Method for treatment of complex organic mixtures from carbonyl compounds and acids

FIELD: chemical technology.

SUBSTANCE: invention relates to the improved method for treatment of organic mixtures from carbonyl compounds and acids by their treatment with sodium sulfite. Method involves using organic mixtures comprising carbonyl compounds and carboxylic acids in the ratio = 1 g-equiv. : 1 g-equiv. or with excess of acids, or with excess of carbonyl compounds. In this case before treatment with sodium sulfite carboxylic acid is added to the parent mixture in the amount to obtain the ratio of carbonyl compounds to acids as 1 g-equiv. per 1 g-equiv. and treatment is carried out with solid sodium sulfite in beaded mill with the mass ratio of the composition charge to glass beads as a grinding agent = 1:(1-2) at the rate of mechanical mixer rotation 1440 rev/min, not less, and in dosing sodium sulfite 1.2-1.5 mole per 1 g-equiv. of carbonyl compounds or excess of acid in the presence of stimulating additive up to practically complete consumption of carbonyl compounds, or carbonyl compounds and acids. Process is carried out in the presence of sodium and potassium hydroxide and acetate and sodium nitrate also as a stimulating additive taken in the amount 1-4% of mass sodium sulfite to be added up to practically complete consumption of carbonyl compounds and acids in composition to be treated. This simple method provides high degree of purification being even in small parent content of carbonyl compounds and acids.

EFFECT: improved method for treatment.

4 cl, 3 tbl, 19 ex

 

The invention relates to one of the cleaning of complex organic mixtures of contained aldehydes, ketones and carboxylic acids and can be used in various industries to improve the quality of such compositions for the intended purpose, utilization of carbonyl compounds in the schemes of waste and environmental pollution, and in many other cases.

Know the use of sodium sulfite to interact with the aldehyde in order to protect the aldehyde groups for further chemical transformations (asscr No. 571472).

Its disadvantage is that the treatment is carried out with an aqueous solution of sodium sulfite, and the desired pH of the aqueous phase of 7.0 to 8.3) support the entry of the corresponding acid supplements.

Closest to the claimed method is the selection of the aldehyde from its containing essential oils (asscr No. 1774616) by treating the latter with an aqueous solution of sodium sulfite and neutralizing the resultant alkali carbon dioxide so that during the process the pH remained in the range of 9.0 to 9.5 with a decrease to 8.0 at the end of the process.

The disadvantage of this method, as specified above, is that the processing of organic compositions are aqueous solution of sodium sulfite. From the point of view of the allocation of aldehyde that may be good, and to point the of view of further use of the remaining organic compositions such processing entails additional washing with water to remove residue containing sodium sulfite and hydrosulfite derived water phase, and then drying, which is not always rational and profitable for technological and economic reasons, and sometimes simply unacceptable.

In addition to the main drawback you can also specify other:

1. Removing the aldehyde does not automatically determines that the same way you can extract and ketones, since the reactivity of the latter is several orders of magnitude less than aldehydes.

2. The extract is present in large quantities in the system aldehyde cannot be identified with the cleaning composition from relatively small quantities of carbonyl compounds. In the first case, 80%extraction of the target component is quite a good result, and the degree of purification of 80% is a very rough clearing.

3. The duration of the extraction process is quite large (for example, 1˜3 hours). You can expect when working with low concentrations of carbonyl compounds (1-4% instead of 40%to 70%), it can further increase substantially.

4. Carbon dioxide to maintain the pH in the neutralization generated in the chemical reactions of alkali is not entirely successful reagent (poorly dissolves in water, carbonic acid is quite weak). In organic media CO2soluble in many cases even worse, and no carbonic acid cannot be formed. In other words, have to deal with heterogeneous g is tiropanis interaction of dissolved CO 2with solid sodium sulfite, which is not the same.

The objective of the proposed solution is to replace the processing of organic composition with an aqueous solution of sodium sulfite to extract from it carbonyl compounds and clear them in parallel from the acid to the processing of dry solid sodium sulfite and distribution of this admission is not only a mixture of aldehydes and carboxylic acids, but also on various ketones and mixtures of aldehydes and ketones individually and in Association with carboxylic acids.

