CN102977179A

CN102977179A - Method for extracting hydroxy group or/and carboxyl group contained natural compounds

Info

Publication number: CN102977179A
Application number: CN2012104369571A
Authority: CN
Inventors: 耿兆翔
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-10-28
Filing date: 2012-10-25
Publication date: 2013-03-20
Anticipated expiration: 2032-10-25
Also published as: CN102977179B; CN102503756A

Abstract

The invention relates to a method for extracting hydroxy group or/and carboxyl group contained natural compounds, and belongs to the technical field of the biological engineering. The method comprises the following steps: adding water to hydroxy group or/and carboxyl group contained natural plants, crushing to destroy cell walls of the plants, carrying out degradation desugaring through using beta-glucosidase, dissolving in hot alkaline water, adding a cationic surfactant, stirring to carry out a chemical combination reaction, cooling, reacting with hydrochloric acid to reduce, and lyophilizing. The method enables dry products containing above 95% of the hydroxy group or/and carboxyl group contained natural compounds to be obtained, and the dry products can be applied to the medical treatment, the healthcare, and biological pesticides.

Description

Natural hydroxyl is or/and the extracting method of carboxylic compound

Affiliated technical field:

The present invention relates to a kind of natural hydroxyl of technical field of bioengineering or/and the extracting method of carboxylic compound, especially natural hydroxyl is or/and the extracting method of carboxylic compound.

Background technology:

Along with the raising of people's living standard and nontoxic to the natural plant source; be conducive to safely and efficiently protect people healthy; it is auxiliary and substitute that the prevent and cure diseases pursuit of natural organic substance, biotherapy become necessity that the Western medicine therapy of synthetic can not lack suddenly day by day.

Simultaneously, because some Traditional Man synthetic pesticides, biological residual quantity is high, and the serious harm people are healthy, are difficult for degraded, and water surrounding and biology are had larger toxicity, and therefore, the natural biological agricultural chemicals in natural plant source is just becoming the pursuit of green agriculture.

But these natural hydroxyls are or/and carboxylic compound simple efficient, fast, and environmentally safe separation and extraction technology is global problem always.Method commonly used has heavy metallic salt precipitate and separate sourer reduction method, organic solvent extractionprocess, macroreticular resin absorbing method and membrane separation process.Organic solvent extraction, macroporous resin adsorption and membrane separation plant have high input, and production efficiency is low, and production cost is high, and the product active constituent content is low, even only has about 30%, and pharmaceutical value is low, is difficult to large-scale industrialized production.And heavy metallic salt precipitation sourer reduction method will produce inevitably the heavy metallic salt of highly water-soluble and the factory effluent of strong acid or strong acid salt, have very large and destruction that be difficult to eliminate to water surrounding.

The use of heavy metallic salt is highstrung, concerns the significant problem of the healthy and water surrounding of people.And be difficult to remove to the safety value to human and environment, heavy metallic salt is very low to the safety value of human and environment, and prior art is difficult to thoroughly remove heavy metallic salt from waste water, and processing cost is high.Carboxylic compound is not just considered the Laboratory Production technology to the human and environment murder by poisoning so the heavy metallic salt precipitator method are extracted natural hydroxyl, is " empty talk " production technology that impossible scale operation is administered in a kind of extensive polluting first afterwards.

Natural flavone glycoside and trans-resveratrol glycosides compound, its biological activity is to be determined rather than by glucosides decision itself, because the active group on the active aglycone in the glucosides (non-sugared body) is destroyed by glycosidic link by wherein aglycone (being active aglycone).Although its chemical property of glucosides is more stable in natural phant, has lost biological activity; The aglycone biological activity is strong, but unstable; Stable in properties and biological activity can not get both.So aglycone free in the natural phant is seldom seen, exists mainly with its corresponding glucosides form.Existing Industrialized processing technique all is to extract flavonoid glycoside (such as soybean isoflavone glycoside from soybean isoflavones, polydatin), rather than active aglycone wherein (aglycone, as, real soybean isoflavones and trans-resveratrol).

Summary of the invention:

The natural hydroxyl that the present invention is alleged is or/and carboxylic compound refers to that mainly the natural acidic triterpene saponin (contains carboxyl-COOH or hydroxyl-OH) compound, natural flavone glycoside (hydroxyl-OH, comprise flavonoid glycosides and isoflavone aglycone), trans-resveratrol glycosides compound (hydroxyl-OH), but do not comprise anthocyanidin.

According to existing knowledge, most natural glucosides are that D-Glucose glycosides and nearly all natural glucosides all are β type glucosides; According to the enzyme liberating substrate specificity, nearly all beta-glucosidase (is called for short BGL, claim again β-D-Glucose glycosides lytic enzyme) relatively poor to the specificity of the glycosyl part structure of substrate, energy cracking C-O glycosidic link, C-S key, C-N key, C-F key etc. also can be hydrolyzed beta-glucoside key and beta galactose glycosidic bond and wood sugar glycosidic bond, cellobiose glycosidic bond simultaneously; Beta-glucosidase is only for the β type glycosidic link in the natural glucosides, and irrelevant with the chemical structure of aglycone in the natural glucosides, and natural glucosides is hydrolyzed into aglycone (such as, soybean isoflavones) and sugared (such as, glucose); Flavonoid Glycosides (hydroxyl-OH, comprise flavonoid glycosides and isoflavone aglycone) all have the basic skeleton structure of C6-C3-C6, and the O-glycosides that great majority connect for the C-O glycosidic link, so glycosidic link does not wherein have essential difference to beta-glucosidase, can both be by its hydrolytic cleavage; Glycosidic link in the polydatin too can be by the beta-glucosidase hydrolytic cleavage; The present invention is with beta-glucoside enzymic hydrolysis flavonoid glycoside and polydatin, and mainly for C-O glycosidic link (by the O bridge among hydroxyl-OH), this is the most weak a kind of glycosidic link of bond energy, and is the easiest of the beta-glucosidase hydrolytic cleavage.Glycosidic link in natural flavone glycoside of the present invention (hydroxyl-OH comprises flavonoid glycosides and isoflavone aglycone) and the polydatin can both be by the beta-glucosidase hydrolytic cleavage.Prior art also discloses the biochemical reaction condition of beta-glucosidase and the mechanism of action of hydrolysis β-glycosidic link thereof, and beta-glucosidase and biochemical reaction condition thereof are the necessary and sufficient conditions of natural β-hydrolysis of glycoside bond fracture.

According to existing knowledge, flavonoid (not comprising anthocyanidin) is insoluble with trans-resveratrol or be insoluble in water, also is insoluble to neutral aqueous solution, but is dissolved in dilute alkaline aqueous solution.

According to existing knowledge, cats product octadecyl trimethyl ammonium chloride and Cetyltrimethylammonium bromide all only are dissolved in hot water, and be insoluble to cold water, so octadecyl trimethyl ammonium chloride or Cetyltrimethylammonium bromide only could ionize out cation group and corresponding chlorine/bromine anions with the long-chain oleophilic group in hot water.And this is with the cation group of long-chain oleophilic group in case by anionic group chemical combination salify of the present invention, and this will be water-insoluble, particularly in cold water, because the salt of this cation group with the long-chain oleophilic group is difficult to ionization in cold water.Equally, n-Hexadecane hydrocarbon oleophilic group in cats product palmityl trimethyl ammonium chloride and the cetyl trimethylammonium bromide also has stronger hydrophobicity, and Flavone aglycone of the present invention/trans-resveratrol aglycon is insoluble or be insoluble in water, so after the anionic group in the sodium salt of the cation group in palmityl trimethyl ammonium chloride or the cetyl trimethylammonium bromide and Flavone aglycone/trans-resveratrol aglycon is combined to neutral salt, this salt formula compound also is difficult to ionization in water, and be water-insoluble, particularly in cold water, the solubleness of salt (ionizing power) also with the temperature correlation of water.The present invention utilizes octadecyl trimethyl ammonium chloride or Cetyltrimethylammonium bromide only to be dissolved in hot water and the critical nature that is insoluble to cold water, realize the extraction of triterpenoid saponin, natural flavonoid (hydroxyl-OH comprises flavonoid and isoflavones), trans-resveratrol.The inventive method also utilize palmityl trimethyl ammonium chloride or cetyl trimethylammonium bromide can be dissolved under the normal temperature cold water and can be in cold water with the sodium salt of water miscible flavonoid aglycon/trans-resveratrol aglycon in anionic group be combined to this critical nature of water-insoluble salt and directly obtain flavonoid aglycon and trans-resveratrol aglycon.

