CN103040880A - Separation and purification method of tribulus terrestris saponin - Google Patents
Separation and purification method of tribulus terrestris saponin Download PDFInfo
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- CN103040880A CN103040880A CN2012105955575A CN201210595557A CN103040880A CN 103040880 A CN103040880 A CN 103040880A CN 2012105955575 A CN2012105955575 A CN 2012105955575A CN 201210595557 A CN201210595557 A CN 201210595557A CN 103040880 A CN103040880 A CN 103040880A
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- tribuloside
- ethanol water
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- silica gel
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Abstract
The invention discloses a separation and purification method of tribulus terrestris saponin. The method comprises the steps that a raw material is cleaned, and fed in from a feeding hopper; an extraction tank unit host rotates to slowly push the material from the front end of a unit backwards; an extraction solvent enters an extraction tank from a liquid inlet tube at the tail end of the unit, passes through the moving material from the back end of the tank, and flows towards the front end; and solid and liquid substances are contacted fully in an inverse motion, so that effective components in the medicinal material are extracted. Dregs are forcibly pushed to a dreg discharge port by a discharge transport and then discharged; a special juice squeezer squeezes the dregs; residual medicine liquor in the dregs is squeezed out of a medicinal material tissue; and the content of the residual medicine liquor in the dregs is reduced. The extraction efficiency is higher, and the extraction is more complete. In addition, the method adopts macroporous resin, and is combined with a silica gel column chromatography, so that a separating effect is better. The finished tribulus terrestris saponin with a maximum yield of 2% and the content of above 95% can be obtained.
Description
Technical field:
The invention belongs to the natural organic chemistry field, relate to a kind of isolation and purification method of tribuloside, particularly relate to a kind of method of utilizing countercurrent extraction associating macroporous adsorbent resin coupling silica gel column chromatography separating purification tribuloside.
Background technology:
Fructus Tribuli, another name thatch, Fructus Tribuli, Fructus Tribuli, bypass, drawer people, end row, jackal plumage, rise push away, be Herba chenopodii, Fructus Atriplicis Sibiricae, Du Fructus Tribuli, stop plumage, drought grass, triangle Fructus Tribuli, three Fructus Gleditsia acupuncture, anise thorn, puncture frame, wild Pedicellus et Pericarpium Trapae, Pedicellus et Pericarpium Trapae, firmly Fructus Tribuli, puncture Herba chenopodii Follicle radish etc., be the dry mature fruit of zygophyllaceae plant Fructus Tribuli.Fruit contains nimbecetin, nimbecetin 3-glucoside, nimbecetin 3-rutinoside, tribuloside, peroxidase etc.Have diuresis, arteriosclerosis, the anti-ageing effect of waiting for a long time.
Tribuloside is mainly steroid oside compound, its ruscogenin be diosgenin (diosgenin) but, Shandong phase ruscogenin (ruscogenin), hecogenin (hecogenin), gitogenin (gitoogenin) etc. contain Fructus Tribuli glycoside (tribuloside), Kaempferol-rutinoside (kaempferol-rutinoside), astragalin (astragalin), Harmane (harmine) etc. in addition.Tribuloside can promote the ketone testis naturally, increases strength, improves whole competitive state, has no side effect, and blood pressure lowering is arranged, the effects such as blood fat reducing, and wherein contained peroxide decomposition enzyme has obvious anti-aging effects.The of a specified duration clothes on the face cicatrix of can dispelling, and make skin tender lubricated.In recent years, it is found that and contain a large amount of tribulosides in the natural plants Fructus Tribuli, therefrom extract tribuloside and obtained encouraging progress, raw material Fructus Tribuli source is wider.
Summary of the invention
The object of the invention is to provide a kind of isolation and purification method of tribuloside; The object of the invention also be to provide a kind of convenient and swift, raw material sources abundant, extraction efficiency is high, separation and purification successful, the production technology of utilizing Continuous Countercurrent Extraction and enriching and purifying macroporous resin tribuloside that dna purity is high.
