Method of separating vanillin from lignin oxidation products

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.

EFFECT: method enables to cut consumption of sodium hydrosulphite and increases the distribution ratio of vanillin into the precipitate and aqueous phase from the organic phase, which reduces the volume of extracts and re-extracts when separating vanillin.

3 ex

 

The invention relates to methods of extraction of vanillin from lignin-containing raw material and relates to the purification and concentration of extracts of vanilla, obtained by oxidation of alkaline solutions of lignin, 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 130C with further reextracting aqueous-alkaline solution (alkali or soda) at pH 10-14 and allocation of vanilla and lilac aldehyde acidification with sulfuric acid to pH 5 (EN 2177935, publ. 10.01.2002).

The disadvantages of this method are the high content of resins obtained in which oncentrate - 33-44 wt.% and the need for 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 disadvantages of this method are the low solubility of vanillin in nonpolar hydrocarbons and the need to use the latest in high volumes.

A known method of extraction of vanillin from one stripped off the benzene extract through its interaction with hydrogen sulfite solution of sodium NaSO3used 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 of NaHSO3concentration of 29 wt.%. Hydrosulfite sodium chemically reacts with the carbonyl group of vanillin with the formation of a fairly strong vanilla-hydrosulfite derived:

where AG-SNO - vanilla.

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 of protege is on a carbonyl group of vanillin, and 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.

However, the main disadvantage of this method is the large consumption of hydrosulfite sodium (concentrate vanilla processed by Hydrosulphite solution twice with a total flow rate of 11 kg 29% solution of NaHSO3per kg of vanillin, which corresponds to 4.6-fold excess of stoichiometry). The second disadvantage of this method is associated with the first and is the large consumption of sulfuric acid for separation of vanillin obtained from hydrosulfite derived. The third disadvantage of this method is the low rate of interaction of aqueous and organic phases (3 hours) due to the high viscosity of the latter.

The closest to the essence of the claimed method is a method of extraction of vanillin from extracts (not one stripped off concentrates) by their interactions with aqueous solutions of hydrosulfite sodium NaHSO3[Tarabanko V.E., Shelbina J.V., Kaigorodov ANY study of the extraction of vanillin. Chemistry of plant raw materials, 2008, No. 4, s.89-94]. In accordance with the known method the vanilla extract in the octanol extravert aqueous solutions of hydrosulfite sodium concentration 50-120 g/L. Extras the CT vanillin in octanol has a low viscosity, and therefore, there is a method devoid of the third disadvantage of the previous method - reextracted vanillin occurs within 1-10 minutes the Main disadvantage of this method is the large consumption of hydrosulfite sodium (8-13-fold excess of stoichiometry). The second disadvantage of this method is associated with the first and is the large consumption of sulfuric acid for separation of vanillin obtained from hydrosulfite derived. Sulfuric acid necessary for the decomposition of excess hydrosulfite sodium during acid digestion vanilla-hydrosulfite derived. The third disadvantage of this method is low distribution coefficients of vanillin in aqueous phase from the organic (k=[Vanillin]aqua/[Vanillin]org=10-20).

The task of the invention is to reduce the consumption of hydrosulfite sodium and sulfuric acid in the process of Stripping the vanilla and increase the distribution coefficient of vanillin in aqueous phase from the organic. The latter ensures the reduction of extracts and reextractors in the process of allocation of vanilla.

The task of the invention is achieved in that in the method of extraction of vanillin from oxidation products of lignin interaction vanrenterghem extracts with aqueous solutions of hydrosulfite sodium NaHSO3according to the invention, use is implemented it solutions with a concentration of 320-400 g/liter, and formed vanilla-hydrosulfite derivative is separated from the excess hydrosulfite sodium in the form of a precipitate by filtration, centrifugation or decantation.

Common features of the claimed invention and prototype - the use of aqueous solutions of hydrosulfite sodium to extract vanillin from extracts.

The hallmark of the invention is the use of high concentrations of hydrosulfite sodium 320-400 g/liter. In this interval due to vicalvaro effect of high concentrations of hydrosulfite sodium vanilla-hydrosulfite derived almost not soluble in the aqueous phase and precipitated in the form of a crystalline precipitate. The second distinctive feature is that the resulting vanilla-hydrosulfite derivative is separated from the excess of Hydrosulphite solution of sodium in the form of a precipitate by filtration, centrifugation or decantation.

Technical results of the invention are to reduce consumption of hydrosulfite sodium and sulfuric acid in the process of Stripping vanilla 5-15 times, and increase the distribution coefficient of vanillin in the sediment and the aqueous phase from the organic on the order of 10-20 in the prototype up to 200 according to the claimed invention. The latter ensures the reduction of extracts and reextractors in the process of allocation of vanilla is A.

Called distinctive features lead to the achievement of the technical result of the claimed invention, because only by increasing the concentration of hydrosulfite sodium increases the distribution coefficient of vanillin from the organic phase in water and rapidly decreases the solubility of vanillin-hydrosulfite derived. 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 160C. the Content of vanillin was determined by means of gas-liquid chromatography. The concentration of vanillin used in the reaction mass was 7.2 g/l

200 ml of the reaction mixture was acidified to pH 7.1 and was twice extracted with octanol portions of 200 ml. combined extract was kept of 3.53 g/l of vanillin, i.e. the recovery was 98%. Lots of vanilla extract amounted to 1.41,

The combined extract was extragonadal 40 ml of Hydrosulphite solution of sodium concentration of 350 g/L. the precipitation was ofcentrifugal and acidified with sulphuric acid Stripping of the emitted sulfur dioxide air flow, and vanilla from the floor of the obtained aqueous solution was led at 10C.