According to existing knowledge, triterpenoid saponin is comprised of triterpenoid sapogenin and sugar (glucose, semi-lactosi, rhamnosyl, pectinose, wood sugar) or uronic acid and other organic acid (containing carboxyl), has found to reach more than 30 types.Triterpenoid saponin has carboxyl more, so be called again acid saponin(e, how water-soluble triterpenoid saponin is.

According to existing knowledge, hydroxyl (OH) is slightly acidic, so though the triterpenoid sapogenin of hydroxyl is water insoluble or neutral brine solution, can be dissolved in dilute alkaline aqueous solution.

For passing through β-glycosidic link (C-O glycosidic link) combination by triterpenoid sapogenin and sugar, and the triterpenoid saponin that one or more acid hydroxy groups are arranged on its triterpenoid sapogenin can extract its highly active triterpenoid sapogenin according to the extracting method of flavonoid aglycon of the present invention/trans-resveratrol aglycon.Triterpenoid sapogenin is general insoluble or be insoluble in water, but hydroxyl (triterpenoid sapogenin OH) can be dissolved in dilute alkaline aqueous solution, so its extracting method is identical with Flavone aglycone of the present invention/trans-resveratrol aglycon extracting method.

Technology of the present invention foothold be exactly carboxyl in triterpenoid saponin (unit), flavonoid glycosides, the polydatin or/and hydroxyl, to this, the inventive method has widely adaptability and feasibility.

For effectively overcoming present natural hydroxyl or/and the defective of the extracting method technology of carboxylic compound; really strong protection people are healthy; prevent and cure diseases; protection of the environment the invention provides a kind of simple and reliablely, and technology is workable; less investment; production cost is low, and is effective, extracts the high natural hydroxyl of product purity or/and the extracting method of carboxylic compound.

The technical solution adopted for the present invention to solve the technical problems is:

1, extracting method of the present invention may further comprise the steps:

One, the extraction of triterpene saponin:

(1) plant adds edible soft water or deionized water pulverizing;

(2) destroy plant cell wall or destroy plant cell wall with the freezing defreezing method that reheats with cellulose degraded; To not needing to destroy the plant of plant cell wall, this step can omit;

(3) above-mentioned product is added, the water soluble anionic surfactant that contain straight chain oleophilic group responsive to cationic substance of 0.2%-0.5%, to improve the solubleness of triterpenoid saponin in the aqueous solution, 30 ℃-60 ℃ of temperature; This step also can be omitted;

(4) with above-mentioned product heated and stirred, 25 ℃-80 ℃ of temperature, stirring velocity 50-200 rev/min, to improve the dissolution rate of triterpenoid saponin in water;

(5) squeeze and filter, the aqueous solution that must contain triterpenoid saponin is for subsequent use;

(6) the above-mentioned aqueous solution that contains triterpenoid saponin is added an amount of NaOH, triterpenoid saponin is neutralized fully, generate water miscible salt; Salt brine solution PH7-12;

(7) the above-mentioned aqueous solution is added cats product octadecyl trimethyl ammonium chloride or Cetyltrimethylammonium bromide again, restir fully reacts the triterpenoid saponin salt in cats product and the aqueous solution; The cats product molecule is connected on the triterpenoid saponin molecule-COO ^-On the dehydrogenation carboxyl or-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; Also chemical combination precipitation of cats product and anion surfactant wherein; And promote that cats product separates with precipitation or the suspension of water with the water-insoluble compound of triterpenoid saponin; 30 ℃-70 ℃ of temperature, rotating speed 100-600 rev/min, time 30-60 minute;

(8) above-mentioned product is cooled to 1 ℃-30 ℃, makes total overall reaction thing precipitation or suspension;

(9) extract above-mentioned precipitation or suspended matter, hydrochloric acid replacement(metathesis)reaction under agitation condition with 2%-30%, rotating speed 50-600 rev/min, reaction times 10-30 minute, 1 ℃-30 ℃ of temperature, notice that hydrochloric acid is only excessive a little, the aqueous solution is controlled between the PH4-6.9 in the time of will react end, and the cats product that adds etc. is precipitated or the separation that suspends by complete reaction; The biological activity of recovery triterpenoid saponin and water-soluble;

Reaction formula: 1. A ₁+ HCl → B ₁+ C ₁↓

Here, A ₁The water-insoluble salt that dehydrogenation carboxyl on expression cats product and the triterpenoid saponin forms; B ₁Former triterpenoid saponin after the expression hydrogen reduction; C ₁Expression is by Cl ^-Water-insoluble octadecyl trimethyl ammonium chloride throw out or suspended substance under the low temperature after the ion reduction;

Reaction formula: 2. A ₂+ HCl → B ₂↓+C ₂↓

A here ₂The water-insoluble compound of expression anion surfactant and cats product.B ₂Expression anion surfactant and H ⁺The water-insoluble compound of ion combination.C ₂Expression cats product and Cl ^-Water-insoluble octadecyl trimethyl ammonium chloride flocculent precipitate or suspended substance under the low temperature that ion combination forms;

Reaction formula: 3. A ₃+ HCl → B ₃↓+H ₂O

A here ₃OH in expression cats product and the alkaline aqueous solution ^-The water-insoluble pseudobase that root chemical combination generates.B ₃The expression cats product is by Cl ^-Octadecyl trimethyl ammonium chloride throw out or suspended substance after the ion reduction;

(10) above-mentioned reactant is filtered, only contained B ₁The water-soluble aqueous solution, vacuum lyophilization obtains the triterpenoid saponin dry product, wherein excessive a little hydrochloric acid (HCl gas) is recovered; 10-24 hours time of drying, freezing temp-40 ℃ is to-20 ℃, pressure≤25Pa;

Two, the extraction of flavonoid aglycon

(1) plant adds edible soft water or deionized water pulverizing;

(2) above-mentioned product is destroyed plant cell wall or destroys plant cell wall with the freezing defreezing method that reheats with cellulose degraded; To not needing to destroy the plant of plant cell wall, this step can omit;

(3) above-mentioned product is added 0.2%-0.5% to the cationic substance sensitivity, contain the water soluble anionic surfactant of straight chain oleophilic group, to improve the solubleness of flavonoid glycoside in the aqueous solution, 30 ℃-60 ℃ of temperature; This step also can be omitted;

(4) heated and stirred, 25 ℃-80 ℃ of temperature, stirring velocity 50-200 rev/min, to improve the dissolution rate of flavonoid glycoside in water;

(5) squeeze and filter must contain the aqueous solution of flavonoid glycoside, and adding water soluble calcium salt or magnesium salts and above-mentioned anion surfactant are combined to water-insoluble salt to remove anion surfactant, and be for subsequent use;

(6) with above-mentioned product in stirring with the beta-glucoside enzyme liberating, the desugar of cracking glycosidic link gets Flavone aglycone, 40 ℃-50 ℃ of temperature, PH4-6.9, rotating speed 30-100 turns, time 10-24 hour; For the C-O glycosidic link;

(7) the above-mentioned aqueous solution that contains Flavone aglycone is added an amount of NaOH, make on the Flavone aglycone-the OH hydroxyl partially or completely neutralized, and generates water miscible salt; The salt brine solution pH value is PH7-12;

(8) the above-mentioned aqueous solution is added again cats product octadecyl trimethyl ammonium chloride or Cetyltrimethylammonium bromide or palmityl trimethyl ammonium chloride or cetyl trimethylammonium bromide, restir fully reacts the Flavone aglycone salt in cats product and the aqueous solution; The cats product molecule is connected on the Flavone aglycone molecule-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; 40 ℃-80 ℃ of temperature, rotating speed 100-600 rev/min, time 30-60 minute;

(9) above-mentioned product is cooled to 1 ℃-30 ℃, makes total overall reaction thing precipitation or suspension;

(10) extract above-mentioned precipitation or suspended matter, hydrochloric acid replacement(metathesis)reaction under agitation condition with 2%-30%, rotating speed 50-600 rev/min, reaction times 10-30 minute, 1 ℃-30 ℃ of temperature, notice that hydrochloric acid is only excessive a little, will react that the aqueous solution is controlled between the PH4-6.9 when finishing, make the cats product that adds etc. by complete reaction/precipitation or suspension separation; Recover the biological activity of Flavone aglycone;

1. octadecyl trimethyl ammonium chloride or Cetyltrimethylammonium bromide, hydrochloric acid reaction formula:

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁↓

Here, A ₁On expression cats product and the Flavone aglycone-O ^-The water-insoluble salt that the dehydrogenation hydroxyl forms; B ₁Former Flavone aglycone after the expression hydrogen reduction; C ₁Expression is by Cl ^-Water-insoluble octadecyl trimethyl ammonium chloride flocculent precipitate or suspended substance under the low temperature after the ion reduction;

