The way to get calcium acetate

 

(57) Abstract:

The invention relates to the production of salts of acetic acid. Calcium acetate is produced by processing the oxide, hydroxide, carbonate or mixtures thereof 52-65% acetic acid with the stoichiometric ratio of the starting components with subsequent crystallization and drying of the product. The crystallization is carried out by exposure of the product for at least 16 h, and drying is carried out at 80-100C. as a result, the output acetate calcium rises to 88-96%, and thus attain a high degree of purity of the product. 1 C.p. f-crystals, 1 table.

The invention relates to methods of producing salts of acetic acid, in particular calcium acetate.

A method of obtaining calcium acetate, which consists in the interaction of calcium carbonate with acetic acid under heating, followed by filtration of the solution and evaporation of the filtrate under constant acidification. After cooling of the filtrate precipitated crystals of calcium acetate is separated in a Buechner funnel and dried at 60-70oC. the Yield of the target product is 53% of the stoichiometric value, purity approximately 100% (Karyakin Y. I., Angels, I. I., Pure substances, M, Chemistry, 1974, S. 153).

The implementation of this method is rather complicated and energy-intensive. Implementation (development) of this method in large-tonnage production is impractical for several reasons. The main disadvantages of the method of crystallization of calcium acetate from dilute solutions the following:

1) low yield of hydrated calcium acetate because of its high solubility in water (~ 30%);

2) separation of the crystals on the filter;

3) the presence of leachate with a high content of dissolved calcium acetate;

4) the problem of determination of calcium acetate from a solution of the filtrate (by evaporation),

5) processing and recycling of the liquid phase (filtrate).

All of the above problems are removed, if the reaction is carried out in solid phase.

A method of obtaining acetate calcium-magnesium interaction dolomite with glacial acetic acid. This method is chosen by the applicant for the prototype (Application Germany 3705618, C 07 C 53/10, 1988). The method consists in the following. The oxides or hydroxides of calcium and magnesium (calcined dolomite and/or limestone, respectively hydrated) is treated with a slight excess (2-10% better 5% relative to the stoichiometric amount) 85-100% acetic acid, the reaction is carried out in the mixer G is removed at a temperature of 110-160oC in the dryer with a movable layer of the substance.

The purity of the finished product is ~ 70% of the content of soluble impurities ~ 30%.

This method is quite technologically advanced, since the reaction is carried out in the solid phase. However, the final product is of low purity (low content of basic substance) as the excess of acetic acid leads to the formation of acid salts. In addition, used in the known method, the amount of acetic acid (relative to the amount of dolomite), and the duration of mixing dolomite with acetic acid do not provide the full completion of the neutralization of acetic acid with dolomite, because in these conditions the reaction proceeds only on the surface of solid particles, and the acid diffusion inside the particles is difficult because of the formation of calcium acetate on their surface. As a consequence, the final product is a mixture of acetate calcium-magnesium (~ 70%) and unreacted hydroxides to oxides of calcium-magnesium, as evidenced by the presence of insoluble impurities in the target product.

The finished product has a technical purpose, it is used for mixing, lowering the freezing point of water.

Such conditions of synthesis of acetate calcium help to improve the purity of the final product, because they ensure full reaction of interaction of calcium compounds with acetic acid. However, the processing of calcium compounds acetic acid in a selected ratio leads to the formation of the intermediate product, containing no liquid phase, which allows the process without filtering. The concentration of acetic acid 52-65% is optimal for the reaction without filtering, because the concentrations of acetic acid below 52% is obtained liquid paste, which should be filtered with the mission of the Department of solid crystals of calcium acetate from a solution containing 25-30% of dissolved calcium acetate. When the acetic acid concentration is above 65% obreshetochnye, as the reaction proceeds on the surface of solid particles, and the acid diffusion inside the particles is difficult because of the resulting acetate on their surface, resulting in the final product is a mixture of acetate calcium source calcium compound. When dissolved in water this product is insoluble residue CaO, Ca(OH)2or GaCO3. When the concentration of the acid 52-65% and the stoichiometric ratio of the starting components is formed a thick paste that does not contain an excess of the liquid phase. When the shutter product synthesis to drying for at least 16 h in a reaction vessel formed of white needle crystals of calcium acetate, soluble in water. Reducing the exposure time does not allow for the neutralization reaction to the end, as evidenced by the decrease in purity of acetate calcium and the presence of impurities of the source of calcium (Ca(OH)2, CaO, CaCO3) in the finished product. Extract product is much more than 16 hours (according to experimental data up to 1.5 months in a closed container) does not affect its quality.

