CN112876523B - Method for recovering tannic acid from fructus momordicae, sweet tea or stevia rebaudiana floc residues - Google Patents
Method for recovering tannic acid from fructus momordicae, sweet tea or stevia rebaudiana floc residues Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
Abstract
The invention provides a method for recovering tannic acid from fructus momordicae, sweet tea or stevia rebaudiana flocculation residues, which comprises the following steps: a) Crushing and sieving the dried flocculated slag to obtain undersize; b) Loading the undersize into a chromatographic column, compacting, sealing two ends of the chromatographic column, and vacuumizing to obtain a chromatographic column filled with the undersize; c) Washing the column with a leaching agent, and collecting an effluent; d) Purifying the effluent to obtain tannic acid product. The method provided by the invention can recover tannic acid from the fructus momordicae, sweet tea or stevia rebaudiana flocculation residues, and has high recovery rate and high purity.
Description
Technical Field
The invention belongs to the technical field of natural product extraction, and particularly relates to a method for recovering tannic acid from fructus momordicae, sweet tea or stevia rebaudiana floc residues.
Background
Tannins, also known as tannins or tannins, are plant polyphenols in the plant kingdom that are composed of glucose (and other polyols) esters of gallic acid (or polymers thereof), polymers of Huang Wanjiao and derivatives thereof, and mixtures of the two. The compounds can combine with proteins to form water insoluble precipitates, so that the compounds can form dense, flexible, difficult-to-putrefaction and difficult-to-permeate leather with the proteins of the animal skin, and are called tannins. Generally pale yellow or colorless powder, is easily soluble in glycerol, soluble in water and ethanol, and insoluble in diethyl ether and chloroform. In medicine, tannic acid has hemostatic and antiallergic effects, and can be made into ointment for topical application for treating scald, ulcer, eczema, hemorrhoid, etc., and also has effects in inhibiting activity of snake venom protein, neutralizing toxicity of snake venom, and in beverage aspect, tannic acid can act as food antioxidant, and can be mixed with antibiotics and amino acids for use, and has the main characteristics of good water solubility, and easy protein coprecipitation, thereby improving shelf life of beverage.
Lo Han Guo, sweet tea and stevia are three major plant materials for the preparation of natural sweeteners. The prior art of the flocculation residues of the fructus momordicae, the sweet tea and the stevia rebaudiana comprises the following aspects:
and (1) recycling the flocculation slag:
aiming at the process of the grosvenor momordica fruit, the sweet tea and the stevia rebaudiana, the technology is mainly used for extracting active ingredients (the grosvenor momordica fruit sweet glycoside, the sweet tea glycoside and the stevioside) in the raw materials, and the research on the utilization of flocculation residues of the raw materials is less.
(II) source of flocculation slag:
in order to obtain a clearer leaching solution when the raw materials of the momordica grosvenori, the sweet tea and the stevia rebaudiana are leached, most of the processes have a flocculation step, and the purpose of flocculation is to perform preliminary impurity removal before column loading, namely, the flocculant is added to promote the coagulation of organic substances such as protein, tannin, pectin and the like in the leaching solution to generate precipitation, so that the organic substances are removed to achieve the purpose of preliminary impurity removal.
(III) general flocculant applied to Momordica grosvenori, sweet tea and stevia comprises:
inorganic flocculants (calcium hydroxide, ferric sulfate, aluminum sulfate, ferric chloride, aluminum chloride, etc.), organic flocculants (chitosan, chitin, polyamide, etc.), or others. The most important applications are calcium hydroxide and iron salts.
(IV) content of active ingredients of flocculation slag: the residue of fructus Siraitiae Grosvenorii flocculation contains about 30% of tannic acid (dry basis), and the residue of sweet tea and stevia flocculation contains about 3% of tannic acid (dry basis). At the same time, the above-mentioned flocculation residue also contains a large quantity of tannins (precipitated by flocculant). If not recovered, it is extremely wasteful.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a method for recovering tannic acid from fructus momordicae, sweet tea or stevia rebaudiana flocculus residue.
