CN112876523A - Method for recovering tannic acid from fructus Siraitiae Grosvenorii, folium Hydrangeae Strigosae or stevia rebaudiana flocculation residues - Google Patents
Method for recovering tannic acid from fructus Siraitiae Grosvenorii, folium Hydrangeae Strigosae or stevia rebaudiana flocculation residues Download PDFInfo
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- CN112876523A CN112876523A CN202110343457.2A CN202110343457A CN112876523A CN 112876523 A CN112876523 A CN 112876523A CN 202110343457 A CN202110343457 A CN 202110343457A CN 112876523 A CN112876523 A CN 112876523A
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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 momordica grosvenori, rubus suavissimus or stevia rebaudiana flocculation residues, which comprises the following steps: A) crushing and sieving the dried flocculation residues to obtain undersize materials; B) filling the undersize into a chromatographic column and compacting, sealing two ends of the chromatographic column and vacuumizing to obtain the chromatographic column filled with the undersize; C) washing the column with an extractant, and collecting effluent liquid; D) purifying the effluent to obtain a tannic acid product. The method provided by the invention can recover tannic acid from 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 momordica grosvenori, rubus suavissimus or stevia rebaudiana flocculation residues.
Background
Tannin is also called tannic acid or tannin, and is plant polyphenol consisting of glucose (and other polyols) ester of gallic acid (or its polymer), polymer of flavanolignan and its derivatives, and mixture of the two. These compounds can bind to proteins to form water-insoluble precipitates, and can form compact, flexible, non-putrefactive, and water-impermeable leathers with the proteins of hides, and are called tannins. Typically a pale yellow or colorless powder, readily soluble in glycerol, soluble in water and ethanol, and insoluble in diethyl ether and chloroform. In medicine, the tannic acid has the effects of stopping bleeding and resisting allergy, can be prepared into ointment for local use to treat scalds, ulcers, eczema, hemorrhoids and the like, can also inhibit the activity of snake venom protein and neutralize the toxicity of snake venom, can be used as a food antioxidant in the aspect of beverages after being mixed with antibiotics and amino acids, and is mainly characterized by good water solubility and easy protein coprecipitation, so that the shelf life of the beverages is prolonged.
Momordica grosvenori, hydrangea aspera and stevia rebaudiana are three main plant materials for preparing natural sweeteners. The prior art of the flocculation residues of the momordica grosvenori, the sweet tea and the stevia rebaudiana at present comprises the following aspects:
the recycling condition of the flocculation residues:
aiming at the processes of the momordica grosvenori, the rubus suavissimus and the stevia rebaudiana, the method mainly stays in the extraction of effective components (mogroside, rubus suavissimus glycoside and stevioside) in the raw materials, and the research on the utilization of flocculation residues is less.
(II) the sources of the flocculation residues:
in order to obtain a relatively clear leaching liquor when raw materials of momordica grosvenori, sweet tea and stevia rebaudiana are leached, most processes have a flocculation step, and the flocculation is to primarily remove impurities before an upper column, namely, a flocculating agent is added to promote organic substances such as protein, tannin, pectin and the like in the leaching liquor to be coagulated to generate precipitates so as to be removed to achieve the purpose of primarily removing the impurities.
(III) the general flocculating agent applied to the grosvenor momordica fruit, the sweet tea and the stevia rebaudiana comprises:
inorganic flocculants (calcium hydroxide, ferric sulfate, aluminum sulfate, ferric chloride, aluminum chloride, etc.), organic flocculants (chitosan, chitin, polyamide, etc.), or others. Calcium hydroxide and iron salts are mainly used at most.
(IV) the content of effective components of the flocculation residues: the fructus Siraitiae Grosvenorii flocculation residues contain about 30% of tannic acid (on dry basis) residues, and folium hydrangeae strigosae and stevia flocculation residues contain about 3% of tannic acid (on dry basis). At the same time, the flocculation residues also contain a large amount of tannin (precipitated by the flocculating agent). If not recycled, it is extremely wasteful.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for recovering tannic acid from momordica grosvenori, rubus suavissimus or stevia rebaudiana flocculation residues, wherein the method provided by the present invention can recover tannic acid from momordica grosvenori, rubus suavissimus or stevia rebaudiana flocculation residues with high recovery rate and high purity.
