flow I in the distillation column, or the same location as for flow I, the liquid streams I and II are mixed in a distillation column, removing water from the upper part of the distillation column, and

the bottom stream containing muravlensky formate, is withdrawn from the distillation column, which differs in that the bottom stream is isolated in the form of a melt containing less than 0.5 wt.% water.

In a preferred form of execution of the method of preparing the liquid flow I, sod is Rashi formic acid, which is a relatively highly concentrated, i.e. contains at least 85 wt.% formic acid. Particularly preferably, the liquid stream 1 contains at least 94 wt.%, in particular 99 wt.%, formic acid. In this case, mainly the use of formic acid such classes, which are commercially available, for example formic acid having a purity of 85, 94 or 99%.

The above-mentioned liquid flow I, containing formic acid, preferably is a water stream.

The inventors have found that if you use concentrated solutions of formic acid, you can get a lower residual water content in the target product, the formic acid diformate than in the melt extracted from the distillation column, in which the mixed liquid flows I and II, in particular the residual water content of less than 0.3 wt.%, preferably in the range from 0.2 to 0.1 wt.% and in particular from 0.1 to 0.05 wt.%.

The inventors also found that if the trend towards the reduction of water content in the liquid stream I and other constant conditions in a distillation column, the water content in the melt is selected in the lower part decreases.

Lower residual water content in the melt decisive effect on the storage stability of the finished end product Muravlenko is on deformity: the lower the residual water content in the final product, the weaker the tendency to caking or be prone to lumping.

A further advantage compared with the process involving a higher water content in the liquid stream I, is that to obtain a melt having a low water content, rather fewer theoretical plates, in particular from 4 to 8 theoretical plates less. Accordingly, the distillation column can also be designed smaller and, therefore, with lower capital and operating costs.

Preferably each of the liquid streams I and II is a water stream.

The method is not limited to specific ways of obtaining liquid flows I and II. Preferably they can be prepared as described in the application DE-A 10321733, which is incorporated by reference in its entirety into this application.

Liquid flow I can be obtained, for example, by partial hydrolysis of methylformate, hereinafter abbreviated as MeFo (stage (a) of the process according to DE-A 10321733), and removal by distillation of unreacted MeFo and methanol.

Liquid flow II can be obtained, for example, various methods described in DE-A 10321733.

According to this document MeFo - and etanolsoderjasimi stream can be converted to stage C) of the process in metal-formate - and in doctorjay stream II by

i) interaction with the base compound with a constant pKandthe conjugate acid of the corresponding state dissociation ≥3, measured at 25°in aqueous solution in the presence of water, and

ii) removal of methanol by distillation.

For a more detailed description of stage C) of the process, reference is made to the aforementioned application DE-A 10321733.

In another alternative embodiment, it is possible to obtain the flow II containing formate metal, by carbonylation of the corresponding metal hydroxide. This method is described in the application DE-A 10237380, the contents of which are thus in detail incorporated in full by reference in this application.

In the next stage of the process of obtaining arabinoxylan formate prepared threads I containing formic acid, and II containing formate, metal, mixed in a distillation column.

In this case it is possible, and likely beneficial to expose the liquid flow I, containing formic acid, and/or liquid flow II containing formate metal, before mixing in a distillation column concentration in formic acid or formate metal, in particular, by removing part of the water by evaporation, preferably by distillation.

It was found that in the operation of the distillation column to supply liquid flow II you must choose a location, RA is placed above the flow of the liquid stream I, or, at least, the same location as for the thread I. it Was found that the presence of formate metal in wide areas of the column, in particular in the areas located above the feed stream containing formic acid, is important for significant removal of water from the bottom of the stream. Significant in this case is that the metal formate in the system column acts as azeotropically for formic acid.

The preferred mode of operation of the distillation column, wherein the temperature in the lower part of the distillation column is limited to a value below 135°With, in particular value below 125°C. To do this, the specialist in this field will set the pressure in the upper part of the column, respectively, considering the well-known parameters, in particular the pressure drop occurring in the column.