The invention provides a method for recovering tannic acid from fructus momordicae, sweet tea or stevia rebaudiana flocculation residues, which comprises the following steps:
a) Crushing and sieving the dried flocculated slag to obtain undersize;
b) Loading the undersize into a chromatographic column, compacting, sealing two ends of the chromatographic column, and vacuumizing to obtain a chromatographic column filled with the undersize;
c) Washing the column with a leaching agent, and collecting an effluent;
d) Purifying the effluent to obtain tannic acid product.
Preferably, the flocculation residue is a precipitate obtained by flocculating leaching liquor obtained by extracting fructus momordicae, sweet tea or sweet She Jujin by a flocculating agent, and the precipitate is subjected to a step of recovering sweet glycosides.
Preferably, the screen is a 6-20 mesh screen.
Preferably, the vacuum degree of the vacuumizing is-0.1 to-0.04 Mpa.
Preferably, the column diameter-to-height ratio of the chromatographic column is 1:3-8, preferably 1:4-6.
Preferably, the leaching agent is used for washing the column in a manner of top column or bottom column;
the leaching agent is a mixed aqueous solution of an alcohol substance, ethyl acetate and alkali, wherein the alcohol substance is selected from methanol or ethanol; the alkali is selected from any one or a combination of more of sodium hydroxide, potassium hydroxide or ammonia water, and the adding amount of the alkali is that the pH value of the leaching agent is 9-13; the volume ratio of the alcohol substance to the ethyl acetate is 1:1-5.
Preferably, the leaching agent further comprises a permeation assisting agent, wherein the permeation assisting agent is one or more of monoglyceride, sucrose ester, tween 20, tween 40, tween 60, tween 80 and tween 100.
Preferably, the volume of the upper column of the leaching agent washing column is 3-5 BV, the flow rate of the upper column is 0.1-1.0 BV/h, and preferably 0.3-0.6 BV/h.
Preferably, the column is washed while auxiliary ultrasonic is carried out, the power of the ultrasonic is 100-1000W, and the frequency is 30-50 KHZ.
Preferably, the purification method is as follows:
the effluent liquid passes through cation exchange resin, then the cation exchange resin is washed with water, then ion exchange eluent is used for eluting, and eluent is collected;
sequentially removing the organic solvent from the eluent, desalting, concentrating, drying, crushing and sieving to obtain tannic acid.
Compared with the prior art, the invention provides a method for recovering tannic acid from fructus momordicae, sweet tea or stevia rebaudiana flocculation residues, which comprises the following steps: a) Crushing and sieving the dried flocculated slag to obtain undersize; b) Loading the undersize into a chromatographic column, compacting, sealing two ends of the chromatographic column, and vacuumizing to obtain a chromatographic column filled with the undersize; c) Washing the column with a leaching agent, and collecting an effluent; d) Purifying the effluent to obtain tannic acid product. The method provided by the invention can recover tannic acid from the fructus momordicae, sweet tea or stevia rebaudiana flocculation residues, and has high recovery rate and high purity.
Detailed Description
The invention provides a method for recovering tannic acid from fructus momordicae, sweet tea or stevia rebaudiana flocculation residues, which comprises the following steps:
a) Crushing and sieving the dried flocculated slag to obtain undersize;
b) Loading the undersize into a chromatographic column, compacting, sealing two ends of the chromatographic column, and vacuumizing to obtain a chromatographic column filled with the undersize;
c) Washing the column with a leaching agent, and collecting an effluent;
d) Purifying the effluent to obtain tannic acid product.
The invention takes fructus momordicae, sweet tea or stevia rebaudiana flocculation residue as raw materials, and recovers tannins from the raw materials.
The source of the flocculation slag is not particularly limited, and the flocculation slag obtained by a method known to a person skilled in the art can be used.
Specifically, the flocculation residue is a precipitate obtained by flocculating leaching liquor obtained by extracting fructus momordicae, sweet tea or sweet She Jujin by a flocculating agent. The flocculant is an inorganic flocculant, an organic flocculant or other flocculants, preferably one or more of calcium hydroxide, ferric sulfate, aluminum sulfate, ferric chloride, aluminum chloride, chitosan, chitin and polyamide, and most preferably calcium hydroxide and ferric salt.