Reaction formula: 2. A ₂+ HCl → B ₂↓+H ₂O

A here ₂OH in expression cats product and the alkaline aqueous solution ^-The water-insoluble pseudobase that root chemical combination generates.B ₂The expression cats product is by Cl ^-Octadecyl trimethyl ammonium chloride throw out or suspended substance after the ion reduction; B ₂With above-mentioned C ₁Identical;

2. palmityl trimethyl ammonium chloride or cetyl trimethylammonium bromide, hydrochloric acid reaction formula:

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁

Here, A ₁On expression cats product and the Flavone aglycone-O ^-The water-insoluble salt that the dehydrogenation hydroxyl forms; B ₁Former Flavone aglycone after the expression hydrogen reduction; C ₁Expression is by Cl ^-Water miscible palmityl trimethyl ammonium chloride under the low temperature after the ion reduction;

Reaction formula: 2. A ₂+ HCl → B ₂+ H ₂O

A here ₂OH in expression cats product and the alkaline aqueous solution ^-The water-insoluble pseudobase that root chemical combination generates.B ₂The expression cats product is by Cl ^-Water miscible palmityl trimethyl ammonium chloride under the low temperature after the ion reduction; B ₂With above-mentioned C ₁Identical;

(11) product among above-mentioned (10) .1 is added NaOH, Sodium Benzoate and anion surfactant fatty acid sodium salt, and be heated to 40 ℃-60 ℃; Aqueous ph value is being adjusted between the PH8-10, after add again the Sodium Benzoate of aqueous solution 1%-2% and the fatty acid sodium salt excessive a little with respect to octadecyl trimethyl ammonium chloride, the excessive degree of fatty acid sodium salt is the 0.2%-0.3% of the aqueous solution; Restir, speed 50-200 rev/min, time 10-30 minute; Again with above-mentioned C ₁Filter removal with the water-insoluble compound of fatty acid sodium salt chemical combination; Adding water soluble calcium salt or magnesium salts fully stir again, and rotating speed 100-200 rev/min, make calcium salt or magnesium salts and above-mentioned excessive fatty acid sodium salt chemical combination, generate water-insoluble compound and be filtered removal; Only have like this Sodium Benzoate and target product B in the aqueous solution ₁, be cooled to again 1 ℃-30 ℃, and with the hydrochloric acid regulating solution pH value to PH7, such target product B ₁Major part Precipitation from the aqueous solution; The effect of Sodium Benzoate here is the collaborative target product B that increases ₁Solubleness in the aqueous solution is convenient to B ₁With other separating substances; The recycling capable of circulation of the Sodium Benzoate aqueous solution; When sodium chloride content was too high in the Sodium Benzoate aqueous solution that recycles and reuses, adjustable water solution was to acid, and the recovery of benzoic acid revaporization concentrates to get the NaCl dry product; Here Sodium Benzoate also can omit; This step is separated the ultimate aim product B ₁Also can adopt following steps, add first an amount of NaOH, making aqueous ph value is PH8-12, and making aqueous temperature is 1 ℃-30 ℃, only has like this target product B ₁Be dissolved in low temperature alkaline aqueous solution and separate with octadecyl trimethyl ammonium chloride, obtain target product B ₁The aqueous solution uses the hydrochloric acid regulating solution pH value to PH7, like this target product B again ₁Precipitation from the aqueous solution is because the water insoluble or neutral aqueous solution of this target product;

Product direct filtration with among above-mentioned (10) .2 obtains target product B ₁And with a small amount of cats product in tap water or this target product of washed with de-ionized water, the cats product starting material have greatly been saved in the recycling capable of circulation of the aqueous solution of compositions comprising cationic surfactants;

(12) with above-mentioned B ₁Vacuum lyophilization obtains the Flavone aglycone dry product, and 1-24 hour time of drying, freezing temp-40 ℃ is to-1 ℃, pressure≤25Pa;

Three, the extraction of trans-resveratrol aglycon

(1) plant adds edible soft water or deionized water pulverizing;

(3) above-mentioned product is added 0.2%-0.5% to the cationic substance sensitivity, contain the water soluble anionic surfactant of straight chain oleophilic group, to improve the solubleness of polydatin in the aqueous solution, 30 ℃-60 ℃ of temperature; This step can be omitted;

(4) heated and stirred, 25 ℃-80 ℃ of temperature, improve the dissolution rate of polydatin in water by stirring velocity 50-200 rev/min;

(5) squeeze and filter must contain the aqueous solution of polydatin, and adding water soluble calcium salt or magnesium salts and above-mentioned anion surfactant are combined to water-insoluble salt to remove anion surfactant, and be for subsequent use;

(6) with above-mentioned product in stirring with the beta-glucoside enzyme liberating, the cracking glycosidic link, desugar gets the trans-resveratrol aglycon, 40 ℃-50 ℃ of temperature, PH4-6.9, rotating speed 30-100 rev/min, time 10-24 hour; For the C-O glycosidic link;

(7) the above-mentioned aqueous solution that contains the trans-resveratrol aglycon is added an amount of NaOH, the hydroxyl on the trans-resveratrol aglycon is partially or completely neutralized, generate water miscible salt; Salt brine solution PH7-12;

(8) the above-mentioned aqueous solution is added again cats product octadecyl trimethyl ammonium chloride or Cetyltrimethylammonium bromide or palmityl trimethyl ammonium chloride or cetyl trimethylammonium bromide, restir fully reacts the trans-resveratrol aglycon salt in cats product and the aqueous solution; The cats product molecule is connected on the resveratrol molecule-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; 40 ℃-70 ℃ of temperature, rotating speed 100-600 rev/min, time 30-60 minute;

(10) extract above-mentioned precipitation or suspended matter, hydrochloric acid replacement(metathesis)reaction under agitation condition with 2%-30%, rotating speed 50-600 rev/min, reaction times 10-30 minute, 1 ℃-30 ℃ of temperature, notice that hydrochloric acid is only excessive a little, will react that the aqueous solution is controlled between the PH4-6.9 when finishing, make the cats product that adds etc. by complete reaction/precipitation or suspension separation; Recover the biological activity of trans-resveratrol;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁↓

Here, A ₁On expression cats product and the trans-resveratrol aglycon-O ^-The water-insoluble salt that the dehydrogenation hydroxyl forms; B ₁Former trans-resveratrol aglycon after the expression hydrogen reduction; C ₁Expression is by Cl ^-Water-insoluble octadecyl trimethyl ammonium chloride flocculent precipitate or suspended substance under the low temperature after the ion reduction;

Reaction formula: 2. A ₂+ HCl → B ₂↓+H ₂O

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁

Here, A ₁On expression cats product and the trans-resveratrol aglycon-O ^-The water-insoluble salt that the dehydrogenation hydroxyl forms; B ₁Former trans-resveratrol aglycon after the expression hydrogen reduction; C ₁Expression is by Cl ^-Water miscible palmityl trimethyl ammonium chloride under the low temperature after the ion reduction;

Reaction formula: 2. A ₂+ HCl → B ₂+ H ₂O

A here ₂OH in expression cats product and the alkaline aqueous solution ^-The water-insoluble pseudobase that root chemical combination generates; B ₂The expression cats product is by Cl ^-Water miscible palmityl trimethyl ammonium chloride under the low temperature after the ion reduction; B ₂With above-mentioned C ₁Identical;

(11) above-mentioned (10) .1 product is added NaOH, Sodium Benzoate and anion surfactant fatty acid sodium salt, and be heated to 40 ℃-60 ℃; Aqueous ph value is being adjusted between the PH8-10, after add again the Sodium Benzoate of aqueous solution 1%-2% and the fatty acid sodium salt excessive a little with respect to octadecyl trimethyl ammonium chloride, the excessive degree of fatty acid sodium salt is the 0.2%-0.3% of the aqueous solution; Restir, speed 50-200 rev/min, time 10-30 minute; Again with above-mentioned C ₁Filter removal with the water-insoluble compound of fatty acid sodium salt chemical combination; Adding water soluble calcium salt or magnesium salts fully stir again, and rotating speed 100-200 rev/min, make calcium salt or magnesium salts and above-mentioned excessive fatty acid sodium salt chemical combination, generate water-insoluble compound and be filtered removal; Only have like this Sodium Benzoate and target product B in the aqueous solution ₁, be cooled to again 1 ℃-30 ℃, and with the hydrochloric acid regulating solution pH value to PH7, such target product B ₁Major part Precipitation from the aqueous solution; The effect of Sodium Benzoate here is the collaborative target product B that increases ₁Solubleness in the aqueous solution is convenient to B ₁With other separating substances; The recycling capable of circulation of the Sodium Benzoate aqueous solution; When sodium chloride content was too high in the Sodium Benzoate aqueous solution that recycles and reuses, adjustable water solution was to acid, and the recovery of benzoic acid revaporization concentrates to get the NaCl dry product; Here Sodium Benzoate also can omit; This step is separated the ultimate aim product B ₁Also can adopt following steps, add first an amount of NaOH, making aqueous ph value is PH8-12, and making aqueous temperature is 1 ℃-30 ℃, only has like this target product B ₁Be dissolved in low temperature alkaline aqueous solution and separate with octadecyl trimethyl ammonium chloride, obtain target product B ₁The aqueous solution uses the hydrochloric acid regulating solution pH value to PH7, like this target product B again ₁Precipitation from the aqueous solution is because the water insoluble or neutral aqueous solution of this target product;