The invention provides a method for recovering tannic acid from momordica grosvenori, rubus suavissimus or stevia rebaudiana flocculation residues, which comprises the following steps:
A) crushing and sieving the dried flocculation residues to obtain undersize materials;
B) filling the undersize into a chromatographic column and compacting, sealing two ends of the chromatographic column and vacuumizing to obtain the chromatographic column filled with the undersize;
C) washing the column with an extractant, and collecting effluent liquid;
D) purifying the effluent to obtain a tannic acid product.
Preferably, the flocculation residues are precipitates obtained by flocculating leaching liquor obtained by leaching fructus momordicae, sweet tea or stevia rebaudiana with a flocculating agent, and the precipitates are subjected to a step of recovering the sweet glycosides.
Preferably, the sieving is performed by a 6-20-mesh sieve.
Preferably, the vacuum degree of the vacuum pumping is-0.1 to-0.04 MPa.
Preferably, the column diameter-height ratio of the chromatographic column is 1: 3-8, and preferably 1: 4-6.
Preferably, the leaching agent is used for washing the column in a mode of top end column loading or bottom end column loading;
the lixiviant 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 more of sodium hydroxide, potassium hydroxide or ammonia water, and the addition amount of the alkali is that the pH 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 penetration enhancer, wherein the penetration enhancer is one or more of monoglyceride, sucrose ester, tween 20, tween 40, tween 60, tween 80 and tween 100.
Preferably, the upper column volume of the leaching agent column washing is 3-5 BV, the upper column flow rate is 0.1-1.0 BV/h, and preferably 0.3-0.6 BV/h.
Preferably, auxiliary ultrasound is carried out while the column is washed, the power of the ultrasound is 100-1000W, and the frequency is 30-50 KHZ.
Preferably, the purification method comprises the following steps:
passing the effluent through cation exchange resin, washing the cation exchange resin with water, eluting with ion exchange eluent, and collecting the eluate;
and sequentially removing the organic solvent from the eluent, desalting, concentrating, drying, crushing and sieving to obtain the tannic acid.
Compared with the prior art, the invention provides a method for recovering tannic acid from momordica grosvenori, rubus suavissimus or stevia rebaudiana flocculation residues, which comprises the following steps: A) crushing and sieving the dried flocculation residues to obtain undersize materials; B) filling the undersize into a chromatographic column and compacting, sealing two ends of the chromatographic column and vacuumizing to obtain the chromatographic column filled with the undersize; C) washing the column with an extractant, and collecting effluent liquid; D) purifying the effluent to obtain a tannic acid product. The method provided by the invention can recover tannic acid from 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 momordica grosvenori, rubus suavissimus or stevia rebaudiana flocculation residues, which comprises the following steps:
A) crushing and sieving the dried flocculation residues to obtain undersize materials;
B) filling the undersize into a chromatographic column and compacting, sealing two ends of the chromatographic column and vacuumizing to obtain the chromatographic column filled with the undersize;
C) washing the column with an extractant, and collecting effluent liquid;
D) purifying the effluent to obtain a tannic acid product.
The method takes momordica grosvenori, sweet tea or stevia rebaudiana flocculation residues as raw materials, and tannic acid is recovered from the raw materials.
The sources of the flocculation residues are not particularly limited in the present invention, and the flocculation residues obtained by the methods known to those skilled in the art can be used.
Specifically, the flocculation residues are precipitates obtained by flocculating leaching liquor obtained by leaching fructus momordicae, sweet tea or stevia rebaudiana with a flocculating agent. The flocculating agent is one or more of inorganic flocculating agent, organic flocculating agent or other flocculating agent, preferably calcium hydroxide, ferric sulfate, aluminum sulfate, ferric chloride, aluminum chloride, chitosan, chitin and polyamide, and most preferably calcium hydroxide and ferric salt.
After obtaining the flocculation residues, drying the flocculation residues, wherein the specific method for 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-0.1-0.07 MPa. The vacuum microwave drying temperature is 50-80 ℃, the preferred temperature is 60-70 ℃, the vacuum degree is-0.1-0.07 MPa, and the microwave frequency is 200-800W, the preferred frequency is 300-700W, and the further preferred frequency is 400-600W.