In a preferred variant of the method, the place of supply of liquid flow II is located at the highest point of the dividing plates of the distillation column, which can significantly reduce costs.

In addition, or alternatively, the mode of operation of the column may influence the choice of the ratio between the liquid flows II and I: the ratio between the liquid flows II and I can be chosen so that the molar ratio of the metal formate and the liquid stream II and formic acid from a liquid stream I is more than 1 less than 1, or preferably between 0.95 and 1.05 by particularly preferably equal to 1. As a result of loss of formic acid in the upper stream of the distillation column can be limited, without zones of enrichment needed for this in a distillation column. In this case, it is possible to select virtually pure water.

When choosing separating internals for distillation columns must primarily take into account the internals with a small pressure drop and at the same time a good separating efficiency, preferably the nozzle columns.

The number of theoretical plates of the distillation column calculated in accordance with the General techniques that are common in this area. For this task separation preference, as a rule, should be given to the number of theoretical plates from 5 to 15.

The invention also relates to the use of arabinoxylan formate obtained by the method according to the invention, for canning and/or acidification of vegetable and/or animal material for processing biological waste or as additives in animal feed and/or as a growth promoter in animals.

Removing the target material, moravcikova formate, in the form of a melt having a water content less than 0.5 wt.%, in which the procedure according to the invention, in particular, in column, in which the mixed liquid streams containing formic acid and formate metal, provides significant economic advantages. In particular, for further processing of the melt is taken from the distillation column, required equipment, other than known apparatus for further processing of the product flows that have a higher water content, which is less complex and less prone to breakage, in particular the system of the cooling roller or the cooling belt conveyor, cooling plates or granulation tower. This reduces capital costs compared to plants for traditional processes that have a higher water content in the product flow.

Further process steps, such as separation of solids/liquids, crystallization and subsequent drying, which were required in the known methods are not necessary.

The invention is described in more detail below with reference to images and illustrative examples.

Figure 1 shows a schematic representation of the first installation for implementing the method according to the invention and

Figure 2 shows a schematic representation of a further preferred installation for implementing the method according to the invention.

In the first form in the execution of the method according to the invention, shown schematically in figure 1, in a distillation column R serves water stream II, containing formate metal and below the flow II serves water flow I, containing formic acid. Above the inlet water flow II is enriching zone. In a distillation column R streams I and II are mixed, and the upper stream mainly containing water, take away, this stream is condensed in the refrigerator in the upper part of the column, partially redirected to the column in reverse flow, and the balance is unloaded. From the bottom of column a melt containing less than 0.5 wt.% water, select and utverjdayut in or on the installation of the downdraft that is, From the installation downdraft E, optionally after processing in the seal, which is not shown, select the product with the desired particle size.

The preferred embodiment represented in the figure 2, differs from the embodiments in figure 1, the water flow II directed to the upper tray of the distillation column R. In this embodiment, the implementation of the distillation column R, respectively, have no zone of enrichment. Also in this embodiment, the method substantially pure water can be discharged in the upper part of the distillation column, provided that the ratio of liquid flow II and I is chosen so, that the RNA the ratio of formate metal from a liquid stream II and formic acid from a liquid stream I is greater than or equal to 1.

Examples of carrying out the invention

In laboratory column, which consisted of three or two sections, each having a diameter of 30 mm and each with 10 nozzle plates were melt diformate potassium.

Column functioned only as othonna column.

Loading consisted of aqueous potassium formate 75% concentration on the upper plate of the column and aqueous formic acid five plates below. Formic acid and sodium formate was applied to the stoichiometric ratio.

Deformat potassium, with different contents of water released from the bottom, and from the upper part of the column produced almost pure water containing residues of formic acid number of less than 1000 mlnc

In the examples, the concentration of formic acid in the loading was changed. In addition, at each concentration of formic acid in the first experiment (hereinafter denoted by the subscript A) was carried out at a higher pressure in the upper part, and the further experiment (hereinafter denoted by the subscript C) was carried out at a lower pressure in the upper part.