The problem is solved in that the processing take organic compounds containing in their structure of carbonyl compounds and carboxylic acids in the ratio 1 g-EQ:1 g-EQ or with an excess of acid, or with an excess of carbonyl compounds, in this case, before treatment with sodium sulfite in the initial mixture is injected additive carboxylic acid in such quantity as to bring the ratio of carbonyl compounds and acid to 1 g-EQ 1 g-EQ and processing are solid sodium sulfite in a bead mill with a mass ratio of load composition and the glass beads of 1:1-2 and speed mechanical mixer of not less than 1440 rpm at the dosage of sodium sulfite 1.2 to 1.5 mol per 1 g-EQ carbonyl compounds or in the excess acid in the presence of stimulating additive to almost p is LEGO spending carbonyl compounds or carbonyl compounds and acids.

At the same time as the added carboxylic acid use acid having as a lower molecular weight and do not interfere in trace quantities using purified compositions by appointment.

As stimulating supplements take hydroxides and acetates of sodium and potassium and the potassium nitrate in the amount of 1-4% by weight entered sodium sulfite, respectively. In the case of original compositions with a nominal viscosity of more than 37 with the viscometer VZ-4 (20° (C) is diluted with an appropriate solvent.

Characteristics of the raw materials used

Sodium sulfite according to GOST 195-77

White spirit according to GOST 3134-78

Benzoic acid according to GOST 10521-78

Formic acid according to GOST 1706-78

Propionic acid on THE TCP 11501-63

Acetic acid according to GOST 61-75

Sodium hydroxide according to GOST 4328-77

The potassium hydroxide according to GOST 4203-65

Sodium acetate according to GOST 199-78

Potassium acetate according to GOST 5820-78

Potassium nitrate according to GOST 4217-65

The clean composition: acid oil (condensation products of volatile and carry out with the flow of air, the degradation products in the oxidation of sunflower oil for film-forming varnish type "oksol" when 120-160°and other vegetable oils, fats and their mixtures in this temperature range, low viscosity (up to 80 with the viscometer VZ-4 at 20° (C) oxidati sunflower and other vegetable oils and their blends with fats, as well as fish oil separately, solutions of oxidative and sour oils in various organic solvents, including blended, various rinsing and washing compositions and extracts etc.

Oxidati vegetable oils were obtained by liquid-phase oxidation in the last columns of the bubbler type with air in the mode of bubbling in the absence of salt catalysts at 100-160°s to a set of corresponding viscosities, depending on the nature of future use.

Some of these oxidation was dissolved in white spirit or any other solvent to form ˜ 55%-s (model drying oils of the type "oksol") and ˜ 75%solutions having a viscosity of not more than 35 with the viscometer VZ-4 at 20°C.

The process stated by the following way. Be cleaned of organic composition to analyze the content of carbonyl compounds and acids. The results of this analysis to decide whether the addition of carboxylic acid and in what quantity. If a positive decision to impose such additive, then, negative decision immediately, the working amount of the composition is placed in a ball mill. Then load the calculated quantity of sodium sulfite and stimulating Supplement. Glass beads injected into the reactor in advance. Include mechanical mixing and this is oment take at the beginning of treatment. During the process, take samples and control them to a residual content of carbonyl compounds and acids. As soon as the results of such monitoring will begin to respond to the task, stop stirring, the reaction mixture (slurry) through the filter wall in the form of a metal grid is separated from the beads and poured into the tank to defend or once allowed for filtration or centrifugation. After separation of the solid phase purified and clarified the composition is directed to the target use. The solid phase is often accumulate for subsequent discharge from her carbonyl compounds and (or) carboxylic acids. In the reactor with the remaining beads in it load a new batch of original songs and are cleaned as specified above.

Example 1

In a ball mill with stainless steel housing and blade stirrer of the same material with a diameter of 80 mm and height 200 mm load 350 g of glass beads and 350 grams of organic compounds with a nominal viscosity of 19 EOI-4 (20° (C)containing 0,056 g-EQ carbonyl compounds and 0,058 g-EQ acids. Acids a few more carbonyl compounds. The objective is to complete removal of carbonyl compounds, and acids. Therefore, sodium sulfite take in relation to the acids of 1.25: 1. Download 10 g of sodium sulfite (contents osnovnoj the substance 91,35%,), as stimulating additives injected sodium acetate (×3H2(O) number 0,140 g include mechanical stirring (speed mechanical stirrer 1570 rpm) and the time taken for the beginning of the experiment. The initial temperature in the reaction zone 14°C.