After the flocculated slag is obtained, the flocculated slag is dried, and the specific method of drying is not particularly limited, and the drying method known to those skilled in the art can be, but is not limited to, vacuum drying, vacuum microwave drying, forced air drying, and the like. Vacuum drying and vacuum microwave drying are preferred.
Wherein the temperature of the vacuum drying is 50-80 ℃, preferably 60-70 ℃, and the vacuum degree is-0.1 to-0.07 MPa. The vacuum microwave drying temperature is 50-80 ℃, preferably 60-70 ℃, the vacuum degree is-0.1-0.07 MPa, the microwave frequency is 200-800W, preferably 300-700W, and further preferably 400-600W.
The invention dries the flocculation slag, removes the moisture in the flocculation slag, and can promote the leaching of tannic acid.
After the dried flocculation slag is obtained, crushing and sieving the flocculation slag to obtain a undersize product. The method of pulverizing is not particularly limited, and may be any known method by those skilled in the art. In the present invention, it may be one or more of crushing, grinding, and mechanical pulverizing. And then, the crushed flocculated slag is filtered by a 6-20 mesh screen, and the undersize is collected.
Then, loading the undersize into a chromatographic column, compacting, sealing two ends of the chromatographic column, and vacuumizing to obtain the chromatographic column filled with the undersize;
wherein the column diameter-to-height ratio of the chromatographic column is 1:3-8, preferably 1:4-6. The vacuum degree of the vacuumizing is-0.1 to-0.04 Mpa, preferably-0.08 to-0.06 Mpa.
In the present invention, before tannic acid recovery, it is preferable to recover the sweet glycoside in the flocculation residue, because: if the sweet glycoside substance is not recycled, the sweet glycoside is recycled along with the tannic acid in the tannic acid recycling process, so that on one hand, the sweet glycoside substance is directly wasted, and on the other hand, the content of the tannic acid product is influenced.
The method for recovering the stevioside comprises the following steps:
washing the column with a stevioside leaching agent, and collecting a stevioside effluent;
and purifying the stevioside effluent to obtain a stevioside product.
Specifically, the column is washed with a stevioside leaching agent. Wherein, the leaching agent is used for washing the column in a way of top column or bottom column;
the sweet glycoside leaching agent is a mixture of an alcohol solvent, a permeation assisting agent and water, wherein the volume fraction of the alcohol solvent is 80% -95%, the mass fraction of the permeation assisting agent is 0-0.1%, the alcohol solvent is ethanol or methanol, and the permeation assisting agent is one or more selected from monoglyceride, sucrose ester, tween 20, tween 40, tween 60, tween 80 and tween 100. Wherein, the use of the permeation assisting agent can promote the leaching agent to fully contact with the flocculation residue particles, thereby improving the recovery rate.
The volume of the upper column of the leaching agent washing column is 3-5 BV, the flow rate of the upper column is 0.1-1.0 BV/h, and preferably 0.3-0.6 BV/h.
In some preferred embodiments of the invention, the column is washed while auxiliary ultrasound is performed, the power of the ultrasound being 100 to 1000W, preferably 200 to 800W, the frequency being 30 to 50KHZ, preferably 35 to 45KHZ. The invention can promote the leaching agent to fully contact with the flocculation slag particles by adopting a vacuum auxiliary ultrasonic mode, and promote the dissolution of the sweet glycoside substances, thereby improving the recovery rate.
And after the column washing is completed, collecting the effluent liquid of the stevioside. And purifying the stevioside effluent to obtain a stevioside product.
The method of purification is not particularly limited, and may be any method known to those skilled in the art. In the invention, the purification method is that macroporous adsorption resin is used for adsorption, then anion and cation exchange decoloration is carried out in sequence, and finally concentration is carried out, and then recrystallization is carried out.
In some embodiments of the invention, the purification method is:
loading the effluent on a macroporous adsorption resin column, washing the column with water, dissolving with an ethanol aqueous solution for one-time desorption, collecting the desorption liquid, evaporating for dealcoholization, diluting to 4-10 brix, sequentially passing through an anion exchange resin and a cation exchange resin, collecting the effluent, concentrating, crystallizing, drying to obtain high-content stevioside, concentrating and drying the crystallized mother liquor to obtain low-content stevioside.
