CN1535970A - Process for extracting sesamin - Google Patents

Abstract

The present invention discloses an extraction process of sesamin. Said process includes: firstly, purification process of sesamin: making sesame oil pass through the cylindrical body container whose interior is filled up with chromatographic adsorbent, at the same time making fat-soluble eluent, pass through the cylindrical body container to elute oily impurity, eluting until the bottom layer colour band of the cylindrical body container is removed; them making extraction process of sesamin: collecting adsorbent color band layer positioned in middle portion of the cylindrical body container, and utilizing solvent capable of dissolving sesamin to extract extract of sesamin containing in the color band layer. Said invention has the advantages of high extraction rate and high purity.

Description

A kind of extraction process of sesamin

Technical field:

The claimed technical scheme of the present invention belongs to the technical field of extracting sesamin technology.

Technical background:

Sesamin (sesamin) is a kind of All Pure Nature composition that is hidden in the til seed, and molecular formula is C ₂₀H ₁₈O ₆, fusing point is 122-123 ℃, its specific rotatory power [a] _D ²⁰Be+64.5 ℃ (chloroforms).Two and the tetrahydrofuran (THF) ring structure of tool, white crystal, water insoluble, be soluble in chloroform, ethyl acetate can be dissolved in hot ether, the hot ethanol equal solvent.Til seed comprises the sesamin of about 0.3-0.5% weight part.Sesame oil comprises the sesamin of about 0.5-1.0% weight part.Except that til seed, all contain sesamin in the root of Chinese wild ginger, Wu Chia Pee, paulownia, gingko, the Bi roots of grass, by discovering and the experiment proved that: sesamin has hypertension and cardiovascular hypertrophy, protects the liver, anti-oxidant, reducing cholesterol, prevent and treat arteriosclerosis, effect such as anticancer, therefore, also more and more urgent to the sesamin Study on extraction process.But few to the extracting method report of sesamin both at home and abroad at present, known two kinds of extraction processes are as follows at present:

A kind of is the underpressure distillation partition method, as the special justice-25764 of Japanese Patent, the disclosed technology of Chinese patent CN1088067C, in general the sesamin of 70% weight part can be included in the resulting overhead product of underpressure distillation partition method in the sesame oil, but foreign matter content is more, peculiar smell is arranged, so overhead product must be through the pre-treatment of deodorization; If further improve the overhead product purity and the rate of recovery, must use for example acetone/methanol, organic solvent such as ethanol or add a large amount of alkali according to the disclosed technology of Chinese patent CN1088067C and carry out saponification reaction.The harm that adds organic solvent is self-evident, carries out saponification reaction and also can corrode facility, contaminate environment and add alkali and fraction; Importantly saponification reaction easily makes sesamin generation isomerization, influences the quality of the finished product.Desired facility investment of underpressure distillation separating technology and operation working cost are bigger in addition, raw material is subject to heat-flash and coking or composition is changed, cause product purity low, the quality instability, so the conditional request of technological reaction is also very harsh, is difficult for grasping, and all can not be reused through the raw material behind the distillation extraction, become industrial residue, therefore the phenomenon of waste and contaminate environment is outstanding.

Also having a kind of extraction process is extraction process, process for extracting as Natural Medicine Chemistry teaching and research room of department of pharmacy of Xian Medical Univ is: sesame 2Kg, the ethanol high-speed breakage extracts 3 times, united extraction liquid, being evaporated to does not have the alcohol flavor, add aqueous suspension after, use ethyl acetate extraction, with acetic acid ethyl ester extract ethanol heating for dissolving, add proper amount of active carbon reflux decolour 20min again, filter the back placement and spend the night; Separate out precipitation, after the filtration throw out is used petroleum ether-ethyl acetate mixed solvent recrystallization again, get white needles solid 2.59 grams, yield 0.15%.This process using solvent method, organic solvent consumes many, and process of producing product easily produces new environmental pollution, and cost has dissolvent residual more greatly and inevitably, and operation is trouble, and workload is big, is not suitable for scale operation.

Summary of the invention:

Technical problem to be solved by this invention is: provide a kind of and guaranteeing under the prerequisite of high extraction, have lowly pollute, chemical residual is few, the sesamin extracting method of stay in grade, technology simple economy.

