Method of purifying vanillin obtained from lignin oxidation products

FIELD: chemistry.

SUBSTANCE: invention relates to a method of purifying vanillin obtained from lignin oxidation products, by reacting vinillin-containing extracts with aqueous solutions sodium bisulphite, followed by decomposition of the vanillin-bisulphite derivative. The method is characterised by that the vanillin-bisulphite derivative is heated in an autoclave to 120-170°C, the vapour-gas phase is released and vanillin is extracted from the obtained mixture or solution, followed by recycling the obtained aqueous solution of sulphurous anhydride and sodium sulphate into a solution of sodium bisulphite.

EFFECT: method enables to avoid the use of sulphuric acid and alkali when purifying vanillin, widely used in food, perfume, cosmetic and pharmaceutical industry.

5 ex

 

The invention relates to methods of extraction of vanillin from lignin-containing raw material and relates to the purification of extracts of vanilla, obtained by extraction of oxidized alkaline lignins, followed by separation of the target product.

Vanillin (4-hydroxy-3-methoxybenzaldehyde) is widely used in food, cosmetic and pharmaceutical industries.

A known method of purification of extracts of vanilla by recrystallization from water-methanol solutions [US 3049566, 1962]. The disadvantage of this method is the low degree of purification of vanillin raw, which requires repeated recrystallization to achieve a satisfactory cleaning. The mentioned disadvantage is due to the low occupancy separation system vanilla - impurities during crystallization from water-methanol solutions.

There is a method of allocation of vanilla and lilac aldehyde from the solution obtained by the oxidation of lignin-containing raw material, extraction of high-boiling alcohols or esters having a boiling point of more than 130°C with further reextracting aqueous-alkaline solution (alkali or soda) at a pH of 10-14 and allocation of vanilla and lilac aldehyde acidification with sulfuric acid to pH 5 (EN 2177935, publ. 10.01.2002).

The disadvantage of this method is the high tar content in the obtained concentrate, 33-44 wt.% and neobhodimosti further purification.

A known method of purification of vanillin raw by extraction with a hydrocarbon solvent, followed by crystallization of the desired product cooling solution [US 3686322, 1972].

The disadvantage of this method is the low solubility of vanillin in nonpolar hydrocarbons and the need to use the latest in high volumes.

The closest to the essence of the claimed method is a method of extraction of vanillin from one stripped off the benzene extract through its interaction with hydrogen sulfite solution of sodium NaHS3used in semi-industrial scale Syas'sky PPM [Kamardine OD, Mass AA Obtaining vanillin from lignosulfonate. - M.: CBTI ZINES, 1959, 38 S.]. In accordance with the known method vanillin from one stripped off extract extravert aqueous solution NaHS3concentration of 29 wt.%. Hydrosulfite sodium chemically reacts with the carbonyl group of vanillin with the formation of a fairly strong vanilla-sulphite derivative:

Ar-CHOorg+NaHSO3aqAr-CH(OH)SO3Naa q,(1)

where Ar-CHO vanillin.

This method has two main advantages: the possibility of concentration of vanillin in the stages of extraction-Stripping and cleaning it in the process of formation of vanillin-hydrosulfite derived. The latter is due to the fact that the reaction proceeds by a carbonyl group of vanillin and its accompanying impurities carbonyl groups are virtually absent. In the vast majority of the resins after bioliteracy remains in the organic phase, and vanilla goes in the water. Vanilla from aqueous solution hydrosulfite derived allocate acidification with sulfuric acid. The cleaned vanilla precipitates, sulfur dioxide is released in the gas phase and then is absorbed by a solution of alkali for regeneration of Hydrosulphite solution of sodium:

2Ar-CH(OH)SO3Na+H2SO42Ar-CHO+Na2SO4+2SO2+2H2O (2)

NaOH+SO2NaHSO3(3)

The main disadvantage of this method is the large consumption of sulfuric acid for separation of vanillin obtained from hydrosulfite derivative and alkali for regeneration of a solution of sodium bisulfite.

The task of the invention is to reduce the cost of sulphuric acid and alkali in the extraction of vanillin from vanilla-bisulfite derivative and regeneration of Hydrosulphite solution of sodium.

The task of the invention is achieved in that in the method of purification of vanillin obtained from the oxidation products of lignin interaction vanrenterghem extracts with aqueous solutions of hydrosulfite sodium with subsequent decomposition vanilla-hydrosulfite derived, according to the invention, vanilla-hydrosulfite derivative is heated in the autoclave to 120-170°C, dropping gas-vapor phase and extracted with vanilla from the mixture or solution with subsequent recycling of the resulting aqueous solution of sulphur dioxide and sodium sulfite in retargetability sodium.