Wherein the macroporous adsorption resin is selected from D101, DM130 or AB-8.
The volume concentration of the ethanol aqueous solution is 65%.
The anion exchange resin is selected from any one of LX-T5, D941 and LXD-762
The cation exchange resin is selected from LXB-001, D732, LSl-010
The method provided by the invention can recover the stevioside from the fructus momordicae, the sweet tea or the stevia rebaudiana flocculation residues, and has high recovery rate and total yield of more than or equal to 95%; and the purity is high, and the content of the prepared momordica glycosides is not less than 70%, the content of the rubusoside is not less than 95% and the content of the stevioside is not less than 95%.
After the recovery of the stevioside in the flocculation residue is completed, continuously maintaining the vacuum state of the chromatographic column, washing the column with a leaching agent, and collecting effluent liquid;
wherein the leaching agent is used for recovering tannic acid, and the leaching agent is used for washing a column in a manner of top column or bottom column, preferably bottom column;
the leaching agent is a mixed aqueous solution of an alcohol substance, ethyl acetate and alkali, wherein the alcohol substance is selected from methanol or ethanol; the alkali is selected from any one or a combination of more of sodium hydroxide, potassium hydroxide or ammonia water, and the adding amount of the alkali is that the pH value of the leaching agent is 9-13; the volume ratio of the alcohol substance to the ethyl acetate is 1:1-5.
In some embodiments of the present invention, the leaching agent further comprises a permeation enhancer, wherein the permeation enhancer is selected from one or more of monoglyceride, sucrose ester, tween 20, tween 40, tween 60, tween 80 and tween 100, and the concentration of the permeation enhancer in the leaching agent is 0.01wt% to 0.1wt%. Wherein, the use of the permeation assisting agent can promote the leaching agent to fully contact with the flocculation residue particles, thereby improving the recovery rate.
In the invention, the volume of the upper column of the leaching agent washing column is 3-5 BV, the flow rate of the upper column is 0.1-1.0 BV/h, and preferably 0.3-0.6 BV/h.
In some embodiments of the invention, the column is washed while auxiliary ultrasound is performed, the power of the ultrasound being 100 to 1000W, preferably 200 to 800W, and the frequency being 30 to 50KHZ, preferably 35 to 45KHZ. The invention can promote the leaching agent to fully contact with the flocculation slag particles by adopting a vacuum auxiliary ultrasonic mode, and promote the dissolution of tannic acid substances, thereby improving the recovery rate.
After the column washing is completed, the tannic acid effluent is collected. And then purifying the tannic acid effluent liquid to obtain a tannic acid product.
The method of purification is not particularly limited, and may be any method known to those skilled in the art. In the present invention, the purification method is as follows:
the effluent liquid passes through cation exchange resin, then the cation exchange resin is washed with water, then ion exchange eluent is used for eluting, and eluent is collected;
sequentially removing the organic solvent from the eluent, desalting, concentrating, drying, crushing and sieving to obtain tannic acid.
The invention first passes the effluent through a cation exchange resin, wherein the cation exchange resin is selected from any one of LXB-001, D732, LSl-010 and D001×16. The volume of the cation exchange resin is 300-700ml, and the column diameter-to-height ratio of the cation exchange resin is 1:3-8, preferably 1:4-6. The flow rate of the cation exchange resin on the column is 0.1-1.0 BV/h, preferably 0.3-0.6 BV/h.
Then, water washing is carried out, wherein the volume of the water washing is 1.5-3 BV, and the flow rate is 1-2 BV/h.
Finally, the ion exchange eluent is eluted, and all the eluent in the step of eluting the ion exchange eluent is collected. The ion exchange eluent is an aqueous solution of inorganic salt or hydrochloric acid. The inorganic salt is any one of sodium chloride, potassium sulfate and sodium sulfate. Wherein the mass concentration of the inorganic salt or the hydrochloric acid in the ion exchange eluent is 0.2-1.5%, preferably 0.5-0.8%; the volume of the eluent is 3-5 BV, the eluting flow rate is 0.1-1.0 BV/h, and more preferably 0.3-0.6 BV/h.