Example 1A

The concentration of formic acid in the loading was 30 wt.%. The convoy consisted of three sections, the pressure drop through the column was approximately 35 mbar. The column operated at a pressure in the top 50 mbar. The temperature at the bottom is Asti was between 132 and 135° C. In the melt in the lower part of the column was achieved by a water content of about 0.45 wt.%.

Example 1V

The concentration of formic acid in the load, the number of sections in the column and the pressure drop through the column remained the same as in example 1A. The column operated at a pressure in the top 20 mbar and the temperature in the lower part between 122 and 127°C. the Melt having a water content of about 0.35 wt.%, were taken from the lower part of the column.

Example 2A

The concentration of formic acid in the loading was 85 wt.%. The convoy consisted of two sections, the pressure drop through the column at approximately 25 mbar. The column operated at a pressure above about 35 mbar. In the melt diformate potassium withdrawn from the lower part of the column was achieved, the temperature in the lower part of about 126°and a water content of between 0.18 and 0.2 wt.%.

Example 2B

The concentration of formic acid in the load, the number of sections in the column and the pressure drop through the column remained the same as in example 2A. The pressure in the upper part reduced to about 25 mbar. In the melt diformate potassium withdrawn from the lower part of the column was achieved, the temperature in the lower part ranges from 124 to 126°and a water content of from about 0.08 to 0.12 wt.%.

Example 3A

The concentration of formic acid in the loading was 94 wt.%. The number of section is in the column and the pressure drop through the column corresponded to example 2A. The column operated at a pressure above about 35 mbar. In the melt diformate potassium withdrawn from the lower part of the column was achieved, the temperature in the lower part ranges from 126 to 128°and a water content of from about 0.08 to 0.1 wt.%.

Example 3B

The concentration of formic acid remained the same as in example 2A. The number of sections in the column, and the pressure drop through the column corresponded to example 2A. The pressure in the upper part reduced to about 25 mbar. In the melt diformate potassium withdrawn from the lower part of the column was achieved, the temperature in the lower part ranges from 124 to 126°and a water content of from approximately 0.05 to 0.07 wt.%.

Example 4A

The concentration of formic acid in the load was 99 wt.%. The number of sections in the column, and the pressure drop through the column corresponded to example 2A. The column operated at a pressure above about 35 mbar. In the melt diformate potassium withdrawn from the lower part of the column was achieved, the temperature in the lower part ranges from 124 to 126°and a water content of from approximately 0.05 to 0.08 wt.%.

Example 4B

At a constant concentration of formic acid in the loading pressure in the upper part reduced to about 25 mbar. The number of sections in the column, and the pressure drop through the column corresponded to example 2A. Temperature is round at the bottom, as well as the water content in the melt diformate potassium withdrawn from the bottom of the column were in the same range as described in example 3A. At high concentrations of formic acid used in examples 3A and 3B, respectively, found no significant influence of pressure in the upper part of the water content in the melt is taken from the bottom of the column, when the pressure in the upper part 35 mbar to 25 mbar.

Examples 2A, 2B, 3A, 3B, 4A and 4B show that in the preferred embodiment of the method using concentrated formic acid as the original thread I reached a particularly low water content in the melt is taken from the bottom of the column.

1. The method of obtaining arabinoxylan formate, which serves

liquid flow I, containing formic acid and

liquid flow II, containing the formate of an alkali metal,

liquid flows I and II served in the distillation column so that the liquid flow II choose the place of filing in a distillation column located above the inlet liquid stream I, or the same location as for flow I,

liquid streams I and II are mixed in a distillation column, removing water from the upper part of the distillation column, and the bottom stream containing muravlensky formate, select the C distillation column, characterized in that the bottom stream is isolated in the form of a melt containing less than 0.5 wt.% water.