Received: crystalline vanillin to 0.92 g of vanillin in the remaining Hydrosulphite solution at 0.42 g of vanillin in solution in octanol - 0,07, the Observed distribution coefficient of vanillin from octanol in the Hydrosulphite solution and crystalline vanillin-hydrosulfite derived

Dn={[mv aq+mv(in sediment))/Vaq}/{mv(octanol)/Vthe octanol}=191.

The remaining Hydrosulphite solution with vanilla brought to the initial concentration by the addition of 0.65 g of hydrosulfite sodium.

The combined raffinate (octanol) with the remaining vanilla divided into two portions and consistently were extracted them a new portion of the reaction mixture (200 ml, 7.2 g/l or 1.44 g of vanillin), as described above. The combined extract contained 3,59 g/l of vanillin, i.e. the degree of extraction was 98%, taking into account remaining from the previous stage extraction of vanillin. Lots of vanilla extract was 1,44,

The combined extract was extragonadal 40 ml of Hydrosulphite solution of sodium concentration of 350 g/l and the content of vanillin from the previous phase extraction 0,42, the precipitation was ofcentrifugal and acidified with sulphuric acid Stripping of the emitted sulfur dioxide air flow, and vanilla from the obtained aqueous solution was led at 10C.

Received: crystalline vanillin - 1.44 g of vanillin in the remaining Rast is the EOS hydrosulfite - 0,41 g of vanillin in solution in octanol - 0,06,

To restore the initial concentration of hydrosulfite sodium in the extract solution was required additive by weight of 1,1, Thus, the consumption of hydrosulfite sodium per kilogram selected vanilla was 0.76 kg, and vanillin is extracted from the reaction mass to 98%.

Consumption of hydrosulfite sodium in the prototype is 0.4 to 1.2 mol of 0.07 mol of vanilla, 1 kg of vanillin in the prototype consumes 3.9 to 11.7 kg of hydrosulfite sodium. Thus, according to the present method, the flow hydrosulfite sodium 5-15 times lower compared to the prototype. The consumption of sulfuric acid is proportional to the flow rate of hydrosulfite, because the first is spent on stoichiometric oxidation and decomposition of the second.

Example 2. The experiment was performed as in example 1, but used the Hydrosulphite solution of sodium concentration of 320 g/l, and the residue vanilla-hydrosulfite derivative was separated by filtration.

Obtained at the first stage extraction - Stripping: crystalline vanillin - 0.65 g of vanillin in the remaining Hydrosulphite solution - 0.64 g of vanillin in solution in octanol - 0,12,

The observed distribution coefficient of vanillin from octanol in the Hydrosulphite solution and crystalline vanillin-hydrosulfite derived

Dn={[mv aq+mv(in sediment))/Vaq/sub> }/{mv(octanol)/Vthe octanol}=107.

After the second stage of extraction of the residual content of vanillin in aqueous solution of the reaction mixture increased to 6% from the original, i.e. the degree of extraction of vanillin decreased from 98% in example 1 to 94% in example 2.

Obtained in the second stage: crystalline vanillin - of 1.36 g of vanillin in the remaining Hydrosulphite solution - 0.65 g of vanillin in solution in octanol to 0.14,

To restore the initial concentration of hydrosulfite sodium in the extract solution was required additive weight of 1.35, Thus, the consumption of hydrosulfite sodium per kilogram selected vanilla was 0.99 kg, and vanillin is extracted from the reaction mass by 94%.

Example 3. The experiment was performed as in example 1, but used the Hydrosulphite solution of sodium concentration of 400 g/l, and the residue vanilla-hydrosulfite derivative was separated by decantation.

Obtained at the first stage extraction - Stripping:

crystalline vanillin - 1.13 g of vanillin in the remaining Hydrosulphite solution - 0,23 g of vanillin in solution in octanol to 0.05,

The observed distribution coefficient of vanillin from octanol in the Hydrosulphite solution and crystalline vanillin-hydrosulfite derived

Dn={[mv aq+mv(in sediment))/Vaq}/{mv(octanol)/Vthe octanol}=270.

P the following second-stage extraction, the residual content of vanillin in aqueous solution the reaction mass was maintained at 98%, as in example 1.

Obtained in the second stage: crystalline vanillin - 1.42 g of vanillin in the remaining Hydrosulphite solution - 0.24 g of vanillin in solution in octanol to 0.05,

To restore the initial concentration of hydrosulfite sodium in the extract solution was required additive weight of 1.48, Thus, the consumption of hydrosulfite sodium per kilogram selected vanilla made 1.04 kg

Thus, in the proposed method of extraction of vanillin from oxidation products of lignin reduced consumption of hydrosulfite sodium and sulfuric acid in the process of Stripping vanilla 5-15 times, and also increased the distribution coefficient of vanillin in the sediment and the aqueous phase from the organic on the order of 10-20 in the prototype up to 200 according to the claimed invention. The latter ensures the reduction of extracts and reextractors in the process of allocation of vanilla.

Method of extraction of vanillin from oxidation products of lignin interaction vanrenterghem extracts with aqueous solutions of hydrosulfite sodium NaHSO3, characterized in that use solutions with the concentration of hydrosulfite sodium 320-400 g/l, and formed vanilla-hydrosulfite derivative is separated from the excess of Hydrosulphite solution of sodium in the form of a precipitate by filtration, centrifugation or decantation.



 

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