And (3) after the eluent is obtained, sequentially removing the organic solvent, desalting, concentrating, drying, crushing and sieving the eluent to obtain the tannic acid.
In the invention, the method for removing the organic solvent comprises the following steps: recovering alcohol and ethyl acetate in the eluent under vacuum condition to obtain concentrated solution. Wherein, the aim of recovering ethanol and ethyl acetate without obvious smell of organic solvent is to realize the recovery of the concentrated solution, including but not limited to rotary vacuum concentration, single/multiple effect evaporation type concentration or falling film evaporation concentration.
The desalination method comprises the following steps: and diluting the solution after removing the organic solvent, rotating the nanofiltration membrane by cross flow, and collecting the trapped fluid. The dilution is performed by pure water.
Specifically, after the concentrated solution is diluted to 1-10 brix, the nanofiltration membrane is rotated by the cross flow. The molecular weight cut-off of the cross-flow rotary nanofiltration membrane is 500-3000 Da.
The desalted retentate was then concentrated and dried. Wherein the concentration is aimed at removing most of the water, the concentration mode is not particularly limited in the invention, and comprises but is not limited to vacuum concentration, single-effect/multi-effect evaporation type concentration and the like. Finally, the retentate was concentrated to 40-65 birx.
Finally, the concentrate is dried, wherein the drying aims at removing water, and the method of drying is not particularly limited, and comprises, but is not limited to, vacuum drying, vacuum microwave drying, vacuum freeze drying or forced air drying.
Pulverizing and sieving the dried product to obtain the high-purity tannin. Wherein, the tannic acid is obtained after crushing and sieving with a 80-mesh sieve.
In the invention, the method for detecting the stevioside preferably adopts a high performance liquid phase method.
The detection method of tannic acid preferably adopts the method for testing tannic acid in Chinese pharmacopoeia (2015 edition, fourth rule).
The method provided by the invention can recover tannic acid from the fructus momordicae, sweet tea or stevia rebaudiana flocculation residues, and has high recovery rate and high purity.
In order to further understand the present invention, the method for recovering tannic acid from fructus momordicae, sweet tea or stevia rebaudiana floc residue provided by the present invention is described below with reference to examples, and the scope of the present invention is not limited by the following examples.
Example 1
Recovery of mogroside V
(1) And (3) drying: 5kg of Momordica grosvenori flocculation slag (with 90% of water content and 8.8% of mogroside V content (dry basis) and 30% of tannic acid content (dry basis)) are taken, spread and placed in a tray, and dried in a blast drier at 70 ℃ until the weight is constant.
(2) Crushing: and (3) crushing the dried flocculated slag, and then sieving the crushed slag with an 18-mesh sieve.
(3) Column leaching i: loading the resultant broken flocculation residue into a glass chromatographic column, sealing the two ends of the column with the diameter-height ratio of 1:5, vacuumizing to-0.5 Mpa, placing the column under ultrasonic conditions (200W, 30 KHZ), and washing the column with leaching agent I (80% (volume concentration) of ethanol, tween 20.02 wt%) from the bottom of the column at a flow rate of 0.5BV/h and an upper column volume of 4BV. The effluent was collected separately.
(4) Preparation of sweet glycosides: and (3) after the collected effluent is combined, loading the mixture on a 700ml D101 macroporous adsorption resin, desorbing the mixture by using 3BV 65% ethanol, removing the ethanol from the desorption solution, diluting the desorption solution to 5Brix, loading the desorption solution on 300ml LX-762 and 200ml LXB-001 chromatographic columns in sequence, collecting the effluent, concentrating the effluent, then recrystallizing the effluent by using ethanol, concentrating and vacuum drying the crystallization mother liquor, and obtaining 52.3g and 14.0g mogroside V respectively.
Through detection, the content of the obtained mogroside V is 74.3 percent and 23.3 percent respectively, and the total yield is 95.73 percent.
Production of tannic acid
(1) Column leaching ii: sealing two ends of the flocculation residue column after the recovery of the stevioside, vacuumizing to-0.5 Mpa, placing under ultrasonic conditions (200W, 30 KHZ), and washing the column from the bottom end of the column with leaching liquor (ethanol: ethyl acetate=1:3, water content of 6%, monoglyceride of 0.02% and pH value of 10 adjusted by sodium hydroxide) at a flow rate of 0.5BV/h and a column loading volume of 4BV. The effluent was collected separately.