2. The method according to claim 1, in which the content in the liquid stream I of formic acid is at least 85 wt.%.

3. The method according to claim 2, in which the content in the liquid stream I of formic acid is at least 94 wt.%, preferably, at least 99 wt.%.

4. The method according to claim 1, in which the liquid flows I and II are water streams.

5. The method according to claim 1, in which the bottom stream contains less than 0.3 wt.% water, preferably between 0.2 and 0.1 wt.% water, particularly preferably from 0.1 to 0.05 wt.% water.

6. The method according to claim 1, in which the temperature in the lower part of the distillation column is limited to below 135°C.

7. The method according to claim 6, in which the temperature in the lower part of the distillation column is limited to below 125°C.

8. The method according to claim 1, in which the place of supply of liquid flow II is chosen at or above the higher of the separation plates of the distillation column.

9. The method according to claim 1, in which the ratio of liquid flow II and I is chosen so that the molar ratio of alkali metal formate from a liquid stream II and formic acid from a liquid stream I is in the range from 0.95 to 1.05, preferably 1.

10. The method according to any one of claims 1 to 9, in which the number of theoretical plates of the rivers is ifications choose columns from 5 to 15.



 

Same patents:

FIELD: chemical industry; methods of production of the manganese salts with the organic acids.

SUBSTANCE: the invention is pertaining to production of the manganese salts with the organic acids in particular, to the salt of the divalent manganese and formic acid. The method is exercised by interaction of manganese, its oxides in the state of the highest valence with the formic acid solution in the organic solvent in the presence of iodine as the stimulating additive. The production process is conducted in the bead grinder of the vertical type having the revertive cooler-condenser, the high-speed paddle stirrer and the glass beads of in the capacity of the grinding agent loaded in the mass ratio to the loading of the liquid phase as (1÷2): 1. The liquid phase consists of the formic acid solution in the organic solvent. The concentration of the acid is taken within the range of 3.5÷10.8 mole/kg. In the loaded liquid phase they dissolve the stimulating additive of iodine in the amount of 0.025-0.100 mole/kg of the liquid phase. The ratio of the masses of the liquid phase and the total of the metallic manganese and the manganese oxide are as(4.9÷11):1. The molar ratio of the metal and the oxide in the loading is as (1.8÷2.,2):1. The metal and the oxide are loaded the last. It is preferable in the capacity of the dissolvent to use the butyl alcohol, ethyl acetate, ethylene glycol, 1.4-dioxane, dimethyl formamide. The production process is started and conducted at the indoor temperature up to practically complete(consumption of the whole loaded manganese oxide. Then the stirring is stopped, the suspension of the salt is separated from the beads and the nonreacted manganese and after that conduct filtration. The filtrate and the nonreacted manganese are returned into the repeated production process, and the filtered out settling of the manganese salt is exposed to purification by recrystallization. The technical result of the invention is - simplification of the method at usage of accessible reactants.

EFFECT: the invention ensures simplification of the method at usage of accessible reactants.

16 ex, 2 tbl

FIELD: concentration of pentaerythrite formate mother liquors in the multi-case evaporation plant with vertical heat exchange tubes for production of high-quality lacquers, additives for oils and other products.

SUBSTANCE: proposed method includes concentration of pentaerythrite formate mother liquors at the first stage by evaporation to saturation state by pentaerythrite and crystallization of pentaerythrite from saturated solution; concentration at the first stage is performed at film flow solution; crystallization is carried out at two stages at forced circulation of suspension thus formed. Secondary vapor is divided into two flows after first stage of evaporation: one flow is delivered to the first stage of crystallization and second flow is delivered to the second stage of crystallization. At the second stage of crystallization boiling point of suspension is maintained at temperature of 45-53°C which is below that at the first stage by 7-20°C. Evaporation plant for processing the pentaerythrite formate mother liquors has two stages of evaporators connected in succession in way of flow of vapor and solution and provided with vertical tubes. Second stage of evaporation plant is just crystallizer provided with circulating loop with pump and vapor separator connected with final condenser by means of vapor pipe line. First stage consists of film liquid flow evaporator; second stage is provided with additional crystallizer with circulating loop and pump and additional condenser connected with vapor separator of additional crystallizer; it is also provided with non-condensable gas discharge unit. Last evaporator of the first stage is provided with additional pipe line for discharge of secondary vapor which is communicated with heating chamber of additional crystallizer. Solution volume of additional crystallizer exceeds that of the first one by 1.5- 2.5 times.