The invention dries the flocculation residues, removes the water in the flocculation residues and can promote the extraction of tannic acid.
And after the dried flocculation residues are obtained, crushing and sieving the flocculation residues to obtain undersize materials. The method for pulverizing the above-mentioned raw materials is not particularly limited in the present invention, and any method known to those skilled in the art may be used. In the present invention, it may be one or more of crushing, grinding, and mechanical pulverization. And then, sieving the crushed flocculation residues by using a 6-20-mesh sieve, and collecting undersize products.
Then, filling the undersize into a chromatographic column and compacting, sealing two ends of the chromatographic column and vacuumizing to obtain the chromatographic column filled with the undersize;
wherein the column diameter height ratio of the chromatographic column is 1: 3-8, preferably 1: 4-6. The vacuum degree of the vacuum pumping is-0.1 to-0.04 Mpa, and preferably-0.08 to-0.06 Mpa.
In the present invention, before the tannin recovery, it is preferable to recover the sweet glycosides from the flocs because: if the sweet glycoside substance is not recycled, the sweet glycoside can be recycled together with the tannic acid in the process of recycling the tannic acid, on one hand, the sweet glycoside substance is directly wasted, and on the other hand, the content of the tannic acid product can be influenced.
The method for recovering the sweet glycosides comprises the following steps:
washing the column with a sweet glycoside extractant, and collecting sweet glycoside effluent;
and purifying the sweet glycoside effluent to obtain a sweet glycoside product.
Specifically, the column is washed by a sweet glycoside extracting agent. Wherein the leaching agent is used for washing the column in a mode of loading the column at the top end or loading the column at the bottom end;
the sweet glycoside leaching agent is selected from a mixture of an alcohol solvent, a penetration enhancer and water, wherein the volume fraction of the alcohol solvent is 80-95%, the mass fraction of the penetration enhancer is 0-0.1%, the alcohol solvent is selected from ethanol or methanol, and the penetration enhancer is selected from one or more of monoglyceride, sucrose ester, tween 20, tween 40, tween 60, tween 80 and tween 100. Wherein, the use of the permeation-assistant agent can promote the lixiviant to fully contact with the flocculation slag particles, thereby improving the recovery rate.
The upper column volume of the leaching agent column washing is 3-5 BV, the upper column flow rate is 0.1-1.0 BV/h, and preferably 0.3-0.6 BV/h.
In some preferred embodiments of the invention, the column washing is performed with auxiliary ultrasound, the power of the ultrasound is 100-1000W, preferably 200-800W, and the frequency is 30-50 KHZ, preferably 35-45 KHZ. The invention can promote the lixiviant to fully contact with the flocculation slag particles and promote the dissolution of the sweet glycoside substance by adopting a vacuum auxiliary ultrasonic mode, thereby improving the recovery rate.
After the column washing is completed, collecting the sweet glycoside effluent liquid. The sweet glycoside effluent is then purified to obtain the sweet glycoside product.
The purification method of the present invention is not particularly limited, and may be a method known to those skilled in the art. In the invention, the purification method comprises the steps of firstly adsorbing by using macroporous adsorption resin, then sequentially carrying out anion and cation exchange decoloration, and finally concentrating and then recrystallizing.
In some embodiments of the invention, the method of purification is:
and (3) loading the effluent liquid onto a macroporous adsorption resin column, washing the column with water, dissolving the column with an ethanol water solution for one-time desorption, collecting the desorption liquid, evaporating the desorption liquid for dealcoholization, diluting the desorption liquid to 4-10 brix, sequentially passing through an anion exchange resin and a cation exchange resin, collecting the effluent liquid, concentrating, crystallizing and drying to obtain high-content sweet glycoside, and concentrating and drying the crystallized mother liquor to obtain low-content sweet glycoside.
Wherein the macroporous adsorption resin is selected from D101, DM130 or AB-8.
The volume concentration of the ethanol water solution is 65%.
