CN1128128C

CN1128128C - Inositol extracting process

Info

Publication number: CN1128128C
Application number: CN 00129627
Authority: CN
Inventors: 王玉兰
Original assignee: Institute of Chemical Metallurgy CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2000-10-08
Filing date: 2000-10-08
Publication date: 2003-11-19
Anticipated expiration: 2020-10-08
Also published as: CN1347863A

Abstract

The present invention relates to a new method for extracting inositol, particularly to a new method for extracting inositol by phytine hydrolysis liquid or phytic-acid hydrolysis liquid. The present invention has the technical scheme that effluent liquid or phytic-acid hydrolysis liquid is concentrated after the phytine hydrolysis liquid passing through cation resin; phosphonic acid in the concentrated substance is removed by lower alcohol, and pure inositol is obtained. The method has no need of anion resin for processing the phytine hydrolysis liquid or the phytic-acid hydrolysis liquid and fundamentally solves the problem of difficult regeneration of anion resin; the present invention has the advantages of simple production process and low production cost.

Description

Extract the novel method of inositol

The present invention relates to a kind of extracting method of inositol, particularly relate to a kind of novel method of extracting inositol by luxuriant and rich with fragrance spit of fland hydrolyzed solution or hydrolysis of phytic acid liquid

Inositol, Inositol is one of vitamin B group, has and vitamin H, the similar effect of VITMAIN B1, and some animal and microorganism are had the activity that promotes growth.Pharmaceutically cooperating or using to handle fat and the catabolic imbalance of cholesterol separately, be used for treating diseases such as liver cirrhosis, fatty liver, carbon tetrachloride poisoning with other drug.In fermentation industry and foodstuffs industry, inositol is used to promote various culture of strains and zymic growth.That inositol also has is anti-loss, strengthen liver, reduce cholesteric effect in the blood, and the people is to requirement gram every day 1～2 of inositol.In healthcare products and food, inositol Chang Zuowei nutrient drug or food enrichment.