(2) Chromatography: the collected effluent was applied to a cation exchange resin LXB-001 in a column volume of 1000ml, an aspect ratio of 1:4, an upper column flow rate of 0.5BV/h, then the column was washed with 2BV water at 1BV/h, followed by elution with 1% sodium chloride at 0.5BV/h, an elution volume of 4BV, and the eluate was collected separately
(3) Removing the organic solvent: the eluate was concentrated in vacuo to remove the organic solvent.
(4) Desalting: diluting the solution with removed organic solvent to 4birx, passing through a cross-flow rotary membrane with a membrane cut-off molecular weight of 500Da, and collecting the permeate
(5) Concentrating and drying: the collected permeate was concentrated in vacuo and then dried by microwave.
(6) Crushing and sieving: pulverizing and sieving with 80 mesh sieve to obtain 142g tannic acid product.
Through detection, the content of tannic acid is 93.5%, and the yield is 88.5%.
Example 2
Recovery of rubusoside
(1) And (3) drying: 5kg of sweet tea flocculation residues (the water content is 76 percent, the rubusoside content is 4.6 percent (dry basis) and the tannic acid content is 3.67 percent (dry basis)) are paved and placed in a tray, and are dried in an 80 ℃ blast dryer to constant weight.
(2) Crushing: and (5) crushing the dried flocculated slag, and sieving the crushed slag with a 10-mesh sieve.
(3) Column leaching i: filling the crushed flocculation residue into a glass chromatographic column, sealing the two ends of the column with the diameter-to-height ratio of 1:4, vacuumizing to-0.08 Mpa, placing the column under ultrasonic conditions (300W, 40 KHZ), and washing the column with a leaching agent I (90% (volume concentration) of ethanol, and Tween 100.05 wt%) from the bottom end of the column at a flow rate of 0.7BV/h and an upper column volume of 5BV. The effluent was collected separately.
(4) Preparation of sweet glycosides: and (3) after the collected effluent is combined, loading the mixture on a 700ml AB-8 type macroporous adsorption resin, desorbing the mixture by using 3BV 65% ethanol, removing the ethanol from the desorption solution, diluting the desorption solution to 5Brix, loading the desorption solution on 300ml D941 and 200ml D732 chromatographic columns in sequence, collecting the effluent, concentrating the effluent, then recrystallizing the effluent by using ethanol, concentrating and vacuum drying the crystallization mother liquor, and obtaining 47.2g and 11.2g rubusoside respectively.
Through detection, the content of the prepared rubusoside product is 97.9% and 66.5%, respectively, and the total yield is 97.20%.
Production of tannic acid
(1) Column leaching ii: sealing two ends of the flocculation residue column after the recovery of the stevioside, vacuumizing to-0.5 Mpa, placing under ultrasonic conditions (200W, 30 KHZ), washing the column from the bottom end of the column with leaching liquor (ethanol: ethyl acetate=1:1, water content of 10%, sucrose ester of 0.05% and pH value of 13 adjusted by sodium hydroxide) at a flow rate of 0.5BV/h and an upper column volume of 4BV. The effluent was collected separately.
(2) Chromatography: the collected effluent was applied to a cation exchange resin D732, column volume was 500ml, diameter-to-height ratio was 1:4, column flow rate was 0.5BV/h, then the column was washed with 2BV water at 1BV/h, followed by elution with 1% sodium chloride at 0.5BV/h, elution volume was 4BV, and the eluate was collected separately.
(3) Removing the organic solvent: the eluate was concentrated in vacuo to remove the organic solvent.
(4) Desalting: diluting the solution with removed organic solvent to 4birx, passing through a cross-flow rotary membrane with a membrane cut-off molecular weight of 500Da, and collecting the permeate
(5) Concentrating and drying: the collected permeate was concentrated in vacuo and then dried by microwave.
(6) Crushing and sieving: pulverizing and sieving with 80 mesh sieve to obtain 44.6g tannic acid product.