The anion exchange resin is any one of LX-T5, D941 and LXD-762
The cation exchange resin is any one of LXB-001, D732 and LSl-010
The method provided by the invention can recover the sweet glycosides from the grosvenor momordica fruit, the sweet tea or the stevia rebaudiana flocculation residues, the recovery rate is high, and the total yield is more than or equal to 95 percent; the purity is high, the content of the prepared momordica glycosides is not less than 70% at most, the content of rubusoside is not less than 95% at most, and the content of stevioside is not less than 95% at most.
After the recovery of the sweet glycosides in the flocculation residues is finished, continuously maintaining the vacuum state of the chromatographic column, washing the chromatographic column with an extractant, and collecting effluent liquid;
wherein the lixiviant is used for recovering tannic acid, and the lixiviant washes the column in a mode of top end upper column or bottom end upper column, preferably bottom end upper column;
the lixiviant 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 more of sodium hydroxide, potassium hydroxide or ammonia water, and the addition amount of the alkali is that the pH 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 includes a penetration enhancer, the penetration 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 penetration enhancer in the leaching agent is 0.01 wt% to 0.1 wt%. Wherein, the use of the permeation-assistant agent can promote the lixiviant to fully contact with the flocculation slag particles, thereby improving the recovery rate.
In the invention, the upper column volume of the leaching agent washing column is 3-5 BV, the upper column flow rate is 0.1-1.0 BV/h, and preferably 0.3-0.6 BV/h.
In some embodiments of the invention, the column washing is performed with auxiliary ultrasound, the power of the ultrasound is 100-1000W, preferably 200-800W, and the frequency is 30-50 KHZ, preferably 35-45 KHZ. The invention can promote the lixiviant to fully contact with the flocculation slag particles and promote the dissolution of tannic acid substances by adopting a vacuum auxiliary ultrasonic mode, thereby improving the recovery rate.
And after the column washing is finished, collecting the effluent of the tannic acid. The tannic acid effluent is then purified to obtain a tannic acid product.
The purification method of the present invention is not particularly limited, and may be a method known to those skilled in the art. In the invention, the purification method comprises the following steps:
passing the effluent through cation exchange resin, washing the cation exchange resin with water, eluting with ion exchange eluent, and collecting the eluate;
and sequentially removing the organic solvent from the eluent, desalting, concentrating, drying, crushing and sieving to obtain the tannic acid.
The effluent is firstly passed through cation exchange resin, wherein the cation exchange resin is any one of LXB-001, D732, LSl-010 and D001 x 16. The volume of the cation exchange resin is 300-700ml, and the column diameter 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.
And then, carrying out water washing, wherein the volume of the water washing is 1.5-3 BV, and the flow rate is 1-2 BV/h.
And finally, eluting by using an ion exchange eluent, and collecting all eluent eluted by using the ion exchange eluent. 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, and the elution flow rate is 0.1-1.0 BV/h, more preferably 0.3-0.6 BV/h.
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 from the eluate under vacuum to obtain concentrated solution. Wherein, the aim is to realize the recovery of the ethanol and the ethyl acetate, and the concentrated solution has no obvious organic solvent odor, and the method comprises but is not limited to rotary vacuum concentration, single/multiple effect evaporation concentration or falling film evaporation concentration.
The desalting method comprises the following steps: diluting the solution without the organic solvent, rotating the nanofiltration membrane by cross flow, and collecting trapped fluid. And the dilution is carried out by pure water.
Specifically, after the concentrated solution is diluted to 1-10 brix, a cross-flow rotating nanofiltration membrane is passed. The molecular weight cutoff of the cross-flow rotating nanofiltration membrane is 500-3000 Da.
Then, the desalted retentate was concentrated and dried. The concentration is performed to remove most of the water, and the present invention is not limited to the above-mentioned concentration method, including but not limited to vacuum concentration, single-effect/multiple-effect evaporative concentration, etc. Finally, the retentate is concentrated to 40-65 birx.
And finally, drying the concentrated solution, wherein the drying is carried out for the purpose of removing water, and the drying method is not particularly limited, and includes but is not limited to vacuum drying, vacuum microwave drying, vacuum freeze drying or forced air drying.
And crushing and sieving the dried product to obtain the high-purity tannin. Wherein, after being crushed, the tannic acid is sieved by a sieve with 80 meshes to obtain the tannic acid.