Inositol extensively is present in the plant with the form of luxuriant and rich with fragrance spit of fland (being phytic acid calcium magnesium), especially often is present in seed, cereal, plumule, the rice bran.Fei Ting can be hydrolyzed to inositol and phosphoric acid salt under High Temperature High Pressure.At present, the method that obtains inositol from the hydrolyzed solution in luxuriant and rich with fragrance spit of fland mainly contains two kinds.First method is the milk of lime neutralisation, promptly domestic " conventional method " commonly used.But because milk of lime and inositol also have certain binding ability, so milk of lime is in precipitate phosphoric acid salt, and inositols quite a lot also precipitate simultaneously.In addition, this method is that impurity such as protein are carbonized the soup compound into black when the hydrolysis of luxuriant and rich with fragrance spit of fland with the thick luxuriant and rich with fragrance spit of fland direct hydrolysis that contains impurity such as protein.More than two kinds of reasons to have caused this method to have a luxuriant and rich with fragrance spit of fland hydrolyzed solution post-processing step numerous and diverse, the low shortcomings such as (40%～60%) of yield of the high and inositol of cost.Second method is an ion-exchange resin purification method (Japanese Patent, clear 61-56142), this method is at first crossed the higher luxuriant and rich with fragrance spit of fland of purity hydrolyzed solution (referring to that luxuriant and rich with fragrance spit of fland purity before hydrolysis is higher) cationic, anionic exchange resin, removes mineral acid and inorganic salt in the hydrolyzed solution with purification.So not only help improving the inositol yield, but and shortened process, reduce production costs.But anionite-exchange resin regeneration difficulty, the regeneration expense is also high, applies the research of still needing.More than two kinds of methods in " chemical industry small commodity production method " book, also given similar evaluation in (thunder must ripple, Wu Xianyun, chemical industry small commodity production method, the 11 collection, Hunan science tech publishing house,, 159～163 pages in 1991).Also have patent (patent CN1081175) to disclose a kind of electrodialytic method in addition, this method adopts electrodialysis that positive and negative ion is separated and takes away by process water, again that inositol concentration is lower solution is retained down inositol less than the semi-permeable membranes of inositol molecular diameter by the aperture and obtains inositol.This method is except existing the shortcoming that the electrodialysis appts investment is big, power consumption is many and semi-permeable membranes is expensive, hydrolyzed solution must dilute (i.e. the lower solution of the said inositol concentration of this patent) in the Sino-Philippines spit of fland of electrodialysis process, the waste liquid amount of crossing semi-permeable membranes is very big, these waste liquids contain with the mineral ion headed by phosphate radical or the hydrogen phosphate, pollute the environment, can not directly discharge, need purifying treatment, cause the inositol production cost further to improve.In addition, the people of contacted luxuriant and rich with fragrance spit of fland hydrolyzed solution can know, owing to contain the protein carbide in the hydrolyzed solution of luxuriant and rich with fragrance spit of fland, all is difficult to filter with general filter paper, usually separates by whizzer.The very big filter cloth of aperture commonly used filters in the factory, and luxuriant and rich with fragrance spit of fland hydrolyzed solution is filtered less than the semi-permeable membranes of inositol molecular diameter in aperture not hard to imagine serious fenestra obstructing problem will occur, cleans or changes semi-permeable membranes and will cause serious difficulty to the industrial production of inositol.So this method is not also used at present.Also have document and patent once to report with high boiling glycol ether (research and development of natural products 1990,2 (2), 101-105) and polyvalent alcohol mainly be that (patent CN1073425 CN1075135) makes solvent, and normal pressure decompose to be produced the method for inositol for ethylene glycol, glycerol and propylene glycol.It is reported: can decompose by normal pressure in Sino-Philippines spit of fland of these high boiling solvents or phytic acid, after decomposed solution concentrates, filter and directly obtain inositol.We once tested this method, but can not obtain inositol according to this method.What obtain behind the decomposed solution thickening filtration is that fusing point is higher than 280 ℃ non-inositol thing.The fusing point of inositol is 224～227 ℃ (American Pharmacopeia NF-11).After if said normal pressure decomposed solution concentrates, filtration can directly obtain inositol, these high boiling solvents should have the inositol solvency power little so, to phosphoric acid or the big performance of phosphoric acid salt solvency power, so just might concentrate cooling back inositol at reaction solution can crystallize out, inorganic salt such as phosphoric acid or phosphoric acid salt can be stayed in the mother liquor, filter and directly can obtain inositol.Test shows that these high boiling solvents do not have above-mentioned difference to inositol, phosphoric acid or phosphatic solubility property.Because these high boiling solvents make that the viscosity of decomposed solution is big, easily foam during boiling in addition, normal pressure concentrates needs very high temperature, and concentrating under reduced pressure is again easily towards liquid.And glycol ether, ethylene glycol, glycerol and propylene glycol price are higher, and these all make the production cost of inositol improve.

The objective of the invention is to overcome the anionite-exchange resin regeneration difficulty that exists in the second method, the shortcoming that production cost is high, provide a kind of have more help suitability for industrialized production, production cost low, can improve productivity effect extract the novel method of inositol by luxuriant and rich with fragrance spit of fland hydrolyzed solution.