(12) with above-mentioned B ₁Vacuum lyophilization obtains trans-resveratrol aglycon dry product, and 1-24 hour time of drying, freezing temp-40 ℃ is to-1 ℃, pressure≤25Pa;

2, described extracting method is preferably:

It is comprised of the following step:

One, the extraction of triterpene saponin:

(1) plant adds edible soft water or deionized water pulverizing;

(2) destroy plant cell wall or destroy plant cell wall with the freezing defreezing method that reheats with cellulose degraded;

(3) above-mentioned product is added 0.3%, the water soluble anionic surfactant that contain straight chain oleophilic group responsive to cationic substance, to improve the solubleness of triterpenoid saponin in the aqueous solution, temperature 50 C;

(4) with above-mentioned product heated and stirred, temperature 50 C, 50 rev/mins of stirring velocitys are to improve the dissolution rate of triterpenoid saponin in water;

(6) the above-mentioned aqueous solution that contains triterpenoid saponin is added an amount of NaOH, triterpenoid saponin is neutralized fully, generate water miscible salt; Salt brine solution PH8;

(7) the above-mentioned aqueous solution is added the cats product octadecyl trimethyl ammonium chloride again, restir fully reacts the triterpenoid saponin salt in cats product and the aqueous solution; The cats product molecule is connected on the triterpenoid saponin molecule-COO ^-On the dehydrogenation carboxyl or-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; Also chemical combination precipitation of cats product and anion surfactant wherein; And promote that cats product separates with precipitation or the suspension of water with the water-insoluble compound of triterpenoid saponin; Temperature 60 C, 400 rev/mins of rotating speeds, 60 minutes time;

(8) above-mentioned product is cooled to 20 ℃, makes total overall reaction thing precipitation or suspension;

(9) extract above-mentioned precipitation or suspended matter, with hydrochloric acid replacement(metathesis)reaction under agitation condition of 10%, 100 rev/mins of rotating speeds, 15 minutes reaction times, 20 ℃ of temperature, notice that hydrochloric acid is only excessive a little, solution ph 5 when reaction finishes makes the cats product that adds etc. be precipitated or the separation that suspends by complete reaction; The biological activity of recovery triterpenoid saponin and water-soluble;

Reaction formula: 1. A ₁+ HCl → B ₁+ C ₁↓

Reaction formula: 2. A ₂+ HCl → B ₂↓+C ₂↓

A here ₂The water-insoluble compound of expression anion surfactant and cats product.B ₂The water-insoluble compound of expression anion surfactant and H+ ion combination.C ₂Expression cats product and Cl ^-Water-insoluble octadecyl trimethyl ammonium chloride flocculent precipitate or suspended substance under the low temperature that ion combination forms;

Reaction formula: 3. A ₃+ HCl → B ₃↓+H ₂O

A here ₃OH in expression cats product and the alkaline aqueous solution ^-The water-insoluble alkali that root chemical combination generates.B ₃The expression cats product is by Cl ^-Octadecyl trimethyl ammonium chloride throw out or suspended substance after the ion reduction;

(10) above-mentioned reactant is filtered, only contained B ₁The water-soluble aqueous solution, vacuum lyophilization obtains the triterpenoid saponin dry product, wherein excessive a little hydrochloric acid (HCl gas) is recovered; 24 hours time of drying, freezing temp-40 ℃, pressure 15Pa;

Two, the extraction of flavonoid aglycon

(1) plant adds edible soft water or deionized water pulverizing;

(2) above-mentioned product is destroyed plant cell wall or destroys plant cell wall with the freezing defreezing method that reheats with cellulose degraded;

(3) above-mentioned product is added 0.3% pair of cationic substance sensitivity, contain the water soluble anionic surfactant of straight chain oleophilic group, to improve the solubleness of flavonoid glycoside in the aqueous solution, temperature 60 C;

(4) heated and stirred, temperature 70 C, 50 rev/mins of stirring velocitys are to improve the dissolution rate of flavonoid glycoside in water;

(5) squeeze and filter must contain the aqueous solution of flavonoid glycoside, and removes above-mentioned anion surfactant with Calcium hydrogen carbonate, and is for subsequent use;

(6) with above-mentioned product in stirring with the beta-glucoside enzyme liberating, the desugar of cracking glycosidic link gets Flavone aglycone, temperature 50 C, PH5,30 rev/mins of rotating speeds, 24 hours time; For the C-O glycosidic link;

(7) the above-mentioned aqueous solution that contains Flavone aglycone is added an amount of NaOH, make on the Flavone aglycone-the OH hydroxyl partially or completely neutralized, and generates water miscible salt; The salt brine solution pH value is PH8;

(8) the above-mentioned aqueous solution is added the cats product octadecyl trimethyl ammonium chloride again, restir fully reacts the Flavone aglycone salt in cats product and the aqueous solution; The cats product molecule is connected on the Flavone aglycone molecule-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; Temperature 60 C, 400 rev/mins of rotating speeds, 60 minutes time;

(9) above-mentioned product is cooled to 20 ℃, makes total overall reaction thing precipitation or suspension;

(10) extract above-mentioned precipitation or suspended matter, with hydrochloric acid replacement(metathesis)reaction under agitation condition of 10%, 50 rev/mins of rotating speeds, 30 minutes reaction times, 20 ℃ of temperature, notice that hydrochloric acid is only excessive a little, the aqueous solution was PH5 when reaction was finished, and the cats product that adds etc. is precipitated or the separation that suspends by complete reaction; Recover the biological activity of Flavone aglycone;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁↓

Reaction formula: 2. A ₂+ HCl → B ₂↓+H ₂O

(11) above-mentioned product is added NaOH, Sodium Benzoate and anion surfactant fatty acid sodium salt, and be heated to 60 ℃; Aqueous ph value is being adjusted to PH10, after add again the Sodium Benzoate of the aqueous solution 1% and the fatty acid sodium salt excessive a little with respect to octadecyl trimethyl ammonium chloride, the excessive degree of fatty acid sodium salt is 0.3% of the aqueous solution; Restir, 200 rev/mins of speed, 30 minutes time; Again with above-mentioned C ₁Filter removal with the water-insoluble compound of fatty acid sodium salt chemical combination; Adding water soluble calcium salt or magnesium salts fully stir again, and 200 rev/mins of rotating speeds make calcium salt or magnesium salts and above-mentioned excessive fatty acid sodium salt chemical combination, generate water-insoluble compound and are filtered removal; Only have like this Sodium Benzoate and target product B in the aqueous solution ₁, be cooled to again 30 ℃, and with the hydrochloric acid regulating solution pH value to PH7, such target product B ₁Major part Precipitation from the aqueous solution; The effect of Sodium Benzoate here is the collaborative target product B that increases ₁Solubleness in the aqueous solution is convenient to B ₁With other separating substances; The recycling capable of circulation of the Sodium Benzoate aqueous solution; When sodium chloride content was too high in the Sodium Benzoate aqueous solution that recycles and reuses, adjustable water solution was to acid, and the recovery of benzoic acid revaporization concentrates to get the NaCl dry product; This step is separated the ultimate aim product B ₁Also can adopt following steps, add first an amount of NaOH, making aqueous ph value is PH8-12, and making aqueous temperature is 1 ℃-30 ℃, only has like this target product B ₁Be dissolved in low temperature alkaline aqueous solution and separate with octadecyl trimethyl ammonium chloride, obtain target product B ₁The aqueous solution uses the hydrochloric acid regulating solution pH value to PH7, like this target product B again ₁Precipitation from the aqueous solution is because the water insoluble or neutral aqueous solution of this target product;