In the present invention, the method for detecting the sweet glycosides is preferably a high performance liquid chromatography.
The method for detecting tannic acid preferably adopts the method for testing tannic acid in Chinese pharmacopoeia (2015 edition fourth general rule).
The method provided by the invention can recover tannic acid from fructus momordicae, sweet tea or stevia rebaudiana flocculation residues, and has high recovery rate and high purity.
For further understanding of the present invention, the method for recovering tannic acid from Momordica grosvenori Swingle, Rubus suavissimus or stevia rebaudiana Bertoni flocculation residues provided by the present invention is illustrated below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
Recovery of mogroside V
(1) Drying: 5kg of fructus momordicae flocculation residues (the water content is 90 percent, the mogroside V content is 8.8 percent (dry basis), and the tannic acid content is 30 percent (dry basis)) are spread and placed in a tray, and the tray is placed in a blast drier at 70 ℃ to be dried to constant weight.
(2) Crushing: the dried flocculation residues are crushed and rolled and then screened by a 18-mesh screen.
(3) Column leaching I: the crushed floc slag is loaded into a glass chromatographic column with the column diameter ratio of 1:5, the two ends are sealed, the column is vacuumized to-0.5 Mpa and placed under the ultrasonic condition (200W, 30KHZ), and an extracting agent I (80% (volume concentration) ethanol, Tween 200.02 wt%) enters the column from the bottom end of the column for washing, the flow rate is 0.5BV/h, and the volume of the column is 4 BV. The effluent was collected separately.
(4) Preparing the sweet glycosides: combining the collected effluent, loading the effluent into a 700ml D101 type macroporous adsorption resin column, desorbing by using 3BV 65% ethanol, removing alcohol from the desorption solution, diluting to 5Brix, loading the eluate into 300ml LX-762 and 200ml LXB-001 chromatographic columns in sequence, collecting the effluent, concentrating, recrystallizing by using ethanol, concentrating the crystallization mother liquor, and drying in vacuum to obtain 52.3g of mogroside V and 14.0g of mogroside V.
Through detection, the content of the prepared mogroside V is 74.3 percent and 23.3 percent respectively, and the total yield is 95.73 percent.
Preparation of (di) tannic acid
(1) Column leaching II: sealing two ends of the flocculation residue column after recovery of the sweet glycosides, vacuumizing to-0.5 Mpa, placing under ultrasonic conditions (200W, 30KHZ), and introducing leaching solution (ethanol: ethyl acetate: 1:3, water content: 6%, monoglyceride 0.02%, and sodium hydroxide to adjust pH to 10) into the column from the bottom end of the column at flow rate of 0.5BV/h and upper column volume of 4 BV. The effluent was collected separately.
(2) Chromatography: loading the collected effluent liquid on cation exchange resin LXB-001 with a column volume of 1000ml and a diameter-height ratio of 1:4 at a column flow rate of 0.5BV/h, washing the column with 2BV water at 1BV/h, eluting with 1% sodium chloride at an elution flow rate of 0.5BV/h and an elution volume of 4BV, and separately collecting the eluate
(3) Removing the organic solvent: the eluate was concentrated in vacuo and the organic solvent was removed.
(4) Desalting: diluting the solution without organic solvent to 4birx, passing through a cross-flow rotating membrane with a molecular weight cutoff of 500Da, and collecting the permeate
(5) Concentrating and drying: and (4) concentrating the collected permeate in vacuum, and then performing microwave drying.
(6) Crushing and sieving: pulverizing, and sieving with 80 mesh sieve to obtain 142g tannic acid product.
Through detection, the content of the prepared tannic acid is 93.5%, and the yield is 88.5%.
Example 2
(I) recovery of rubusoside
(1) Drying: 5kg of sweet tea flocculation residues (the water content is 76 percent, the sweet tea glycoside content is 4.6 percent (dry basis), the tannic acid content is 3.67 percent (dry basis)) are flatly paved and placed in a tray, and the tray is placed in a blast drier at the temperature of 80 ℃ to be dried to constant weight.
(2) Crushing: the dried flocculation residues are crushed and rolled and then screened by a 10-mesh screen.