After having now found that luxuriant and rich with fragrance spit of fland hydrolyzed solution is crossed resin cation (R.C.), effluent liquid concentrates, and can remove phosphoric acid in the enriched material with methyl alcohol or ethanol then, obtains inositol.In the second approach, after luxuriant and rich with fragrance spit of fland hydrolyzed solution is crossed resin cation (R.C.), mainly contain inositol and phosphoric acid in the effluent liquid.This situation is the same with the hydrolyzed solution that the phytic acid direct hydrolysis obtains.Inositol and the phosphoric acid solubleness in methyl alcohol or ethanol differs greatly.Inositol is insoluble in anhydrous methanol or the ethanol basically, or is slightly soluble in below ambient temperature in the methyl alcohol or aqueous ethanolic solution more than 90%, and phosphoric acid dissolves in methyl alcohol or the ethanol.Methyl alcohol and alcoholic acid low price are because methyl alcohol some toxicity, preferred alcohol and aqueous ethanolic solution.They can be by simple distillation recycling.Further handle distillation and reclaim methyl alcohol or alcoholic acid mother liquor, can also obtain phosphoric acid product.In out-of-date methods, the regeneration of anionite-exchange resin not only needs a large amount of regenerator (alkali, acid or salt), and the regeneration expense is big, but also needs a large amount of distilled water or deionized water rinsing resin.The water that washed resin pollutes the environment, and can not directly discharge, and needs purifying treatment.The novel method of extraction inositol provided by the invention is compared with out-of-date methods not only has the regeneration difficulty that has overcome anionite-exchange resin, the shortcoming that the regeneration expense is big, reduced production cost, make it more to help suitability for industrialized production and improve the advantage of productivity effect, and reduced the pollution of environment and saved great amount of water resources.

Embodiment provided by the invention is as follows:

When 5 gram content be 98% luxuriant and rich with fragrance spit of fland sodium raw materials hydrolysis reaction fully after, the cooling reaction solution filters and obtains luxuriant and rich with fragrance spit of fland hydrolyzed solution.After luxuriant and rich with fragrance spit of fland hydrolyzed solution was crossed resin cation (R.C.), concentrating under reduced pressure obtained semi-solid enriched material.Add 10 milliliters of dehydrated alcohols and fully soak the enriched material after-filtration, use 5 milliliters of absolute ethanol washing crystal then, obtain 1.1 gram inositols, 222～225 ℃ of fusing points.The water recrystallization obtains the pure inositol of 1.0 grams, 224～226 ℃ of (American Pharmacopeia NF-11 inositol quality index: 224～227 ℃ of fusing points of fusing point; Inositol content is more than 97%).

When 5 gram content be 90% luxuriant and rich with fragrance spit of fland potassium raw material hydrolysis reaction fully after, the cooling reaction solution filters and obtains luxuriant and rich with fragrance spit of fland hydrolyzed solution.After luxuriant and rich with fragrance spit of fland hydrolyzed solution was crossed resin cation (R.C.), concentrating under reduced pressure obtained semi-solid enriched material.Add 10 milliliters of anhydrous methanols and fully soak the enriched material after-filtration, use 5 milliliters of anhydrous methanol washing crystals then, obtain 0.85 gram inositol, 220～228 ℃ of fusing points.The water recrystallization obtains the pure inositol of 0.78 gram, 224～227 ℃ of fusing points.

When 5 gram content be 95% luxuriant and rich with fragrance spit of fland ammonia raw material hydrolysis reaction fully after, the cooling reaction solution filters and obtains luxuriant and rich with fragrance spit of fland hydrolyzed solution.After luxuriant and rich with fragrance spit of fland hydrolyzed solution was crossed resin cation (R.C.), concentrating under reduced pressure obtained semi-solid enriched material.Add 6 milliliter of 95% aqueous ethanolic solution and fully soak the enriched material after-filtration, with 5 milliliter of 95% aqueous ethanolic solution washing crystal, obtain 1.2 gram inositols, 222～228 ℃ of fusing points then.The water recrystallization obtains the pure inositol of 1.1 grams, 224～227 ℃ of fusing points.

When 5 gram content be 93% luxuriant and rich with fragrance spit of fland raw material hydrolysis reaction fully after, the cooling reaction solution filters and obtains luxuriant and rich with fragrance spit of fland hydrolyzed solution.After luxuriant and rich with fragrance spit of fland hydrolyzed solution was crossed resin cation (R.C.), concentrating under reduced pressure obtained semi-solid enriched material.Aqueous ethanolic solution recrystallization with 50% obtains the pure inositol of 0.91 gram, 225～227 ℃ of fusing points.