Common features of the claimed invention and prototype - purification of vanillin obtained from the oxidation products of lignin interaction vanrenterghem extracts with aqueous solutions of hydrosulfite sodium NaHSO3with the subsequent decomposition of vanilla-hydrosulfite derived.

Distinctive features of the invention consist in the fact that vanilla-hydrosulfite derivative is heated in the autoclave to 120-170°C, dropping gas-vapor phase and extracted with vanilla from the mixture or solution with subsequent recycling of the resulting aqueous solution of sulphur dioxide and sulphite sodium Hydrosulphite solution of sodium.

The technical result of the invention is, in principle, reduce costs of sulphuric acid and alkali in the process of allocation of vanilla from its sodium bisulfite derivative. Thus, in accordance with the known method the consumption of hydrosulfite sodium is 3.2 kg per kg of vanillin, which corresponds to 4.6-fold excess of stoichiometry. For acidification requires 3 kg of concentrated sulfuric acid, and to absorb the emitted sulfur dioxide - 1,2 kg of caustic soda. According to the claimed method, the cost of these reagents is reduced to zero, more precisely, to the level of technological losses, i.e. about a hundred times.

Nathanielmichelle signs lead to the achievement of the technical result of the claimed invention, because heat Hydrosulphite solution of sodium and vanilla-hydrosulfite derived to high temperatures, 120-170°C, hydrolysis occurs hydrosulfite-ion water with the removal of the sulfur dioxide in the vapor phase together with excess water:

2NaHSO3Na2SO3+SO2+H2O.(4)

By reducing the concentration of hydrosulfite ion in solution decomposition vanilla-hydrosulfite derived to vanillin and sodium sulfite:

2Ar-CH(OH)SO3Naaq2Ar-CHOaq+Na2SO3+SO3+H2O.(5)

After extraction of vanillin balance of sodium sulfite (reaction (4)) it is enough to mix kondensator, a solution of sulphur dioxide, obtained in reactions (4) and (5), and to obtain a regenerated Hydrosulphite solution of sodium for treatment of new portions of vanilla:

Na2SO3+SO2+H2O2NaHSO3.(6)

Reactions (4) - (5) proceed at a sufficient depth only at elevated temperatures, where the acidity of the water increases so that the water as sulfuric acid at low temperatures, protonium the bisulfite ion in sulphurous acid, which decomposes to sulfur dioxide and water. Hence, the technical results and the distinctive features of the proposed method are in causal contact with each other.

The method is confirmed by concrete examples:

Example 1. In these examples used the reaction mass obtained by oxidation of lignosulfonates Syas'sky PPM in alkaline solution with oxygen of air at 160°C, with a concentration of vanillin 7.2 g/liter 1 liter of the reaction mixture was acidified to pH 4 and was extracted three times with octanol portions of 100 ml of the combined extract consisted of 6.9 g of vanillin.

The combined extract Tr is GDI was extragonadal 20 ml of Hydrosulphite solution of sodium concentration of 250 g/L. The residual content of vanillin in the solution of octanol was 0.21 g, as in the Hydrosulphite solution was transferred 6,69 g of vanillin.

The resulting solution was vanilla-hydrosulfite derived was loaded into the autoclave with a capacity of 0.5 liters and heated to 140°C, and then through the valve has released steam and gas phase in the cooler-condenser. The autoclave was cooled, the solid residue were Proektirovanie ethanol, and vanilla from the extract obtained by distillation of the solvent. Received 6,35 g of vanillin (95% of the contained in the Hydrosulphite solution). The solid residue of sodium sulfite was analyzed for residual vanilla. Found in the solid residue 0.31 g of vanillin (4.6% of the contained in the Hydrosulphite solution).

The obtained solid residue of sodium sulfite with the remnants of vanilla mixed with the condensate in an aqueous solution of sulphurous anhydride, obtained after condensation of vapor-gas mixture from the autoclave, added water up to a volume of 60 ml and received Hydrosulphite solution of sodium used in example 2.

Example 2. The experiment was performed as in example 1, including the stage of Stripping of vanilla, but it used the Hydrosulphite solution of sodium obtained in example 1. In Hydrosulphite solution after Stripping was found to 6.95 g of vanillin.