(12) with above-mentioned B ₁Vacuum lyophilization obtains the Flavone aglycone dry product, 3 hours time of drying, freezing temp-40 ℃, pressure 15Pa;

Three, the extraction of trans-resveratrol aglycon

(1) plant adds edible soft water or deionized water pulverizing;

(3) above-mentioned product is added 0.3% pair of cationic substance sensitivity, contain the water soluble anionic surfactant of straight chain oleophilic group, to improve the solubleness of polydatin in the aqueous solution, temperature 50 C;

(4) heated and stirred, temperature 50 C, 200 rev/mins of stirring velocitys improve the dissolution rate of polydatin in water;

(5) squeeze and filter must contain the aqueous solution of polydatin, adds Calcium hydrogen carbonate and removes above-mentioned anion surfactant, and is for subsequent use;

(6) with above-mentioned product in stirring with the beta-glucoside enzyme liberating, the cracking glycosidic link, desugar gets the trans-resveratrol aglycon, temperature 50 C, PH5,30 rev/mins of rotating speeds, 24 hours time; For the C-O glycosidic link;

(7) the above-mentioned aqueous solution that contains the trans-resveratrol aglycon is added an amount of NaOH, the hydroxyl on the trans-resveratrol aglycon is partially or completely neutralized, generate water miscible salt; Salt brine solution PH8;

(8) the above-mentioned aqueous solution is added the cats product octadecyl trimethyl ammonium chloride again, restir fully reacts the trans-resveratrol aglycon salt in cats product and the aqueous solution; The cats product molecule is connected on the resveratrol molecule-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; Temperature 60 C, 400 rev/mins of rotating speeds, 60 minutes time;

(10) extract above-mentioned precipitation or suspended matter, with hydrochloric acid replacement(metathesis)reaction under agitation condition of 10%, 200 rev/mins of rotating speeds, 30 minutes reaction times, 20 ℃ of temperature, notice that hydrochloric acid is only excessive a little, the aqueous solution was PH5 when reaction was finished, and made the cats product that adds etc. by complete reaction/precipitation or the separation that suspends; Recover the biological activity of trans-resveratrol;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁↓

Reaction formula: 2. A ₂+ HCl → B ₂↓+H ₂O

(11) above-mentioned product is added NaOH, Sodium Benzoate and anion surfactant fatty acid sodium salt, and be heated to 60 ℃; Aqueous ph value is being adjusted between the PH10, after add again the Sodium Benzoate of the aqueous solution 1% and the fatty acid sodium salt excessive a little with respect to octadecyl trimethyl ammonium chloride, the excessive degree of fatty acid sodium salt is 0.3% of the aqueous solution; Restir, 200 rev/mins of speed, 30 minutes time; Again with above-mentioned C ₁Filter removal with the water-insoluble compound of fatty acid sodium salt chemical combination; Adding water soluble calcium salt or magnesium salts fully stir again, and 200 rev/mins of rotating speeds make calcium salt or magnesium salts and above-mentioned excessive fatty acid sodium salt chemical combination, generate water-insoluble compound and are filtered removal; Only have like this Sodium Benzoate and target product B in the aqueous solution ₁, be cooled to again 30 ℃, and with the hydrochloric acid regulating solution pH value to PH7, such target product B ₁Major part Precipitation from the aqueous solution; The effect of Sodium Benzoate here is the collaborative target product B that increases ₁Solubleness in the aqueous solution is convenient to B ₁With other separating substances; The recycling capable of circulation of the Sodium Benzoate aqueous solution; When sodium chloride content was too high in the Sodium Benzoate aqueous solution that recycles and reuses, adjustable water solution was to acid, and the recovery of benzoic acid revaporization concentrates to get the NaCl dry product; This step is separated the ultimate aim product B ₁Also can adopt following steps, add first an amount of NaOH, making aqueous ph value is PH8-12, and making aqueous temperature is 1 ℃-30 ℃, so only

Target product B is arranged ₁Be dissolved in low temperature alkaline aqueous solution and separate with octadecyl trimethyl ammonium chloride, obtain target product B ₁The aqueous solution uses the hydrochloric acid regulating solution pH value to PH7, like this target product B again ₁Precipitation from the aqueous solution is because the water insoluble or neutral aqueous solution of this target product;

(12) with above-mentioned B ₁Vacuum lyophilization obtains trans-resveratrol aglycon dry product, 24 hours time of drying, freezing temp-40 ℃, pressure 15Pa;

The invention has the beneficial effects as follows:

The present invention is compared with prior art:

One, production efficiency is high, and production cost is low, and is good with Environmental compatibility, can realize the discharging of water pollution-free thing, is fit to large-scale industrialized production.

Two, isolated water-insoluble compound incendivity provides heat energy from final product, reduces energy consumption, and recyclable hydrogen chloride gas, NO ₂Gas, recycle or supply raw materials for other industry.

Three, the high directional separation of selecting, product purity is high, can reach more than 96% (may also contain a certain amount of fully not dry moisture content).Efficient, rationally and take full advantage of and opened up new feasible road for development for natural organic-compound.

Four, production unit is simple, and energy consumption is low, energy-conservation, safety in production.

Five, extract triterpenoid saponin of the present invention, natural flavonoid (hydroxyl-OH comprises flavonoid and isoflavones), trans-resveratrol are that new road has been opened up in China's herbal medicine and biological pesticide development.

Six, the present invention reacts reduction step or/and the ultimate aim product B with cats product combination reaction, cooling down, its resultant with hydrochloric acid displaces ₁With separating step and the combination thereof of cats product etc. be that core technology of the present invention is namely innovated essential features.

Embodiment:

Below just embodiment the invention will be further described:

Embodiment 1:

Carry out as follows during extraction:

One, the extraction of the glossy ganoderma saponin(e (or ginsenoside) of triterpene saponin:

(1) plant adds edible soft water or deionized water pulverizing;

(3) above-mentioned product is added the fatty acid sodium salt of the aqueous solution 0.3%, to improve the solubleness of glossy ganoderma saponin(e in the aqueous solution, temperature 50 C;

(4) with above-mentioned product heated and stirred, temperature 50 C, 200 rev/mins of stirring velocitys are to improve the dissolution rate of glossy ganoderma saponin(e in water;

(5) squeeze and filter, the aqueous solution that must contain the glossy ganoderma saponin(e is for subsequent use;

(6) the above-mentioned aqueous solution that contains the glossy ganoderma saponin(e is added an amount of NaOH, the glossy ganoderma saponin(e is neutralized fully, generate water miscible salt; Salt brine solution PH8;

(7) the above-mentioned aqueous solution is added the cats product octadecyl trimethyl ammonium chloride again, restir fully reacts the glossy ganoderma saponin(e salt in cats product and the aqueous solution; The cats product molecule is connected to the dehydrogenation carboxyl-COO on the glossy ganoderma saponin(e molecule ^-Go up or dehydrogenation hydroxyl-O ^-On, obtain water-insoluble salt; Also chemical combination precipitation of cats product and anion surfactant wherein; And promote that cats product separates with precipitation or the suspension of water with the water-insoluble compound of glossy ganoderma saponin(e; Temperature 50 C, 200 rev/mins of rotating speeds, 60 minutes time;

(8) above-mentioned product is cooled to 30 ℃, makes total overall reaction thing precipitation or suspension;

(9) extract above-mentioned precipitation or suspended matter, with hydrochloric acid replacement(metathesis)reaction under agitation condition of 20%, 100 rev/mins of rotating speeds, 30 minutes reaction times, 30 ℃ of temperature, notice that hydrochloric acid is only excessive a little, the aqueous solution is controlled at PH5 in the time of will react end, and the cats product that adds etc. is precipitated or the separation that suspends by complete reaction; The biological activity of recovery glossy ganoderma saponin(e and water-soluble;

Reaction formula: 1. A ₁+ HCl → B ₁+ C ₁↓

Here, A ₁The water-insoluble salt that dehydrogenation carboxyl on expression cats product and the glossy ganoderma saponin(e forms; B ₁Former glossy ganoderma saponin(e after the expression hydrogen reduction; C ₁Expression is by Cl ^-Water-insoluble octadecyl trimethyl ammonium chloride throw out or suspended substance under the low temperature after the ion reduction;

Reaction formula: 2. A ₂+ HCl → B ₂↓+C ₂↓

Reaction formula: 3. A ₃+ HCl → B ₃↓+H ₂O

(10) above-mentioned reactant is filtered, only contained B ₁The water-soluble aqueous solution, vacuum lyophilization obtains glossy ganoderma saponin(e dry product, wherein excessive a little hydrochloric acid (HCl gas) is recovered; 24 hours time of drying, freezing temp-40 ℃, pressure 15Pa;