EFFECT: improved quality of crystalline products; increased degree of extraction of pentaerythrite from solution; increased rate of processing the solutions.

6 cl, 1 dwg, 1 tbl

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

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

FIELD: chemistry.

SUBSTANCE: invention concerns platinum-group metal salt synthesis, particularly of palladium salts, namely palladium (II) acetate applied as catalyst or for obtaining basic salt to produce other palladium salts. The method for obtaining palladium acetate involves dissolution of metal palladium in concentrated nitric acid, evaporation of obtained solution and reaction with acetic acid, where, after evaporation but prior to palladium (II) nitrate crystallisation, the palladium nitrate solution is processed by a mix of acetic acid, acetic acid ethyl alcohol and acetic anhydride at (60-80)°C with (2.0-3.0) l of ice-cold acetic acid, (0.8-1.0) l of ethylacetate and (0.4-0.6) l of acetic anhydride per 1 kg of dissolved palladium for at least 1 hour, the resulting solution is heated at (90-110)°C for at least 3 hours and at (135-145)°C for at least 6 hours.

EFFECT: obtaining high yield of monophase palladium (II) acetate without admixture of insoluble polymeric palladium (II) acetate and palladium (II) nitritoacetate.

3 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention concerns platinum-group metal salt synthesis, particularly of palladium salts, namely palladium (II) acetate applied as catalyst or for obtaining basic salt for production of other palladium salts. The method for obtaining palladium acetate involves dissolution of metal palladium in concentrated nitric acid, filtration and evaporation of palladium nitrate solution and reaction with acetic acid, where after evaporation but prior to palladium (II) nitrate crystallisation the palladium nitrate solution is processed by distilled water in the volume of (2-5) l per 1 kg of palladium in the initial nitrate solution, then by acetic acid diluted with water, with acid concentration of (30-70)% and volume of (1.5-2.5) l of acetic acid per 1 kg of palladium in the initial nitrate solution, the resulting solution being matured for at least 8 hours at (15-40)°C.

EFFECT: streamlined method for obtaining palladium (II) acetate and its synthesis in monophase condition without admixture of insoluble polymeric palladium (II) acetate and palladium (II) nitritoacetate.

2 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry of derivative transition metal and can be used in chemical industry while producing transition metal carboxylate and refers to improved method of zirconium carboxylate production through interreacting of zirconium chloride with carboxylate derivatives of general formula RCOOM, where R-linear and branched alkyl CnH2n+1 or non-saturated acid residue, where n=0-16, and M - proton or cation of alcali metal, in which alkali acid of aliphatic or non-saturated acids are used as RCOOM compounds, interacting of zirconium chloride with the compounds leads to solvent absence in solid with mechanical activation at mole ratio ZrCl4: RCOOM within 1<m<4.5, where m is integral and broken number with the following extraction of derived zirconium carboxylate with an organic solvent.

EFFECT: duration decrease and efficiency increase of zirconium carboxylate production; elimination of chemically pollutant effluents formation.