(3) Column leaching I: the crushed flocculation slag is filled into a glass chromatographic column, the height ratio of the column diameter is 1:4, after two ends are sealed, the glass chromatographic column is vacuumized to-0.08 Mpa and placed under the ultrasonic condition (300W, 40KHZ), an extracting agent I (90% (volume concentration) ethanol, Tween 1000.05 wt%) enters the column from the bottom end of the column for washing, the flow rate is 0.7BV/h, and the volume of the upper column is 5 BV. The effluent was collected separately.
(4) Preparing the sweet glycosides: combining the collected effluent, loading the effluent into a column of 700ml AB-8 type macroporous adsorption resin, desorbing by using 3BV 65% ethanol, removing alcohol from the desorption solution, diluting to 5Brix, loading the desorption solution into columns of 300ml D941 and 200ml D732 chromatography in sequence, collecting the effluent, concentrating, recrystallizing by using ethanol, and concentrating and vacuum-drying the crystallized mother liquor to obtain 47.2g and 11.2g of rubusoside.
Through detection, the content of the prepared rubusoside product is 97.9 percent and 66.5 percent respectively, and the total yield is 97.20 percent.
Preparation of (di) tannic acid
(1) Column leaching II: sealing two ends of the flocculation residue column after recovery of the sweet glycosides, vacuumizing to-0.5 Mpa, placing under ultrasonic conditions (200W, 30KHZ), and introducing the leaching solution (ethanol: ethyl acetate 1:1, water content 10%, sucrose ester 0.05%, and sodium hydroxide to adjust pH to 13) into the column from the bottom end of the column at a flow rate of 0.5BV/h and a column volume of 4 BV. The effluent was collected separately.
(2) Chromatography: the collected effluent was applied to cation exchange resin D732 at a column volume of 500ml, a diameter to height ratio of 1:4, and an application flow rate of 0.5BV/h, and then the column was washed with 2BV of water at 1BV/h, followed by elution with 1% sodium chloride at an elution flow rate of 0.5BV/h and an elution volume of 4BV, and the eluates were separately collected.
(3) Removing the organic solvent: the eluate was concentrated in vacuo and the organic solvent was removed.
(4) Desalting: diluting the solution without organic solvent to 4birx, passing through a cross-flow rotating membrane with a molecular weight cutoff of 500Da, and collecting the permeate
(5) Concentrating and drying: and (4) concentrating the collected permeate in vacuum, and then performing microwave drying.
(6) Crushing and sieving: grinding and sieving with a 80-mesh sieve to obtain 44.6g of tannic acid product.
Through detection, the content of the prepared tannic acid is 92.10%, and the yield is 93.3%.
Example 3
Recovery of stevioside
(1) Drying: taking 5kg of stevia flocculation residues (with water content of 79%, stevioside content of 5.6% (dry basis), and tannic acid content of 2.67% (dry basis)), spreading and placing in a tray, and drying in a 70 deg.C microwave dryer to constant weight.
(2) Crushing: grinding and crushing the dried flocculation residues, and sieving the crushed flocculation residues with a 20-mesh sieve.
(3) Column leaching I: the crushed flocculated slag is filled into a glass chromatographic column, the height ratio of the column diameter is 1:6, after two ends are sealed, the glass chromatographic column is vacuumized to-0.1 Mpa and placed under the ultrasonic condition (700W, 30KHZ), an extracting agent I (95% (volume concentration) methanol, 0.03 wt% of monoglyceride) enters the column from the bottom end of the column for washing, the flow rate is 0.2BV/h, and the volume of the upper column is 3 BV. The effluent was collected separately.
(4) Preparing the sweet glycosides: combining the collected effluent, loading the effluent on a column to 700ml AB-8 type macroporous adsorption resin, desorbing by using 3BV 65% ethanol, removing alcohol from the desorption solution, diluting to 5Brix, loading the desorption solution on a 300ml D941 and 200ml D732 chromatographic columns in sequence, collecting the effluent, concentrating, recrystallizing by using methanol, and concentrating and vacuum-drying the crystallized mother liquor to obtain 46.8g stevioside and 15.6g stevioside respectively.