During the process, take samples of the reaction mixture, separating the liquid phase from the solid using centrifugation and define the content of carbonyl compounds and acids in the liquid phase samples. After 20 min after the start of mixing these compounds are in trace quantities. The degree of removal of carbonyl compounds and acids exceeded 98%.

Stop stirring bead mill. The reaction mixture at this point in time, had a temperature of 19°C. It is poured through the mesh and thus separated from the glass beads, bringing the suspension into the container for centrifugation. After the last within 5 min to separate the liquid phase from the precipitate, which is used for the purpose. The precipitate is collected in a separate container for accumulation with subsequent allocation of carbonyl compounds.

Released ball mill purified from the residue of the processed composition, if necessary. In further work with related compositions principle is ipiales necessary in this treatment no.

Examples No. 2-7

The reactor, the nature of the composition, the preparation of a composition for the handling, loading, operation and unloading of the reaction mixture similar to that described in example 1. Differ by a ratio of content of carbonyl compounds and acids in the composition, the input of additional acid, its nature and amount, nature and number of stimulating supplements, time and temperature characteristics of the process, methods of separation of solids of the final slurry. The results obtained are summarized in table 1. Designation: MC, MC, PC, BC - formic, acetic, propionic and benzoic acid; GN, SC, an, AK, NK - hydroxides of sodium and potassium acetates of sodium and potassium, the potassium nitrate; Oh, f, C - sedimentation, filtration, centrifugation.

Table 1
Features original compositions, download, process and separation of solids from the final suspensionExample No.
234567
Original composition:
[>C=O]0, g-EQ/kg0,150,331,050,470,750,2
[-C(O)HE]0, g-EQ/kg0,050,170,530,480,850,04
viscosity by viscometer VZ-4 at 20°s141619131714
Additional acid:
NatureMKMCPC--BC
the quantity of 102n, g-EQ3,55,5217,36--6,62
Download:
composition without added acid, g350345330340290315
sodium sulfite, g8,6919,3261,1830,8451,0015,53
a stoichiometric excess of sodium sulfite1,201,231,281,371,501,43
Stimulating Supplement:
natureAKENNC GNGKEN
amount, % by weight of sulfite1,02,53,72,94,01,9
The mass ratio of the load and glass bead1:1,11:1,21:11:1,31:21:1,5
Temperature:
initial,°192325262721
end,°222528303024
The process duration, min172432351915
The degree of purification from
carbonyl compounds, %989899999998
acids (including added), %˜1009898989898
The method of removing the solid phase from the final suspensionOCOthe FF

Examples No. 8-13

The reactor, the procedure for the preparation of a composition for the handling, loading, execution of the process of unloading the reaction mixture similar to that described in example 1. Differ by the nature of the used composition, carbonyl compounds and acids in it, a stoichiometric excess of sodium sulfite, nature and number of stimulating additives, temperature and time characteristics of the process, speed mechanical stirrer in a bead mill, and a way of separating the solid phase from the final reaction mixture. The results obtained are summarized in table 2. Designations are given in table 2 examples 2-7.

Table 2
Features original compositions, download, process and separation of solids from the final suspensionExample No.
8910111213
Original composition:
[>C=O]0, g-EQ/kg0,230,210,240,200,190,24
of them, ketones (acetone, cyclohexanone), g-EQ/kg000 0,210,120,140,070,05
[-C(O)HE]0, g-EQ/kg0,130,120,110,080,070,05
viscosity by viscometer VZ-4 at 20°s161817191817
Additional acid:
natureBCBCMKMKMCPC
number, 10 n, g-EQ3,002,703,903,603,605,70
Download:
composition without added acid, g300300300300300300
sodium sulfite, g11,9010,8612,4111,17to 10.6213,41
a stoichiometric excess of sodium sulfite1,251,251,251,351,351,35
Stimulating Supplement:ÈA;
natureENENNCNCAKAK
amount, % by weight of sulfite2,52,42,42,42,52,5
The mass ratio of the load and glass bead1:1,451:1,451:1,451:1,51:1,51:1,5
Temperature:
initial,°303030282828
end,°333333313131

Continuation of table 2
Features original compositions, download, process and separation of solids from the final suspensionExample No.
8910111213
The speed of mechanical stirrer, rpm96014401570157015701440
The process duration, min1093142455047
The degree of purification from
carbonyl compounds, %799798989898
acids (including added), %899898989898
The method of removing the solid phase from the final suspensionFCCCOF