5 cl, 1 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to perfection of the method of obtaining manganese salicylate (II), which can be used as a reagent and catalyst of chemical transformations in laboratory and industrial practicale. The method involves reaction of metallic manganese and its dioxide with acid in the presence of an organic solvent and an iodine stimulating additive in a vertical type bead mill with glass bead as a grinding agent in the absence of supply of external heat. The content of salicylic acid and iodine in the load is 0.8÷2.2 and 0.04÷0.07 mol/kg respectively. Manganese dioxide is taken in molar ratio to the acid of 1: (4.0÷4.2) and 1:(1.9÷2.3) to metal. Mass ratio of the load to the glass beads is 1:1.5. The load is taken in the order glass beads, solvent, acid, stimulating additive, metal and then its dioxide. The process itself is started with mixing and is carried out at room temperature until complete exhaustion of the metal dioxide, after which mixing is stopped. The suspension of the product is separated from the glass beads and particles of unreacted manganese by passing through a filtering partition wall in form of a net with cell dimensions of 0.4÷0.5 mm. The obtained product residue from filtering is washed in liquid solvent, after which it is taken for cleaning by re-crystallisation. The filtrate, washed by the solvent and unreacted metal is returned for a repeated process.

EFFECT: obtaining manganese salicylate with direct reaction with salicylic acid in solutions at room temperature.

2 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to the perfection of the method of obtaining iron benzoate (III) from magnetite and crushed cast iron with their reaction with benzoic acid. The method is achieved through reaction of iron and its oxide with benzoic acid in an organic solvent in the presence of a stimulation additive in a small vertical mill. The liquid phase used is a 2.0-3.5 mol/kg solution of benzoic acid in a mixture of dimethyl formamide and an h-butyl spirit in a volume ratio of 2:3. The liquid phase is dosed with glass beads in a ratio of 1:1 and crushed pieces of cast iron with maximum linear diameter of up to 5 mm in a ratio of (3.3-4):1. The iron oxide Fe3O4 (magnetite) is loaded in a molar ratio to the acid of 1:(14-20). The stimulating additive used is molecular bromine or iodine in a quantity of 0.1 mol/kg. The process starts with preparation of the solution of the benzoic acid in a mixture solvent with heating, and addition and dissolving of the stimulating additive. At the end, the crushed cast iron and the iron oxide are added and heated to 70-90°C, with routine control using the method of selecting samples for accumulation of iron (II) and (III) salt in the reaction mixture until a practically quantitative disintegration of the acid. Stirring is then stopped. The reaction mixture is the separated from the glass beads and unreacted particles of cast iron, by passing through a filtering partition wall in the form of a group openings with diameter of 0.6-0.8 mm in the field of a magnet, are cooled down to 5-14°C with stirring and are taken for filtration. The sediment of the product is washed in a cooled solvent of a liquid phase, which is mixed with the primary filtrate and returned into the repeated process. The salt is accumulated and taken for cleaning through crystallisation.

EFFECT: obtained product accumulates in the solid phase in the reaction mixture and can be easily separated through usual filtration.

1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to the improved method of obtaining iron benzoate (III) through interaction of crushed iron with an acid with sparging air as an oxidising agent with use of stimulating additives in the reactor with a high speed blade mixer, in which the liquid phase is in the form of a 3.5-3.9 mol/kg solution of benzoic acid in a mixture of dimethyl formamide and n-butyl alcohol in mass ratios 1:1-1:1.5, containing 0.03-0.07 mol/kg iodine as a stimulating additive, which is brought into intensive contact with the crushed iron in mass ratio 4.44:1. The process itself starts with preparation of a solution of benzoic acid and iodine in a solvent mixture and is put into a vertical bead mill with mass ratios of the liquid phase to the glass bead of 1:1 with sparging air at a rate of 0.3-0.5 l/min for 1 kg of the liquid phase and temperature between 70°C and 80°C, maintained through a liquid heating bath, until full expenditure of the loaded acid. Mixing is then stopped. The reaction mixture is separated from the glass beads and unreacted particles of iron by passing through a metallic net, located in the field of a magnet. Filtering is then carried out. The residue obtained at the filter is dried or heated for recrystallisation from acetone, and the filtrate is analysed for content of iron salts and is returned to the repeated process.