Through detection, the content of the prepared rubusoside product is 96.5 percent and 71.4 percent respectively, and the total yield is 95.75 percent.
Preparation of (di) tannic acid
(1) Column leaching II: sealing two ends of the flocculation residue column after recovery of the sweet glycosides, vacuumizing to-0.5 Mpa, placing under ultrasonic conditions (200W, 30KHZ), and introducing leaching solution (methanol: ethyl acetate 1:5, water content 13%, Tween 1000.01%, and sodium hydroxide to adjust pH to 10) into the column from the bottom end thereof at flow rate of 0.5BV/h and upper column volume of 4 BV. The effluent was collected separately.
(2) Chromatography: loading the collected effluent on cation exchange resin LSI-010 with column volume of 500ml, diameter-height ratio of 1:4, column flow rate of 0.5BV/h, washing the column with 2BV water at 1BV/h, eluting with 1% sodium chloride at 0.5BV/h and elution volume of 4BV, collecting the eluates separately
(3) Removing the organic solvent: the eluate was concentrated in vacuo and the organic solvent was removed.
(4) Desalting: diluting the solution without organic solvent to 4birx, passing through a cross-flow rotating membrane with a molecular weight cutoff of 500Da, and collecting the permeate
(5) Concentrating and drying: and (4) concentrating the collected permeate in vacuum, and then performing microwave drying.
(6) Crushing and sieving: pulverizing, and sieving with 80 mesh sieve to obtain 28.1g tannic acid product.
Through detection, the content of the prepared 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 refer to the methods of examples 1 to 3, wherein the recovery method of the sweet glycosides is kept consistent, only the process parameters of the tannin recovery step are changed, and the recovery of the tannins is performed according to the process conditions in table 1.
TABLE 1 conditions of tannic acid extraction
In Table 1, "/" indicates that this step was not performed.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for recovering tannic acid from grosvenor momordica fruit, sweet tea or stevia rebaudiana flocculation residues is characterized by comprising the following steps:
A) crushing and sieving the dried flocculation residues to obtain undersize materials;
B) filling the undersize into a chromatographic column and compacting, sealing two ends of the chromatographic column and vacuumizing to obtain the chromatographic column filled with the undersize;
C) washing the column with an extractant, and collecting effluent liquid;
D) purifying the effluent to obtain a tannic acid product.
2. The method as claimed in claim 1, wherein the flocculation residue is a precipitate obtained by flocculating a leaching solution obtained by leaching momordica grosvenori, rubus suavissimus or stevia with a flocculant, and the precipitate is subjected to a sweet glycoside recovery step.
3. The method according to claim 1, wherein the sieving is performed by a 6-20 mesh sieve.
4. The method of claim 1, wherein the degree of vacuum of the vacuum is-0.1 to-0.04 Mpa.
5. The method according to claim 1, wherein the column diameter-height ratio of the chromatography column is 1: 3-8, preferably 1: 4-6.
6. The method of claim 1, wherein the lixiviant is washed in a top or bottom column;
the lixiviant 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 more of sodium hydroxide, potassium hydroxide or ammonia water, and the addition amount of the alkali is that the pH of the leaching agent is 9-13; the volume ratio of the alcohol substance to the ethyl acetate is 1: 1-5.
7. The method of claim 6, wherein the leaching agent further comprises a penetration enhancer, and the penetration enhancer is one or more of monoglyceride, sucrose ester, Tween 20, Tween 40, Tween 60, Tween 80 and Tween 100.
8. The method according to claim 1, wherein the upper column volume of the lixiviant column wash is 3-5 BV, and the upper column flow rate is 0.1-1.0 BV/h, preferably 0.3-0.6 BV/h.
9. The method according to claim 1, wherein the column washing is carried out simultaneously with auxiliary ultrasound, the power of the ultrasound is 100-1000W, and the frequency is 30-50 KHZ.
10. The method of claim 1, wherein the purification method is:
passing the effluent through cation exchange resin, washing the cation exchange resin with water, eluting with ion exchange eluent, and collecting the eluate;
and sequentially removing the organic solvent from the eluent, desalting, concentrating, drying, crushing and sieving to obtain the tannic acid.
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