Examples No. 14-19

The reactor, the procedure for the preparation of compositions based on oxidation sunflower oil processing, load, process, unload the reaction mixture similar to that described above in example 1. Different initial viscosity OPM to dilution with white spirit and after dilution, with the holding carbonyl compounds and acids in the composition to be processed, the input quantities of acetic acid and sodium acetate, a stoichiometric excess of sodium sulfite, temperature and time characteristics of the process, as well as a way of separating the solid phase from the end of the suspension. The results obtained are summarized in table 3

Table 3
The characteristics of the original PSO, the composition after dilution with white spirit, load, process, and separation of solids from suspensionsExample No.
141516171819
The viscosity of the original PSO, the viscometer of the OT-4 (20°)343775Outside the operation of the device
The viscosity of the composition to be processed, with the viscometer VZ-4 (20°)343715212531
The content in composition:
[>C=O]0, g-EQ/kg0,090,140,060,150,140,17
[-C(O)HE]0, g-EQ/kg0,100,090,04 0,080,110,09
102n CH3COOH g-EQ0,001,750,702,451,052,80
Download
the amount of composition to be processed, g350350350350350350

Continuation of table 3
The characteristics of the original PSO, the composition after dilution with white spirit, load, process, and separation of solids from suspensionsExample No.
141516171819
sodium sulfite, g6,288,794,0610,148,1112,31
a stoichiometric excess of sodium sulfite1,31,31,41,41,21,5
sodium acetate, % by weight of sulfite1,91,02,53,14,02,8
The mass ratio retrieve and and glass bead 1:1,51:1,21:1,31:1,11:11:1,6
Temperature:
initial,°151615172024
end,°181818192226
The process duration, min283315181721
The degree of purification from
carbonyl compounds, %979798989898
acids (including added), %969798989898
The method of removing the solid phase from the final suspensionOOFOOF

The positive effect of the proposed solution consists in the following:

1. From the process of purification of organic compositions from carbonyl compounds and acid water is completely excluded, and hence drying the purified composition is from moisture, which in some cases is of paramount importance.

2. This method allows you to clean organic compositions from many aldehydes, ketones and mixtures thereof, and provides a fairly high degree of cleaning even at low initial concentrations of carbonyl compounds and acids.

3. The method is simple, does not require the use of external heat and any special and more unique equipment.

4. The method does not exclude the utilization of recoverable carbonyl compounds and acids, provided that there would be accumulation of separated solid phases obtained in the processing of suspensions.

5. Efficiency and other characteristics of the proposed solution significantly improved when he becomes one of the stages of the gross process of obtaining not containing carbonyl compounds and acids compositions.

1. The method of purification of complex organic liquid mixtures from carbonyl compounds and acids by treating them with sodium sulfite, characterized in that the processing take organic compounds containing in their structure of carbonyl compounds and carboxylic acids in the ratio 1 g-EQ : 1 g-EQ or with an excess of acid, or with an excess of carbonyl compounds, in this case, before treatment with sodium sulfite in the initial mixture is injected additive carboxylic acid in such quantity that privest the ratio of carbonyl compounds and acid to 1 g-EQ 1 g-EQ, and handling are solid sodium sulfite in a bead mill with a mass ratio of load composition and glass beads as pereirago agent 1 : 1 - 2 speed mechanical mixer of not less than 1440 rpm at the dosage of sodium sulfite 1.2 to 1.5 mol per 1 g-EQ carbonyl compounds or in the excess acid in the presence of stimulating additive to practically complete consumption of carbonyl compounds or carbonyl compounds and acids.

2. The method according to claim 1, characterized in that as the added carboxylic acid use acid having as a lower molecular weight and do not interfere in trace quantities using purified compositions by appointment.

3. The method according to claim 1, characterized in that as stimulating supplements take hydroxides and acetates of sodium and potassium and the potassium nitrate in the amount of 1-4% by weight of the injected sodium sulfite, respectively.

4. The method according to claim 1, characterized in that in the case of original compositions with a nominal viscosity of more than 37 with the viscometer VZ-4 (20° (C) before entering sodium sulfite their diluted with an appropriate solvent.



 

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EFFECT: improved method for removing.

29 cl, 5 dwg, 13 ex

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