The way in experienced production as follows: to a reactor filled stoichiometric quantity of a solution of acetic acid and poured slowly the source connection of the th portions, with stirring, poured a calcium compound within 15-30 minutes and add the remaining amount of acetic acid, cooled the reaction mass to room temperature, the semi-product is left in the reactor or unload in a plastic container and incubated at room temperature in closed containers for at least 16 hours during this time, the formation of crystals of calcium acetate. Wet acetate is dried at a temperature of 80-100oC and atmospheric pressure for 4-5 hours Drying is possible at temperatures below 80oC, however, at the same time, dehydration increases in 2-3 times. Drying at temperatures above 100oC is impractical, because there is a decomposition of calcium acetate calcium oxide and acetone.

Example 1. Synthesis of CaO

The synthesis is carried out in the mixer brand CM-25 of 25 liters, equipped with a jacket for cooling water and two Z - shaped agitators.

Calcium oxide by weight of 4.5 kg is weighed on a dial scale.

Measure 16.5 l a 55% aqueous solution of acetic acid. From this amount is poured into the mixer 8.5 l, serves cooling water in the jacket of the mixer includes a mixer and small portions sprinkled 4.5 kg CaO for 25-30 minutes the Reaction proceeds with pratury 40-50oC poured the remaining acetic acid 8,0 l

When the temperature reached in the reaction mass 25oC, the finished product is unloaded in the intermediate tank with a volume of 30-50 l, cover with a lid and incubated at atmospheric pressure and room temperature for 16 hours

Example 2. Synthesis of Ca(OH)2< / BR>
For synthesis take 6,0 kg Ca(OH)2and 16.7 l a 55% aqueous solution of acetic acid.

Synthesis is carried out as in example 1.

Example 3. Synthesis of CaCO3< / BR>
For synthesis take 6,0 kg CaCO3and 12.4 l a 55% aqueous solution of acetic acid.

Synthesis is carried out as in example 1.

Example 4. Synthesis of acetate from a mixture of calcium oxide, hydroxide and calcium carbonate carried out as in example 1, with the necessary volume of 50% acetic acid are calculated according to the formula

V.acid =aCaO3,67+BCa(OH)22,78+CCaCO3to 2.06< / BR>
whereaCaO,BCa(OH)2,CCaCO3- mass fraction of the components CaO, Ca(OH)2and CaCO3respectively;

V.acid - volume acetic acid.

For example, for the synthesis of take 6 kg of mixture (2 kg CaO, Ca(OH)2and CaCO3and

V. acid =2kgCaO3,67+2kgCa(OH)2and the qualitative characteristics of the target product are presented in table where in examples 1-11 shows the data related to the claimed invention.

Examples N 12-23 shown for comparison and contain data about the synthesis conditions outside the declare.

The table below shows results show the following:

1. Purity offered by way of acetate calcium is 100,1-101,4%, which is considerably higher than by a known method. The yield is from 88.1 to 96.4%

2. When using acetic acid above the stoichiometric ratio is formed sour salt (examples 12-14), which reduces the purity of the product;

3. If the shutter speed is wet acetate less than 16 h recrystallization of the product does not pass to the end and when dissolved in water dry acetate there insoluble impurity source of calcium, in this case, the removed product purity and yield (examples 15-17);

4. With increasing acetic acid concentration is above 65%, the reaction in the solid phase does not pass until the end and when dissolved in water dry acetate is also available insoluble impurity source of calcium, in this case decreases the purity of the product and output (examples 18-20);

5. Increasing drying temperature of more than 100oC reduces BP is LASS="ptx2">

Literature

1. Karjakin Y. I., Angels And. And. Pure substances. M. Ed. Chemistry. 1974. S. 153.

2. The application of Germany N 3705618, IPC G 07 C 3/10, priority 21.02.87.

1. The way to obtain calcium acetate, including the processing of oxide, hydroxide, carbonate or mixtures thereof with acetic acid, crystallization and drying of the product, wherein the treatment is carried out 52 - 65% acetic acid with the stoichiometric ratio of the starting components, the crystallization is carried out by exposure time product of the synthesis of at least 16 hours

2. The method according to p. 1, characterized in that the drying of the product is carried out at 80 - 100oC.

 

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