Through detection, the content of tannic acid is 92.10%, and the yield is 93.3%.
Example 3
Recovery of steviol glycosides
(1) And (3) drying: taking 5kg of stevia rebaudiana flocculation residues (with the water content of 79%, the stevioside content of 5.6% (dry basis) and the tannic acid content of 2.67% (dry basis)), spreading and placing in a tray, and drying in a microwave dryer at 70 ℃ until the weight is constant.
(2) Crushing: and (5) crushing the dried flocculated slag, and then sieving the crushed slag with a 20-mesh sieve.
(3) Column leaching i: filling the crushed flocculation residue into a glass chromatographic column, sealing the two ends of the column with the diameter-height ratio of 1:6, vacuumizing to-0.1 Mpa, placing the column under ultrasonic conditions (700W, 30 KHZ), and washing the column with a leaching agent I (95% (volume concentration) of methanol and 0.03wt% of monoglyceride) from the bottom end of the column at a flow rate of 0.2BV/h and a column loading volume of 3BV. The effluent was collected separately.
(4) Preparation of sweet glycosides: and (3) after the collected effluent is combined, loading the mixture on a 700ml AB-8 type macroporous adsorption resin, desorbing the mixture by using 3BV 65% ethanol, removing the ethanol from the desorption solution, diluting the desorption solution to 5Brix, loading the desorption solution on 300ml D941 and 200ml D732 chromatographic columns in sequence, collecting the effluent, concentrating the effluent, then recrystallizing the effluent by using methanol, concentrating and vacuum drying the crystallization mother liquor, and obtaining 46.8g and 15.6g stevioside respectively.
Through detection, the content of the prepared rubusoside products is 96.5% and 71.4%, respectively, and the total yield is 95.75%.
Production of tannic acid
(1) Column leaching ii: sealing two ends of the flocculation residue column after the recovery of the stevioside, vacuumizing to-0.5 Mpa, placing under ultrasonic conditions (200W, 30 KHZ), washing the column from the bottom end of the column with leaching solution (methanol: ethyl acetate=1:5, water content of 13%, tween of 100.01% and pH value of 10 adjusted by sodium hydroxide) at a flow rate of 0.5BV/h and an upper column volume of 4BV. The effluent was collected separately.
(2) Chromatography: the collected effluent was applied to a cation exchange resin LSI-010, the column volume was 500ml, the aspect ratio was 1:4, the column loading flow rate was 0.5BV/h, then the column was washed with 2BV water at 1BV/h, followed by elution with 1% sodium chloride, the elution flow rate was 0.5BV/h, the elution volume was 4BV, and the eluate was collected separately
(3) Removing the organic solvent: the eluate was concentrated in vacuo to remove the organic solvent.
(4) Desalting: diluting the solution with removed organic solvent to 4birx, passing through a cross-flow rotary membrane with a membrane cut-off molecular weight of 500Da, and collecting the permeate
(5) Concentrating and drying: the collected permeate was concentrated in vacuo and then dried by microwave.
(6) Crushing and sieving: pulverizing and sieving with 80 mesh sieve to obtain 28.1g tannic acid product.
Through detection, the content of tannic acid is 90.30%, and the yield is 90.5%.
Comparative examples 1 to 3
Comparative examples 1 to 3 correspond to examples 1 to 3, respectively, and reference is made to the methods of examples 1 to 3, wherein the recovery method of the sweet glycoside is kept uniform, and the recovery of the tannic acid is carried out under the process conditions shown in Table 1 by changing only the process parameters of the tannic acid recovery step.