The scheme that solves the problems of the technologies described above is: at first be the purge process of sesamin: promptly sesame oil is by the column container of filling chromosorb, cross column shape container wash-out oiliness impurity with fat-soluble elutriant simultaneously, elutriant is washed till the stripping of column shape container bottom colour band; Be the proposition process of sesamin subsequently: promptly collect the sorbent material colour band layer that occupy the column shape container middle part, utilize the extractives that contains sesamin in the outstanding belt of solvent extraction that dissolves sesamin again.The present invention to the extraction yield of sesamin can reach more than 80%, purity can reach more than 75%, and because of chromatography can be carried out at normal temperatures and pressures, energy-conservation, the technology of being brought is simple, avoid the technique effect of sesamin pyrolytic decomposition more outstanding, the isolating sesamin quality of institute is simple in the adsorption layer, other contained impurity is less, thereby need not the deodorization processing, for further providing more good, used chemical reagent is also corresponding to be reduced, and pollutes also to be minimized.

For improving the purity of sesamin, extractives carries out being dissolved in or directly being dissolved in the sesamin crystallization solution after the saponification, will separate out crystallization behind the solution left standstill, and the sesamin purity of this xln primary crystallization can reach more than 96%.

In the aforesaid method, when sorbent material is the neutral alumina powder effect for best, can also with sesame oil through the neutral alumina chromatography after, directly be dissolved in the sesamin crystallization solution crystallization through the resulting extractives of proposition process and separate out.When using the neutral alumina powder, be that sesame oil/neutral alumina is not higher than 100/70 than upper column quantity as chromosorb; The best is 100/75-80; Internal diameter/post height=1/4-5, flow velocity are that the gram weight number of milliliter number and used neutral alumina of effluent liquid in 1-1.5 hour is suitable.Find through experiment: neutral alumina is strong especially to the absorption specificity of sesamin, and the boundary of adsorption layer is particularly evident clear.Therefore it is higher than the sesamin purity of prior art gained, and extractives need not to carry out the saponification processing just can direct crystallization.Other nutritive ingredient loss of the chromatography filtrate of sesame oil is few in addition, can be used as the raw material of edible blend oil.

For further improving the extraction efficiency of sesamin, to occupy the sorbent material colour band layer taking-up of column shape container middle part and place reflux vessel, by reflux extraction extractives in the colour band layer is proposed with the solvent of the dissolving sesamin that is equivalent to 2-5 times of sorbent material colour band layer weight, return time is 2-6 hour, and reflux temperature is not less than the solvent boiling point of dissolving sesamin.

In the purge process of above-mentioned technology, to flowing out elutriant when detecting following situation, stop wash-out, promptly flow out elutriant and mix vibration with 36% concentrated hydrochloric acid and 2% furfural water solvent solution, scarlet appears in water can stop wash-out.

Above-mentioned elutriant is a sherwood oil.The solvent of dissolving sesamin is the above ethanol of 70% (V/V).The solvent of crystallization sesamin is an ether, is 20-25 ℃ in envrionment temperature, and the ether consumption is that the 8-10% of sesame oil weight is the best.

Positively effect of the present invention is embodied in: 1, the present invention adopts adsorption chromatography to extract sesamin, has very high extraction yield and purity, have low pollute, need not that deodorization, reagent consume less, the advantage of stay in grade, technology simple economy.2, special feature of the present invention is to adopt neutral alumina as sorbent material, and it is strong especially to the absorption specificity of sesamin, and therefore the purity of extracting is also high, sesame oil after the extraction can be used as the edible blend oil comprehensive utilization, without any loss, environmental pollution is little, and economic benefit has more significantly.3, after the present invention especially passes through the chromatography of neutral alumina, can remove from and think in the traditional concept that indispensable saponification reaction carries out separating process, not only shortened the operational path that extracts, also avoided the isomerization of sesamin to guarantee the quality of sesamin, and thoroughly avoided alkali pollution.4, the present invention compares with the vacuum fractionation method, and from complete process, its high purity sesamin extraction efficiency is suitable with it even better.

Embodiment:

Each embodiment extracts the technical process of high purity sesamin from sesame oil as follows: the chromatography column that sesame oil 100 was restrained the chromosorb described in following each embodiment of sherwood oil filling, use pure sherwood oil (boiling range 60-90 ℃) elutriant to cross oiliness impurity outside the chromatography column wash-out sesamin simultaneously, the wash-out effluent liquid is used and 36% concentrated hydrochloric acid and 2% furfural water solvent solution jolting, scarlet appears in water can stop wash-out, and upper, middle and lower is three kinds of colour bands in the post at this moment; Go up and to be the crest, in be yellow band, be down the oil reservoir colour band; Take out the sorbent material belt that occupy the chromatography column middle part subsequently and place the thermal backflow container, 95% (v/v) medical ethanol that utilizes weight to be equivalent to the sorbent material belt weight of 5 times of taking-ups carries out thermal backflow and extracts, reflux temperature is 80 ℃, after the described time, extracting solution obtains the oily extractives after reclaiming ethanol through following each embodiment.