When 5 gram content be 92% luxuriant and rich with fragrance spit of fland sodium raw materials hydrolysis reaction fully after, the cooling reaction solution filters and obtains luxuriant and rich with fragrance spit of fland hydrolyzed solution.After luxuriant and rich with fragrance spit of fland hydrolyzed solution was crossed resin cation (R.C.), concentrating under reduced pressure obtained semi-solid enriched material.Aqueous ethanolic solution recrystallization with 50% obtains the pure inositol of 0.94 gram, 224～227 ℃ of fusing points.

When 5 gram content be 98% luxuriant and rich with fragrance spit of fland sodium raw materials hydrolysis reaction fully after, the cooling reaction solution filters and obtains luxuriant and rich with fragrance spit of fland hydrolyzed solution.After luxuriant and rich with fragrance spit of fland hydrolyzed solution was crossed resin cation (R.C.), concentrating under reduced pressure obtained semi-solid enriched material.Add 10 milliliters of dehydrated alcohols and methanol solution, fully soak the enriched material after-filtration, use 5 milliliters of absolute ethanol washings and methyl alcohol crystal then, obtain 0.99 gram inositol, 222～227 ℃ of fusing points.The water recrystallization obtains the pure inositol of 0.95 gram, 224～227 ℃ of fusing points.

7. be that 70% phytic acid is dissolved in hydrolysis in 20 ml distilled waters with 5 gram content, after reacting completely, the cooling reaction solution filters and obtains hydrolysis of phytic acid liquid.Hydrolysis of phytic acid liquid concentrating under reduced pressure obtains semi-solid enriched material.Add 10 milliliters of dehydrated alcohols and fully soak the enriched material after-filtration, use 5 milliliters of absolute ethanol washing crystal then, obtain 1.1 gram inositols, 222～225 ℃ of fusing points.The water recrystallization obtains the pure inositol of 0.88 gram, 224～227 ℃ of (American Pharmacopeia NF-11 inositol quality index: 224～227 ℃ of fusing points of fusing point; Inositol content is more than 97%).

Claims

1. one kind is extracted the method for inositol by luxuriant and rich with fragrance spit of fland hydrolyzed solution or hydrolysis of phytic acid liquid, it is characterized in that (1) luxuriant and rich with fragrance spit of fland hydrolyzed solution is crossed resin cation (R.C.) after, effluent liquid concentrates, and removes phosphoric acid in the enriched material with methyl alcohol or ethanol or its aqueous solution then, obtains pure inositol; Or after (2) hydrolysis of phytic acid liquid concentrates, remove phosphoric acid in the enriched material with methyl alcohol or ethanol or its aqueous solution, obtain pure inositol.

2. according to the method for the extraction inositol of claim 1, wherein said luxuriant and rich with fragrance spit of fland hydrolyzed solution is that purity is the complete hydrolysis liquid of luxuriant and rich with fragrance spit of fland more than 90%, luxuriant and rich with fragrance spit of fland sodium, luxuriant and rich with fragrance spit of fland potassium and Fei Ting amine raw material.

3. according to the method for the extraction inositol of claim 1, wherein said method of removing the phosphoric acid in the enriched material comprises with methyl alcohol or ethanol or its aqueous solution soaking, washing or recrystallization enriched material and to obtain the method for pure inositol to remove phosphoric acid wherein.

4. according to the method for the extraction inositol of claim 1, wherein said methyl alcohol or ethanol or its aqueous solution comprise the mixing solutions of methyl alcohol and alcoholic acid mixing solutions, methyl alcohol or ethanol and water, and wherein the mixing solutions of ethanol and water is the aqueous ethanolic solution more than 90%.

5. according to the method for the extraction inositol of claim 1, wherein said hydrolysis of phytic acid liquid is that purity is the complete hydrolysis liquid of the phytic acid raw material more than 50%.