The present invention seeks to be achieved through the following technical solutions.
A kind of isolation and purification method of tribuloside, its step is as follows:
(1) Fructus Tribuli is cleaned the rear continuous countercurrent extracting tank ethanol water reflux, extract, that adds;
(2) extracting liquid filtering that will process through (1) gets the tribuloside crude extract;
(3) gained tribuloside crude extract is concentrated, get the thick concentrated solution of tribuloside;
(4) with the thick concentrated solution thin up of gained tribuloside, and filter, get filtrate;
(5) with the upper broad spectrum type macroporous resin adsorption post of gained filtrate, adsorb the complete impurity that washes with water, use again the ethanol aqueous wash impurity of low powered posterior chamber, then use the ethanol water eluting of the high number of degrees, get the tribuloside eluent;
(6) the gained eluent is condensed into cream, gets the tribuloside condensed cream;
(7) the tribuloside condensed cream is mixed silica gel, and the mixture that will mix through ethyl acetate and petroleum ether mixed liquor eluting, gets eluent as for the silicagel column top;
(8) eluent is reclaimed solvent after concentrate drying get the tribuloside semi-finished product;
(9) the tribuloside semi-finished product are dissolved with ethanol water, filter, Recycled ethanol, concentrated, place crystallize out, sucking filtration gets the tribuloside finished product.
In the described step (1), Fructus Tribuli carries out the ethanol water reflux, extract, after cleaning again, and the extraction solvent is 50%～85% ethanol water.
In the described step (1), the equipment that extracts is the countercurrent extraction production line, comprises elevator, charging transmission, countercurrent extraction tank group main frame 1, draws glassware 1, Juice squeezer 1, countercurrent extraction tank group main frame 2, draws glassware 2, Juice squeezer 2, discharging transmission, line pump, Pump for giving-out, temporary tank, heat exchanger, liquid flowing valve etc.Raw material is at the uniform velocity added by elevator charge door place behind the crushing screening, and extracting solution pumps via Pump for giving-out continuously from flowing to temporary storage tank.
In the described step (1), adverse current production line parameter is elevator frequency 15～30Hz, main frame 1 frequency 18～20Hz, Juice squeezer 1 frequency 45～50Hz, main frame 2 frequencies 20～22Hz, Juice squeezer 2 frequencies 40～45Hz, Pump for giving-out flow 0.5～2T/h, charging 100～400kg/h.
In the described step (4), the dilution water yield is 5 times of concentrated solution volume, filters to such an extent that impurity discards.
In the described step (5), the macroporous resin adsorption step adopts wet method dress post, keeps liquid level, and filtrate is passed through adsorption column, flow velocity per minute 0.05ml/g resin, and the resin model is HPD400, HPD100, DM-130 or AB-8 broad spectrum type macroporous adsorbent resin.
In the described step (5), the macroporous adsorptive resins ratio of height to diameter is 10～5: 1, the ethanol water of low powered posterior chamber is 5%～20% ethanol water, the ethanol water of the high number of degrees is 50%～80% ethanol water, washing the impurity water yield is 3～5BV, the ethanol water amount of washing the impurity low powered posterior chamber is 1～2BV, and the ethanol water amount of the high number of degrees of eluting is 4BV.
In the described step (7), the silica gel column chromatography step adopts wet method dress post, keep liquid level, condensed cream is mixed the rear silica gel of activation by weight at 1: 1, and the mixture that will mix places silicagel column top, and eluent is ethyl acetate: the petroleum ether volume ratio is 50～85: 15 ethyl acetate and petroleum ether mixture, elution flow rate per minute 0.1ml/g silica gel, elution volume is 5BV, and the silica gel activating condition is 110 ℃ of 30min.
In the described step (9), the tribuloside semi-finished product are measured 60 ℃ of thermosols of 50% ethanol water with 12～16 times, and concentrated density is d=1.03～1.05.