Two, the extraction of isoflavone genin

(1) plant adds edible soft water or deionized water pulverizing;

(2) above-mentioned product is added the fatty acid sodium salt of the aqueous solution 0.3%, to improve the solubleness of soybean isoflavone glycoside from soybean isoflavones in the aqueous solution, temperature 50 C;

(3) heated and stirred, temperature 70 C, 100 rev/mins of stirring velocitys are to improve the dissolution rate of soybean isoflavone glycoside from soybean isoflavones in water;

(4) squeeze and filter must contain the aqueous solution of soybean isoflavone glycoside from soybean isoflavones, adds Calcium hydrogen carbonate and stirs and remove above-mentioned anion surfactant, and is for subsequent use;

(5) with above-mentioned product in stirring with the beta-glucoside enzyme liberating, the desugar of cracking glycosidic link gets isoflavone genin, temperature 50 C, PH5, rotating speed 50 turns, 10 hours time; For the C-O glycosidic link;

(6) the above-mentioned aqueous solution that contains isoflavone genin is added an amount of NaOH, make on its aglycon-the OH hydroxyl partially or completely neutralized, and generates water miscible salt; The salt brine solution pH value is PH8;

(7) the above-mentioned aqueous solution is added the cats product octadecyl trimethyl ammonium chloride again, restir fully reacts the isoflavone genin salt in cats product and the aqueous solution; The cats product molecule is connected on the Flavone aglycone molecule-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; Temperature 50 C, 100 rev/mins of rotating speeds, 30 minutes time;

(9) extract above-mentioned precipitation or suspended matter, with hydrochloric acid replacement(metathesis)reaction under agitation condition of 10%, 200 rev/mins of rotating speeds, 30 minutes reaction times, 30 ℃ of temperature notice that hydrochloric acid is only excessive a little, make the cats product that adds etc. by complete reaction/precipitation or the separation that suspends; Recover the biological activity of isoflavone genin; Aqueous ph value was PH5 when reaction finished;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁↓

Here, A ₁On expression cats product and the isoflavone genin-O ^-The water-insoluble salt that the dehydrogenation hydroxyl forms; B ₁Former isoflavone genin after the expression hydrogen reduction; C ₁Expression is by Cl ^-Water-insoluble octadecyl trimethyl ammonium chloride flocculent precipitate or suspended substance under the low temperature after the ion reduction;

Reaction formula: 2. A ₂+ HCl → B ₂↓+H ₂O

A here ₂OH in expression cats product and the alkaline aqueous solution ^-The water-insoluble alkali that root chemical combination generates.B ₂The expression cats product is by Cl ^-Octadecyl trimethyl ammonium chloride throw out or suspended substance after the ion reduction; B ₂With above-mentioned C ₁Identical;

(10) above-mentioned product is added NaOH, Sodium Benzoate and anion surfactant fatty acid sodium salt, and be heated to 50 ℃; Aqueous ph value is being adjusted to PH10, after add again the Sodium Benzoate of the aqueous solution 1% and the fatty acid sodium salt excessive a little with respect to octadecyl trimethyl ammonium chloride, the excessive degree of fatty acid sodium salt is 0.3% of the aqueous solution; Restir, 100 rev/mins of speed, 30 minutes time; Again with above-mentioned C ₁Filter removal with the water-insoluble compound of fatty acid sodium salt chemical combination; Adding water soluble calcium salt or magnesium salts fully stir again, and 200 rev/mins of rotating speeds make calcium salt or magnesium salts and above-mentioned excessive fatty acid sodium salt chemical combination, generate water-insoluble compound and are filtered removal; Only have like this Sodium Benzoate and target product B in the aqueous solution ₁, be cooled to again 30 ℃, and with the hydrochloric acid regulating solution pH value to PH7, such target product B ₁Major part Precipitation from the aqueous solution; The effect of Sodium Benzoate here is the collaborative target product B that increases ₁Solubleness in the aqueous solution is convenient to B ₁With other separating substances; The recycling capable of circulation of the Sodium Benzoate aqueous solution; When sodium chloride content was too high in the Sodium Benzoate aqueous solution that recycles and reuses, adjustable water solution was to acid, and the recovery of benzoic acid revaporization concentrates to get the NaCl dry product; This step is separated the ultimate aim product B ₁Also can adopt following steps, add first an amount of NaOH, making aqueous ph value is PH8-12, and making aqueous temperature is 1 ℃-30 ℃, only has like this target product B ₁Be dissolved in low temperature alkaline aqueous solution and separate with octadecyl trimethyl ammonium chloride, obtain target product B ₁The aqueous solution uses the hydrochloric acid regulating solution pH value to PH7, like this target product B again ₁Precipitation from the aqueous solution is because the water insoluble or neutral aqueous solution of this target product;

(11) with above-mentioned B ₁Vacuum lyophilization obtains the isoflavone genin dry product, 4 hours time of drying, freezing temp-40 ℃, pressure 15Pa;

Three, the extraction of trans-resveratrol aglycon

(1) plant adds edible soft water or deionized water pulverizing;

(3) above-mentioned product is added the fatty acid sodium salt of the aqueous solution 0.3%, to improve the solubleness of polydatin in the aqueous solution, temperature 50 C;

(6) with above-mentioned product in stirring with the beta-glucoside enzyme liberating, the cracking glycosidic link, desugar gets the trans-resveratrol aglycon, temperature 50 C, PH5,50 rev/mins of rotating speeds, 10 hours time; For the C-O glycosidic link;

(8) the above-mentioned aqueous solution is added the cats product octadecyl trimethyl ammonium chloride again, restir fully reacts the trans-resveratrol aglycon salt in cats product and the aqueous solution; The cats product molecule is connected on the resveratrol molecule-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; Temperature 50 C, 200 rev/mins of rotating speeds, 60 minutes time;

(9) above-mentioned product is cooled to 30 ℃, makes total overall reaction thing precipitation or suspension;

(10) extract above-mentioned precipitation or suspended matter, with hydrochloric acid replacement(metathesis)reaction under agitation condition of 10%, 100 rev/mins of rotating speeds, in 30 minutes reaction times, 30 ℃ of temperature notice that hydrochloric acid is only excessive a little, and aqueous ph value was PH5 when reaction finished; Make the cats product that adds etc. by complete reaction/precipitation or suspend and separate; Recover the biological activity of trans-resveratrol;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁↓

Reaction formula: 2. A ₂+ HCl → B ₂↓+H ₂O

A here ₂OH in expression cats product and the alkaline aqueous solution _-The water-insoluble pseudobase that root chemical combination generates.B ₂The expression cats product is by Cl ^-Octadecyl trimethyl ammonium chloride throw out or suspended substance after the ion reduction; B ₂With above-mentioned C ₁Identical;

(11) above-mentioned product is added NaOH, Sodium Benzoate and anion surfactant fatty acid sodium salt, and be heated to 50 ℃; Aqueous ph value is being adjusted to PH10, after add again the Sodium Benzoate of the aqueous solution 1% and the fatty acid sodium salt excessive a little with respect to octadecyl trimethyl ammonium chloride, the excessive degree of fatty acid sodium salt is 0.3% of the aqueous solution; Restir, 100 rev/mins of speed, 30 minutes time; Again with above-mentioned C ₁Filter removal with the water-insoluble compound of fatty acid sodium salt chemical combination; Adding water soluble calcium salt or magnesium salts fully stir again, and 200 rev/mins of rotating speeds make calcium salt or magnesium salts and above-mentioned excessive fatty acid sodium salt chemical combination, generate water-insoluble compound and are filtered removal; Only have like this Sodium Benzoate and target product B in the aqueous solution ₁, be cooled to again 30 ℃, and with the hydrochloric acid regulating solution pH value to PH7, such target product B ₁Major part Precipitation from the aqueous solution; The effect of Sodium Benzoate here is the collaborative target product B that increases ₁Solubleness in the aqueous solution is convenient to B ₁With other separating substances; The recycling capable of circulation of the Sodium Benzoate aqueous solution; When sodium chloride content was too high in the Sodium Benzoate aqueous solution that recycles and reuses, adjustable water solution was to acid, and the recovery of benzoic acid revaporization concentrates to get the NaCl dry product; This step is separated the ultimate aim product B ₁Also can adopt following steps, add first an amount of NaOH, making aqueous ph value is PH8-12, and making aqueous temperature is 1 ℃-30 ℃, only has like this target product B ₁Be dissolved in low temperature alkaline aqueous solution and separate with octadecyl trimethyl ammonium chloride, obtain target product B ₁The aqueous solution uses the hydrochloric acid regulating solution pH value to PH7, like this target product B again ₁Precipitation from the aqueous solution is because the water insoluble or neutral aqueous solution of this target product;

(12) with above-mentioned B ₁Vacuum lyophilization obtains trans-resveratrol aglycon dry product, 5 hours time of drying, freezing temp-40 ℃, pressure 15Pa.