EFFECT: perfection of the method.

2 cl, 17 ex, 2 tbl

FIELD: organic compounds technology and industrial ecology.

SUBSTANCE: target products can be used for preparing electrolytic copper coating electrolytes, for inhibiting equipment corrosion, as fungicides and agricultural copper microfertilizers, for antibacterial treatment of water, and for other purposes. Compounds of copper(II) with amino carboxylic acids are prepared via crystallization from aqueous solution prepared by mixing amino carboxylic acid or its alkaline metal salt with radioelectronic production waste, namely with spent solutions used for etching different circuit plates and containing, as chief components, copper(II), mineral acid, ammonium or cupric salt, ammonia, and ammonium salt.

EFFECT: reduced expenditures on preparation of target compounds, extended assortment of materials for preparation thereof, and enabled reuse of toxic radioelectronic production waste.

13 cl, 5 ex

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to technology for synthesis of organic compounds, in particular, to a method for synthesis of neodymium carboxylates used as catalysts in the stereospecific polymerization reaction of butadiene-1,3. Invention describes a method for synthesis of neodymium carboxylates by dosing carboxylic acid sodium salt of acid number 0.5-0.7 as a solution in sodium hydroxide at pH 9-10 to neodymium nitrate nitric acid solution at pH 0.4-0.6. The process is carried out in organic solvent under control of acid number value and pH values of solutions of the parent compounds. Proposed method provides excluding formation of by-side products and provides synthesis of stable carboxylate solutions without addition of stabilizing additives with required amount of free acid that exerts significant effect on stability and viscosity of the ready product.

EFFECT: improved method of synthesis.

2 ex

FIELD: organic synthesis.

SUBSTANCE: invention concerns an improved method for synthesis of manganese(II) succinate tetrahydrate wherein manganese(II) carbonate is portionwise added to succinic acid aqueous solution at molar ratio 1:1:4.5, respectively, under continuous stirring and, while maintaining constant temperature 60-65°C, each subsequent portion being added after complete dissolution of preceding manganese carbonate portion, after which desired product is isolated via recrystallization. Method can be used under industrial-scale conditions.

EFFECT: improved purity of product and minimum reactants used.

3 dwg, 2 tbl, 5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of saturated aliphatic carboxylic acids with stable carbon isotopes (1-13C). Method involves the hydrocarboxylation reaction of α-olefins with carbon monoxide (13CO) and water at temperature 100-170°C and under pressure not exceeding 5 MPa in the presence of a solvent and catalytic system containing palladium compound as complex PdCl2(PPh3)2 and triphenylphosphine PPh3 taken in the ratio from 1:2 to 1:100, respectively. Synthesized carboxylic acids can be used as diagnostic test-preparations in medicine practice and in criminology, scientific investigations and in other fields. Invention provides synthesis of enanthic acid and caprylic acid labeled by stable carbon isotope 13C at position 1 for a single step, to increase yield of acids as measured for isotope raw, to decrease cost price of acids and to obtain derivatives of (1-13C)-caprylic acid - (1-13C0-caprylate sodium and (carboxy-13C)-trioctanoine.

EFFECT: improved methods of synthesis.

9 cl, 6 ex

FIELD: organic chemistry, chemical technology, medicine, pharmacy.

SUBSTANCE: invention relates to novel synthetic 2-(α-hydroxypentyl)benzoates of the general formula (I): wherein M means a monovalent metal ion, bivalent metal ion or a basic organic group chosen from a aniline group, benzylamino-group, morpholinyl group or diethylamino-group and wherein n = 1 or 2. Also, invention relates to methods for synthesis of these compounds and pharmaceutical compositions containing these salts as active components. Also, invention relates to using abovementioned compounds in prophylaxis and treatment of heart ischemia, brain ischemia, occlusion of heart and brain arteries.

EFFECT: valuable medicinal properties of compounds and pharmaceutical compositions.

14 cl, 3 tbl, 20 ex

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