The present invention discloses a kind of isolation and purification method of tribuloside, the method is: drop into from cast hopper after raw material is cleaned, the rotation of extraction pot group main frame, material is slowly advanced backward from the unit front end, the feed tube that extracts simultaneously solvent slave group end enters in the extraction pot, pass mobile material forward end by the tank rear end and flow, the biphase material of solid-liquid is fully contact in this reverse movement, thereby with extracts active ingredients in the medical material out.Medicinal residues are forced to be pushed to slag notch and are discharged through the discharging conveyer, and special Juice squeezer pushes medicinal residues, and medicinal residues Shen residual liquor is extruded the medical material tissue, reduces medicinal residues Shen residual liquor content.Extraction efficiency is higher, extraction is more complete.
The present invention selects macroporous adsorbent resin and binding silica gel column chromatography purification simultaneously, and separating effect is better.
The specific embodiment:
Embodiment 1:
Take by weighing Fructus Tribuli 2T, at the uniform velocity added by the speed of elevator charge door with 400kg/h after cleaning, 75% ethanol water is added by feed tube with the flow of tubing pump with 2T/h, the elevator frequency setting is 30Hz, main frame 1 frequency setting is 20Hz, and Juice squeezer 1 frequency setting is 50Hz, and main frame 2 frequency settings are 22Hz, Juice squeezer 2 frequency settings are 45Hz, get tribuloside crude extract 10T; The tribuloside crude extract is concentrated to concentration tank via the Pump for giving-out continuous pump from flowing to temporary storage tank, gets the thick concentrated solution 600L of tribuloside; The gained concentrated solution is added the dilution of 3T water, remove by filter impurity; Filtrate is crossed the HPD400 macroporous adsorbent resin, and the resin column ratio of height to diameter is 5: 1, adsorbs saturated rear 6T washing impurity, 2T5% ethanol aqueous wash impurity, and 8T80% ethanol water eluting gets tribuloside eluent 7.8T; Eluent concentrates to get tribuloside condensed cream 400kg; The tribuloside condensed cream is mixed the 400kg activated silica gel, places the silicagel column top, and eluent is ethyl acetate: the petroleum ether volume ratio is 85: 15 ethyl acetate and petroleum ether mixture, and elution flow rate per minute 0.1ml/g silica gel gets eluent 2000kg; Concentrate drying got tribuloside semi-finished product 120kg after eluent reclaimed solvent; The tribuloside semi-finished product filter with 60 ℃ of thermosols of 1500L50% ethanol water, and Recycled ethanol is concentrated into d=1.05, place crystallize out, and sucking filtration gets tribuloside finished product 40kg, content 96.5%.
Embodiment 2:
Take by weighing Fructus Tribuli 800kg, at the uniform velocity added by the speed of elevator charge door with 200kg/h after cleaning, 65% ethanol water is added by feed tube with the flow of tubing pump with 1T/h, the elevator frequency setting is 25Hz, main frame 1 frequency setting is 18Hz, and Juice squeezer 1 frequency setting is 50Hz, and main frame 2 frequency settings are 22Hz, Juice squeezer 2 frequency settings are 45Hz, get tribuloside crude extract 4T; The tribuloside crude extract is concentrated to concentration tank via the Pump for giving-out continuous pump from flowing to temporary storage tank, gets the thick concentrated solution 250L of tribuloside; The gained concentrated solution is added the dilution of 1.25T water, remove by filter impurity; Filtrate is crossed the AB-8 macroporous adsorbent resin, and the resin column ratio of height to diameter is 5: 1, adsorbs saturated rear 6T washing impurity, 2T20% ethanol aqueous wash impurity, and 8T600% ethanol water eluting gets tribuloside eluent 7.8T; Eluent concentrates to get tribuloside condensed cream 150kg; The tribuloside condensed cream is mixed the 150kg activated silica gel, places the silicagel column top, and eluent is ethyl acetate: the petroleum ether volume ratio is 65: 15 ethyl acetate and petroleum ether mixture, and elution flow rate per minute 0.1ml/g silica gel gets eluent 750kg; Concentrate drying got tribuloside semi-finished product 50kg after eluent reclaimed solvent; The tribuloside semi-finished product filter with 60 ℃ of thermosols of 600L50% ethanol water, and Recycled ethanol is concentrated into d=1.04, place crystallize out, and sucking filtration gets tribuloside finished product 14kg, content 95%.