Embodiment 2:

Extract as follows:

One, the extraction of the Potenlini of triterpene saponin:

(1) plant adds edible soft water or deionized water pulverizing;

(3) above-mentioned product is added the fatty acid sodium salt of the aqueous solution 0.3%, to improve the solubleness of Potenlini in the aqueous solution, temperature 50 C;

(4) with above-mentioned product heated and stirred, temperature 50 C, 200 rev/mins of stirring velocitys are to improve the dissolution rate of Potenlini in water;

(5) squeeze and filter, it is for subsequent use to contain the Radix Glycyrrhizae aqueous acid;

(6) the above-mentioned Radix Glycyrrhizae aqueous acid that contains is added an amount of NaOH, Potenlini is neutralized fully, generate water miscible salt; Salt brine solution PH8;

(7) the above-mentioned aqueous solution is added the cats product octadecyl trimethyl ammonium chloride again, restir fully reacts the glycyrrhetate in cats product and the aqueous solution; The cats product molecule is connected on the Potenlini molecule-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; Also chemical combination precipitation of cats product and anion surfactant wherein; And promote that cats product separates with precipitation or the suspension of water with the water-insoluble compound of Potenlini; Temperature 50 C, 200 rev/mins of rotating speeds, 60 minutes time;

(9) extract above-mentioned precipitation or suspended matter, with hydrochloric acid replacement(metathesis)reaction under agitation condition of 20%, 100 rev/mins of rotating speeds, 30 minutes reaction times, 30 ℃ of temperature, notice that hydrochloric acid is only excessive a little, the aqueous solution is controlled at PH5 in the time of will react end, and the cats product that adds etc. is precipitated or the separation that suspends by complete reaction; The biological activity of recovery Potenlini and water-soluble;

Reaction formula: 1. A ₁+ HCl → B ₁+ C ₁↓

Here, A ₁The water-insoluble salt that dehydrogenation hydroxyl on expression cats product and the Potenlini forms; B ₁Former Potenlini after the expression hydrogen reduction; C ₁Expression is by Cl ^-Water-insoluble octadecyl trimethyl ammonium chloride throw out or suspended substance under the low temperature after the ion reduction;

Reaction formula: 2. A ₂+ HCl → B ₂↓+C ₂↓

Reaction formula: 3. A ₃+ HCl → B ₃↓+H ₂O

(10) above-mentioned reactant is filtered, only contained B ₁Water-soluble, vacuum lyophilization obtains the Potenlini dry product, wherein excessive a little hydrochloric acid (HCl gas) is recovered; 24 hours time of drying, freezing temp-40 ℃, pressure 15Pa;

Two, the extraction of rutin aglycon:

(1) plant adds edible soft water or deionized water pulverizing;

(2) above-mentioned product is added the fatty acid sodium salt of the aqueous solution 0.3%, to improve the solubleness of rutin glycosides in the aqueous solution, temperature 50 C;

(3) heated and stirred, temperature 70 C, 100 rev/mins of stirring velocitys are to improve the dissolution rate of rutin glycosides in water;

(4) squeeze and filter must contain the aqueous solution of rutin glycosides, adds Calcium hydrogen carbonate and stirs and remove above-mentioned anion surfactant, and is for subsequent use;

(5) with above-mentioned product in stirring with the beta-glucoside enzyme liberating, the desugar of cracking glycosidic link gets the rutin aglycon, temperature 50 C, PH5, rotating speed 50 turns, 10 hours time; For the C-O glycosidic link;

(6) the above-mentioned aqueous solution that contains the rutin aglycon is added an amount of NaOH, make on its aglycon-the OH hydroxyl partially or completely neutralized, and generates water miscible salt; The salt brine solution pH value is PH8;

(7) the above-mentioned aqueous solution is added the cats product palmityl trimethyl ammonium chloride again, restir fully reacts the rutin aglycon salt in cats product and the aqueous solution; The cats product molecule is connected on the rutin aglycon molecule-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; Temperature 50 C, 100 rev/mins of rotating speeds, 30 minutes time;

(8) above-mentioned product is cooled to 2 ℃, makes total overall reaction thing precipitation or suspension;

(9) extract above-mentioned precipitation or suspended matter, with hydrochloric acid replacement(metathesis)reaction under agitation condition of 10%, 200 rev/mins of rotating speeds, in 30 minutes reaction times, 30 ℃ of temperature notice that hydrochloric acid is only excessive a little, make the cats product that adds by complete reaction; Recover the biological activity of rutin aglycon; Aqueous ph value was PH5 when reaction finished;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁

Here, A ₁On expression cats product and the rutin aglycon-O ^-The water-insoluble salt that the dehydrogenation hydroxyl forms; B ₁Former rutin aglycon after the expression hydrogen reduction; C ₁Expression is by Cl ^-Water miscible palmityl trimethyl ammonium chloride under the low temperature after the ion reduction;

Reaction formula: 2. A ₂+ HCl → B ₂+ H ₂O

(10) with above-mentioned product direct filtration, obtain target product B ₁And with a small amount of cats product in tap water or this target product of washed with de-ionized water, the cats product starting material have greatly been saved in the recycling capable of circulation of the aqueous solution of compositions comprising cationic surfactants;

(11) with above-mentioned B ₁Vacuum lyophilization obtains rutin aglycon dry product, 4 hours time of drying, freezing temp-40 ℃, pressure 15Pa;

Three, the extraction of trans-resveratrol aglycon:

(1) plant adds edible soft water or deionized water pulverizing;

(8) the above-mentioned aqueous solution is added the cats product palmityl trimethyl ammonium chloride again, restir fully reacts the trans-resveratrol aglycon salt in cats product and the aqueous solution; The cats product molecule is connected on the resveratrol molecule-O ^-On the dehydrogenation hydroxyl, obtain water-insoluble salt; Temperature 50 C, 200 rev/mins of rotating speeds, 60 minutes time;

(9) above-mentioned product is cooled to 2 ℃, makes total overall reaction thing precipitation or suspension;

(10) extract above-mentioned precipitation or suspended matter, with hydrochloric acid replacement(metathesis)reaction under agitation condition of 10%, 100 rev/mins of rotating speeds, in 30 minutes reaction times, 30 ℃ of temperature notice that hydrochloric acid is only excessive a little, and aqueous ph value was PH5 when reaction finished; Make the cats product that adds by complete reaction; Recover the biological activity of trans-resveratrol;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁

Reaction formula: 2. A ₂+ HCl → B ₂+ H ₂O

(11) with above-mentioned product direct filtration, obtain target product B ₁And with a small amount of cats product in tap water or this target product of washed with de-ionized water, the cats product starting material have greatly been saved in the recycling capable of circulation of the aqueous solution of compositions comprising cationic surfactants;

Claims

1. natural hydroxyl is or/and the extracting method of carboxylic compound, and its feature is that mainly it is comprised of the following step:

One, the extraction of triterpene saponin:

(1) plant adds edible soft water or deionized water pulverizing;

(3) above-mentioned product is added, the water soluble anionic surfactant that contain straight chain oleophilic group responsive to cationic substance of 0.2%-0.5%, to improve the solubleness of triterpenoid saponin in the aqueous solution, 30 ℃-60 ℃ of temperature;

Reaction formula: 1. A ₁+ HCl → B ₁+ C ₁↓

Reaction formula: 2. A ₂+ HCl → B ₂↓+C ₂↓

Reaction formula: 3. A ₃+ HCl → B ₃↓+H ₂O

(10) above-mentioned reactant is filtered, only contained B ₁The water-soluble aqueous solution, vacuum lyophilization obtains the triterpenoid saponin dry product, wherein excessive a little hydrochloric acid (HCl gas) is recovered; 10-24 hour time of drying, freezing temp-40 ℃ is to-20 ℃, pressure≤25Pa;

Two, the extraction of flavonoid aglycon

(1) plant adds edible soft water or deionized water pulverizing;

(3) above-mentioned product is added 0.2%-0.5% to the cationic substance sensitivity, contain the water soluble anionic surfactant of straight chain oleophilic group, to improve the solubleness of flavonoid glycoside in the aqueous solution, 30 ℃-60 ℃ of temperature;