TABLE 1 conditions for tannic acid extraction
In Table 1, "/" indicates that this step is not performed.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A method for recovering tannic acid from luo han guo, sweet tea or stevia rebaudiana floc residue, comprising the steps of:
crushing and sieving the dried flocculated slag to obtain undersize;
loading the undersize into a chromatographic column, compacting, sealing two ends of the chromatographic column, and vacuumizing to obtain a chromatographic column filled with the undersize; the vacuum degree of the vacuumizing is-0.1 to-0.04 Mpa;
washing the column with a stevioside leaching agent, and collecting a stevioside effluent after the column washing is completed, wherein the stevioside leaching agent is selected from a mixture of an alcohol solvent, a permeation assisting agent and water;
after the recovery of the sweet glycoside in the flocculation residue is completed, continuously maintaining the vacuum state of the chromatographic column, washing the column with a tannic acid leaching agent, and collecting effluent liquid;
the tannic acid leaching agent is a mixed aqueous solution of an alcohol solvent, ethyl acetate and alkali, and the tannic acid leaching agent also comprises a permeation assisting agent;
the alcohol solvent is selected from methanol or ethanol; the alkali is selected from any one or more of sodium hydroxide, potassium hydroxide or ammonia water, and the permeation promoter is selected from one or more of monoglyceride, sucrose ester, tween 20, tween 40, tween 60, tween 80 and Tween 100; the addition amount of the alkali is that the pH value of the tannic acid leaching agent is 9-13; the volume ratio of the alcohol solvent to the ethyl acetate is 1:1-5;
the column washing process is carried out under vacuum condition, auxiliary ultrasonic is carried out while the column is washed, the power of the ultrasonic is 100-1000W, and the frequency is 30-50 KHZ;
purifying the effluent to obtain tannic acid product.
2. The method according to claim 1, wherein the flocculation residue is a precipitate obtained by flocculating a leaching solution obtained by extracting fructus momordicae, sweet tea or sweet She Jujin with a flocculant.
3. The method of claim 1, wherein the sieving is through a 6-20 mesh screen.
4. The method of claim 1, wherein the column diameter to height ratio of the chromatography column is 1:3-8.
5. The method of claim 1, wherein the column diameter to height ratio of the chromatography column is 1:4-6.
6. The method of claim 1, wherein the leaching agent is washed in a top column or a bottom column.
7. The method of claim 1, wherein the leaching agent wash column has an upper column volume of 3-5 BV and an upper column flow rate of 0.1-1.0 BV/h.
8. The method of claim 1, wherein the upper column flow rate of the leaching agent wash column is 0.3-0.6 BV/h.
9. The method according to claim 1, wherein the purification method is:
the effluent liquid passes through cation exchange resin, then the cation exchange resin is washed with water, then ion exchange eluent is used for eluting, and eluent is collected;
sequentially removing the organic solvent from the eluent, desalting, concentrating, drying, crushing and sieving to obtain tannic acid.
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| FR2611140B1 (en) * | 1987-02-20 | 1991-02-22 | Lamaison Jean Louis | PROCESS FOR OBTAINING TANNIC PRINCIPLES OF PLANT ORIGIN, COSMETOLOGICAL COMPOSITION AND PHARMACEUTICAL COMPOSITION CONTAINING THE PURIFIED TANNIC PRINCIPLE OBTAINED ACCORDING TO THE PROCESS |
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| CN101993460B (en) * | 2010-12-02 | 2012-07-25 | 南宁圣特生物科技有限公司 | Method for separating and purifying ellagitannic acid in raspberry |
| CN103408607A (en) * | 2013-08-13 | 2013-11-27 | 南京标科生物科技有限公司 | Preparation method of cassia tannin D1 |
| CN104311676B (en) * | 2014-10-15 | 2016-08-24 | 贵州绿农生物科技有限公司 | A kind of extraction food starch method of by-product tannic acid from rubber seed core |
| CN107266508B (en) * | 2017-05-27 | 2019-07-26 | 皖西学院 | A method of extracting tannin from Shaniodendron subaequalum |
| CN108752392B (en) * | 2018-05-04 | 2020-10-02 | 湖南华诚生物资源股份有限公司 | Method for recovering sweet tea polyphenol from sweet tea flocculation residues after sweet tea glycoside extraction |
| CN112851739B (en) * | 2021-03-30 | 2022-02-08 | 湖南华诚生物资源股份有限公司 | Method for recovering sweet glycosides from fructus Siraitiae Grosvenorii, folium Hydrangeae Strigosae or stevia rebaudiana flocculation residues |
| CN113527383B (en) * | 2021-06-28 | 2023-02-17 | 中南林业科技大学 | High-purity plant tannin prepared from industrial tannin extract and preparation method thereof |
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