Embodiment 3:
Take by weighing Fructus Tribuli 1.6T, at the uniform velocity added by the speed of elevator charge door with 100kg/h after cleaning, 75% ethanol water is added by feed tube with the flow of tubing pump with 500kg/h, the elevator frequency setting is 25Hz, main frame 1 frequency setting is 18Hz, and Juice squeezer 1 frequency setting is 50Hz, and main frame 2 frequency settings are 22Hz, Juice squeezer 2 frequency settings are 45Hz, get tribuloside crude extract 8T; The tribuloside crude extract is concentrated to concentration tank via the Pump for giving-out continuous pump from flowing to temporary storage tank, gets the thick concentrated solution 500L of tribuloside; The gained concentrated solution is added the dilution of 2.5T water, remove by filter impurity; Filtrate is crossed the DM-130 macroporous adsorbent resin, and the resin column ratio of height to diameter is 5: 1, adsorbs saturated rear 6T washing impurity, 2T15% ethanol aqueous wash impurity, and 8T70% ethanol water eluting gets tribuloside eluent 7.8T; Eluent concentrates to get tribuloside condensed cream 310kg; The tribuloside condensed cream is mixed the 310kg activated silica gel, places the silicagel column top, and eluent is ethyl acetate: the petroleum ether volume ratio is 75: 15 ethyl acetate and petroleum ether mixture, and elution flow rate per minute 0.1ml/g silica gel gets eluent 1.5T; Concentrate drying got tribuloside semi-finished product 110kg after eluent reclaimed solvent; The tribuloside semi-finished product filter with 60 ℃ of thermosols of 1.6T50% ethanol water, and Recycled ethanol is concentrated into d=1.03, place crystallize out, and sucking filtration gets tribuloside finished product 28kg, content 98%.
Claims (9)
1. the isolation and purification method of a tribuloside is characterized in that the method comprises the steps:
(1) Fructus Tribuli is cleaned the rear continuous countercurrent extracting tank ethanol water reflux, extract, that adds;
(2) extracting liquid filtering that will process through (1) gets the tribuloside crude extract;
(3) gained tribuloside crude extract is concentrated, get the thick concentrated solution of tribuloside;
(4) with the thick concentrated solution thin up of gained tribuloside, and filter, get filtrate;
(5) with the upper broad spectrum type macroporous resin adsorption post of gained filtrate, adsorb the complete impurity that washes with water, use again the ethanol aqueous wash impurity of low powered posterior chamber, then use the ethanol water eluting of the high number of degrees, get the tribuloside eluent;
(6) the gained eluent is condensed into cream, gets the tribuloside condensed cream;
(7) the tribuloside condensed cream is mixed silica gel, and the mixture that will mix through ethyl acetate and petroleum ether mixed liquor eluting, gets eluent as for the silicagel column top;
(8) eluent is reclaimed solvent after concentrate drying get the tribuloside semi-finished product;
(9) the tribuloside semi-finished product are dissolved with ethanol water, filter, Recycled ethanol, concentrated, place crystallize out, sucking filtration gets the tribuloside finished product.
2. the production new technique of tribuloside according to claim 1 is characterized in that in the described step (1), and Fructus Tribuli carries out the ethanol water reflux, extract, after cleaning again, and the extraction solvent is 50%～85% ethanol water.