The resulting solution was vanilla-hydrosulfite derived was loaded into the autoclave capacity is d 0.5 liters and heated to 170°C, then through the valve has released steam and gas phase in the cooler-condenser.

Received to 6.67 g of vanillin (96% of the contained in the Hydrosulphite solution). The solid residue of sodium sulfite was analyzed for residual vanilla. Found in the solid residue 0.24 g of vanillin (3.4% of the contained in the Hydrosulphite solution).

Example 3. The experiment was performed as in example 1, but the solution of vanillin-hydrosulfite derived in the autoclave was heated to 120°C, and through the valve has released steam and gas phase in the cooler-condenser so that approximately half of the water remained in the autoclave. Received a suspension of vanillin in the solution of sulfite, hydrosulfite and vanilla-hydrosulfite was derived Proektirovanie with ethyl acetate.

Received 5,28 g of vanillin (79% contained in the Hydrosulphite solution). The solid residue of sodium sulfite was analyzed for residual vanilla. Found in the solid residue of 1.31 g of vanillin (19.6% from contained in the Hydrosulphite solution).

Example 4. The experiment was performed as in example 1, but the solution of vanillin-hydrosulfite derived boiled at atmospheric pressure and 102-105°C to almost complete evaporation of the water, and are condensed vapor-gas phase in the cooler-condenser. The precipitate was Proektirovanie with methanol, the extract was evaporated.

Received 2,13 the vanilla (31.8% of the contained in the Hydrosulphite solution). The solid residue of sodium sulfite was analyzed for residual vanilla (in the form of undecomposed vanilla-hydrosulfite derived). Found in the solid residue 4.42 g of vanillin (66% of the contained in the Hydrosulphite solution).

Example 5. The experiment was performed as in example 1, but the solution of vanillin-hydrosulfite derived in the autoclave was heated to 180°C, and through the valve has released steam and gas phase in the cooler-condenser so that approximately half of the water remained in the autoclave. Received a suspension of vanillin in the solution of sulfite, hydrosulfite and vanilla-hydrosulfite was derived Proektirovanie with ethyl acetate.

Received 5,64 g of vanillin (84% of the contained in the Hydrosulphite solution). Received the vanilla had a dark color and required additional purification. The solid residue of sodium sulfite was analyzed for residual vanilla. Found in the solid residue 0.27 g of vanillin (4% contained in the Hydrosulphite solution). Loss of vanillin as a result of its pitch at high process temperature was 12%.

Thus, the presented examples show that the proposed method of extraction of vanillin from oxidation products of lignin compared to prototype virtually eliminated the consumption of sulphuric acid and caustic soda in the process of purification of vanillin, biolife what funding and ensured the return of hydrosulfite sodium in the production cycle without the cost of reagents. The key stage of the process, the hydrolysis vanilla-hydrosulfite derived, effectively takes place in an autoclave at 120-170°C. At lower temperatures the degree of hydrolysis is small, and most of vanillin is unable to allocate a simple extraction, and at temperatures above 170°C vanilla partially osmoses.

The method of purification of vanillin obtained from the oxidation products of lignin interaction vanrenterghem extracts with aqueous solutions of hydrosulfite sodium with subsequent decomposition vanilla-hydrosulfite derivative, characterized in that the vanilla-hydrosulfite derivative is heated in the autoclave to 120-170°C, dropping gas-vapor phase and extracted with vanilla from the mixture or solution with subsequent recycling of the resulting aqueous solution of sulphur dioxide and sulphite sodium Hydrosulphite solution of sodium.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of separating vanillin, which is widely used in food, perfume-cosmetic and pharmaceutical industries, from lignin oxidation products by reacting vanillin-containing extracts with aqueous sodium hydrosulphite NaHSO3 solutions. The solutions used have sodium hydrosulphite concentration of 320-400 g/l and the vanillin-hydrosulphite derivative formed is separated from excess sodium hydrosulphite solution in form of a precipitate by filtration, centrifuging or decantation.

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3 ex

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1 tbl, 2 ex

FIELD: chemistry.

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1 tbl, 2 ex

FIELD: chemistry.

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7 ex

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< / BR>
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FIELD: chemistry.

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3 ex

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1 tbl, 16 ex

FIELD: chemical technology.

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5 cl, 3 tbl, 26 ex

FIELD: chemical technology.

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4 cl, 3 tbl, 19 ex

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The invention relates to a method for producing vanillin and lilac aldehyde products of fine organic synthesis
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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

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