(6) with above-mentioned product in stirring with the beta-glucoside enzyme liberating, the desugar of cracking glycosidic link gets Flavone aglycone, 40 ℃-50 ℃ of temperature, PH4-6.9, rotating speed 30-100 rev/min, time 10-24 hour; For the C-O glycosidic link;

(10) extract above-mentioned precipitation or suspended matter, hydrochloric acid replacement(metathesis)reaction under agitation condition with 2%-30%, rotating speed 50-600 rev/min, reaction times 10-30 minute, 1 ℃-30 ℃ of temperature, notice that hydrochloric acid is only excessive a little, the aqueous solution is controlled between the PH4-6.9 in the time of will reacting end, makes the cats product that adds by complete reaction/precipitation or suspension; Recover the biological activity of Flavone aglycone;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁↓

Reaction formula: 2. A ₂+ HCl → B ₂↓+H ₂O

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁

Reaction formula: 2. A ₂+ HCl → B ₂+ H ₂O

A here ₂OH in expression cats product and the alkaline aqueous solution ^-The water-insoluble pseudobase that root chemical combination generates.B ₂The expression cats product is by Cl ^-Water miscible palmityl trimethyl ammonium chloride after the ion reduction; B ₂With above-mentioned C ₁Identical;

(11) product among above-mentioned (10) .1 is added NaOH, Sodium Benzoate and anion surfactant fatty acid sodium salt, and be heated to 40 ℃-60 ℃; Aqueous ph value is being adjusted between the PH8-10, after add again the Sodium Benzoate of aqueous solution 1%-2% and the fatty acid sodium salt excessive a little with respect to octadecyl trimethyl ammonium chloride, the excessive degree of fatty acid sodium salt is the 0.2%-0.3% of the aqueous solution; Restir, speed 50-200 rev/min, time 10-30 minute; Again with above-mentioned C ₁Filter removal with the water-insoluble compound of fatty acid sodium salt chemical combination, wherein also there is the hydroxide radical (OH in octadecyl trimethyl ammonium chloride and the aqueous solution in this ^-) negative ion chemical combination water-insoluble pseudobase compound and removed simultaneously; Adding water soluble calcium salt or magnesium salts fully stir again, and rotating speed 100-200 rev/min, make calcium salt or magnesium salts and above-mentioned excessive fatty acid sodium salt chemical combination, generate water-insoluble compound and be filtered removal; Only have like this Sodium Benzoate and target product B in the aqueous solution ₁, be cooled to again 1 ℃-30 ℃, and with the hydrochloric acid regulating solution pH value to PH7, such target product B ₁Major part Precipitation from the aqueous solution; The effect of Sodium Benzoate here is the collaborative target product B that increases ₁Solubleness in the aqueous solution is convenient to B ₁With other separating substances; The recycling capable of circulation of the Sodium Benzoate aqueous solution; When sodium chloride content was too high in the Sodium Benzoate aqueous solution that recycles and reuses, adjustable water solution was to acid, and the recovery of benzoic acid revaporization concentrates to get the NaCl dry product; This step is separated the ultimate aim product B ₁Also can adopt following steps, add first an amount of NaOH, making aqueous ph value is that PH8-12, aqueous temperature are 1 ℃-30 ℃, only has like this target product B ₁Be dissolved in low temperature alkaline aqueous solution and separate with octadecyl trimethyl ammonium chloride throw out or suspended substance, obtain target product B ₁The aqueous solution uses the hydrochloric acid regulating solution pH value to PH7, like this target product B again ₁Major part Precipitation from the aqueous solution is because the water insoluble or neutral aqueous solution of this target product;

Product direct filtration with among above-mentioned (10) .2 obtains target product B ₁And with tap water or washed with de-ionized water a small amount of cats product wherein; The recycling capable of circulation of the aqueous solution of compositions comprising cationic surfactants; (12) with above-mentioned B ₁Vacuum lyophilization obtains the Flavone aglycone dry product, and 1-24 hour time of drying, freezing temp-40 ℃ is to-1 ℃, pressure≤25Pa;

Three, the extraction of trans-resveratrol aglycon

(1) plant adds edible soft water or deionized water pulverizing;

(3) above-mentioned product is added 0.2%-0.5% to the cationic substance sensitivity, contain the water soluble anionic surfactant of straight chain oleophilic group, to improve the solubleness of polydatin in the aqueous solution, 30 ℃-60 ℃ of temperature;

(4) heated and stirred, 25 ℃-80 ℃ of temperature, improve the dissolution rate of trans-resveratrol in water by stirring velocity 50-200 rev/min;

(5) squeeze and filter must contain the aqueous solution of polydatin, and adding water soluble calcium salt or magnesium salts and above-mentioned anion surfactant are combined to water-insoluble salt to remove anion surfactant again, and be for subsequent use;

(10) extract above-mentioned precipitation or suspended matter, hydrochloric acid replacement(metathesis)reaction under agitation condition with 2%-30%, rotating speed 50-600 rev/min, reaction times 10-30 minute, 1 ℃-30 ℃ of temperature, notice that hydrochloric acid is only excessive a little, the aqueous solution is controlled at PH4-6.9 in the time of will reacting end, makes the cats product that adds by complete reaction/precipitation or suspension;

Recover the biological activity of trans-resveratrol;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁↓

Reaction formula: 2. A ₂+ HCl → B ₂↓+H ₂O

A here ₂OH in expression cats product and the alkaline aqueous solution ^-The water-insoluble pseudobase that root chemical combination generates.B ₂The expression cats product is by Cl ^-Octadecyl trimethyl ammonium chloride throw out or suspended substance after the ion reduction;

Reaction formula: 1. A ₁+ HCl → B ₁↓+C ₁

Reaction formula: 2. A ₂+ HCl → B ₂+ H ₂O

(11) product with above-mentioned (10) .1 adds NaOH, Sodium Benzoate and anion surfactant fatty acid sodium salt, and is heated to 40 ℃-60 ℃; Aqueous ph value is being adjusted between the PH8-10, after add again the Sodium Benzoate of aqueous solution 1%-2% and the fatty acid sodium salt excessive a little with respect to octadecyl trimethyl ammonium chloride, the excessive degree of fatty acid sodium salt is the 0.2%-0.3% of the aqueous solution; Restir, speed 50-200 rev/min, time 10-30 minute; Again with above-mentioned C ₁Filter removal with the water-insoluble compound of fatty acid sodium salt chemical combination, wherein also there is the hydroxide radical (OH in octadecyl trimethyl ammonium chloride and the aqueous solution in this ^-) negative ion chemical combination water-insoluble pseudobase compound and removed simultaneously; Adding water soluble calcium salt or magnesium salts fully stir again, and rotating speed 100-200 rev/min, make calcium salt or magnesium salts and above-mentioned excessive fatty acid sodium salt chemical combination, generate water-insoluble compound and be filtered removal; Only have like this Sodium Benzoate and target product B in the aqueous solution ₁, be cooled to again 1 ℃-30 ℃, and with the hydrochloric acid regulating solution pH value to PH7, such target product B ₁Major part Precipitation from the aqueous solution; The effect of Sodium Benzoate here is the collaborative target product B that increases ₁Solubleness in the aqueous solution is convenient to B ₁With other separating substances; The recycling capable of circulation of the Sodium Benzoate aqueous solution; When sodium chloride content was too high in the Sodium Benzoate aqueous solution that recycles and reuses, adjustable water solution was to acid, and the recovery of benzoic acid revaporization concentrates to get the NaCl dry product; This step is separated the ultimate aim product B ₁Also can adopt following steps, add first an amount of NaOH, making aqueous ph value is that PH8-12, aqueous temperature are 1 ℃-30 ℃, only has like this target product B ₁Be dissolved in low temperature alkaline aqueous solution and separate with octadecyl trimethyl ammonium chloride throw out or suspended substance, obtain target product B ₁The aqueous solution uses the hydrochloric acid regulating solution pH value to PH7, like this target product B again ₁Major part Precipitation from the aqueous solution is because the water insoluble or neutral aqueous solution of this target product;

Product direct filtration with among above-mentioned (10) .2 obtains target product B ₁And with tap water or washed with de-ionized water a small amount of cats product wherein; The recycling capable of circulation of the aqueous solution of compositions comprising cationic surfactants;

(12) with above-mentioned B ₁Vacuum lyophilization obtains trans-resveratrol aglycon dry product, and 1-24 hour time of drying, freezing temp-40 ℃ is to-1 ℃, pressure≤25Pa.