3. the production new technique of tribuloside according to claim 1 is characterized in that in the described step (1), the equipment that extracts is the countercurrent extraction production line, comprises elevator, charging transmission, countercurrent extraction tank group main frame 1, draws glassware 1, Juice squeezer 1, countercurrent extraction tank group main frame 2, draws glassware 2, Juice squeezer 2, discharging transmission, line pump, Pump for giving-out, temporary tank, heat exchanger, liquid flowing valve etc.Raw material is at the uniform velocity added by elevator charge door place behind the crushing screening, and extracting solution pumps via Pump for giving-out continuously from flowing to temporary storage tank.
4. the production new technique of tribuloside according to claim 1 is characterized in that in the described step (1), adverse current production line parameter is elevator frequency 15～30Hz, main frame 1 frequency 18～20Hz, Juice squeezer 1 frequency 45～50Hz, main frame 2 frequencies 20～22Hz, Juice squeezer 2 frequencies 40～45Hz, Pump for giving-out flow 0.5～2T/h, charging 100～400kg/h.
5. the production new technique of tribuloside according to claim 1 is characterized in that in the described step (4), and the dilution water yield is 5 times of concentrated solution volume, filters to such an extent that impurity discards.
6. the production new technique of tribuloside according to claim 1 is characterized in that in the described step (5), the macroporous resin adsorption step adopts wet method dress post, keep liquid level, filtrate is passed through adsorption column, flow velocity per minute 0.05ml/g resin, resin model are HPD400, HPD100, DM-130 or AB-8 broad spectrum type macroporous adsorbent resin.
7. the production new technique of tribuloside according to claim 1 is characterized in that in the described step (5), the macroporous adsorptive resins ratio of height to diameter is 10～5: 1, the ethanol water of low powered posterior chamber is 5%～20% ethanol water, the ethanol water of the high number of degrees is 50%～80% ethanol water, washing the impurity water yield is 3～5BV, the ethanol water amount of washing the impurity low powered posterior chamber is 1～2BV, and the ethanol water amount of the high number of degrees of eluting is 4BV.
8. the production new technique of tribuloside according to claim 1 is characterized in that in the described step (7), the silica gel column chromatography step adopts wet method dress post, keep liquid level, condensed cream is mixed the rear silica gel of activation by weight at 1: 1, and the mixture that will mix places the silicagel column top, eluent is ethyl acetate: the petroleum ether volume ratio is 50～85: 15 ethyl acetate and petroleum ether mixture, elution flow rate per minute 0.1ml/g silica gel, and elution volume is 5BV.The silica gel activating condition is 110 ℃ of 30mn.
9. the production new technique of tribuloside according to claim 1 is characterized in that in the described step (9), and the tribuloside semi-finished product are measured 60 ℃ of thermosols of 50% ethanol water with 12～16 times, and concentrated density is d=1.03～1.05.
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| CN201210595557.5A CN103040880B (en) | 2012-12-13 | 2012-12-13 | A kind of isolation and purification method of tribuloside |
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Cited By (3)
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| WO2017143798A1 (en) * | 2016-02-22 | 2017-08-31 | 彭海英 | Health preserving and kidney tonifying okra wine and preparation method therefor |
| CN111494440A (en) * | 2020-04-24 | 2020-08-07 | 武汉轻工大学 | Extraction, purification and preparation technology of blood sugar reducing component saponin in caltrop, caltrop saponin extract and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105125599A (en) * | 2015-08-14 | 2015-12-09 | 内蒙古鑫吉利生物科技有限公司 | Preparation method of caltrop saponin contained tribulus terrestris extract |
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| WO2017143798A1 (en) * | 2016-02-22 | 2017-08-31 | 彭海英 | Health preserving and kidney tonifying okra wine and preparation method therefor |
| CN111494440A (en) * | 2020-04-24 | 2020-08-07 | 武汉轻工大学 | Extraction, purification and preparation technology of blood sugar reducing component saponin in caltrop, caltrop saponin extract and application |
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