Table one:

Numbering	Chromatography agent kind	Elution time	The colour band sharpness	Return time	The extractives smell	The extractives color and luster	The sesamin yield	The sesamin rate of recovery	Sesamin purity
										Embodiment 1	Silica gel	12 hours	Fuzzy	5 hours	Do not have	Pale brown look	0.55 gram	??78.5％	??75.3％
Embodiment 2	Neutral alumina	12 hours	More clear	5 hours	Do not have	Yellow	0.55 gram	??78.5％	??81.2％

In this table, the internal diameter of chromatography column/post height ratio=1/8 is=1: 1 than upper column quantity, and elution speed is that flow velocity is that the milliliter number of 1.5 hours effluent liquid equates with the weight number (gram) of used chromatography agent.The rate of recovery of sesamin be in the extractives sesamin and raw materials used in the weight percent of sesamin.Utilize the method for shining high effective liquid chromatography for measuring sesamin content to record and contain 0.7 gram sesamin in the 100 gram sesame oil.Sesamin purity is the weight percent of sesamin and isolate gross weight in the isolate.Select that silica gel that chromatography uses and chromatography use for use neutral alumina.(following each embodiment is identical), this table show that extraction yield of the present invention can reach about 80%, and purity still has much room for improvement.

Table two: this table is the chromatography effluent liquid more than heating half an hour under the 60-90 ℃ of condition, flings to sherwood oil, measures every index by the method for GB8233-87.

Numbering	Smell	Transparency	Color and luster	Moisture content and volatile matter	Impurity	Acid value	Heat test	Saponified matter content
									Embodiment 1	Free from extraneous odour	Little turbid	Yellow	??0.2	??0.5	??5.0	Separate out	??0.02
Embodiment 2	Free from extraneous odour	Transparent	Yellow	??0.1	??0.1	??1.0	Nothing is separated out	??0.02

Last table shows, reaches the quality standard of edible sesame oil by the quality index of the effluent liquid after the absorption of neutral alumina chromatography comprehensively.

More than explanation neutral alumina and silica gel are strong to the absorption parsing power of sesamin, but neutral alumina absorption specificity is better.

Table three: measure silica gel and the extraction situation of neutral alumina under different return times as stated above:

This table shows that recovery time is proper at 2-4.5 hour

Numbering		Return time	The sesamin yield	The sesamin rate of recovery	Sesamin purity
						Embodiment 3	Silica gel	100 minutes	0.23 gram	??32.8％	????59.8％
Embodiment 4	2 hours	0.49 gram	??70.0％	????73.2％
					Embodiment 5	4 hours		0.54 gram	??77.1％	????79.3％
Embodiment 6	6 hours	0.61 gram	??87.1％	????80.6％
					Embodiment 7	6.5 hour		0.62 gram	??88.6％	????81.3％
Embodiment 8	Neutral alumina	100 minutes	0.24 gram	??34.3％							????79.9％
					Embodiment 9	2 hours	0.51 gram	??72.8％	????81.6％
Embodiment 10		4 hours	0.56 gram	??80.0％						????83.4％
					Embodiment 11	6 hours	0.62 gram	??88.6％	????86.8％
Embodiment 12		6.5 hour	0.62 gram	??88.6％						????87.1％

Table four: the dissolving of selecting and ethanol identical with embodiment 10 other conditions to vary in weight under the situation proposes situation, and ethanol weight is the multiple of the sorbent material belt weight that is equivalent to take out:

Numbering	Ethanol weight	The sesamin yield	The sesamin rate of recovery	Sesamin purity
					Embodiment 13	1.5 doubly	0.21 gram	??30.0％	????78.9％
Embodiment 14	2 times	0.50 gram	??71.4％	????85.0％
					Embodiment 15	3 times	0.52 gram	??74.3％	????87.1％
Embodiment 16	4 times	0.54 gram	??77.1％	????87.9％
					Embodiment 17	6 times	0.63 gram	??90.0％	????88.4％

More than explanation ethanol consumption doubly is suitable for the 2-5 of the sorbent material belt weight of taking-up.

Table five: select identical and dissolvings proposition situations under the alcohol concn different situations with embodiment 10 other conditions,

Numbering	Alcohol concn	The sesamin yield	The sesamin rate of recovery	Sesamin purity
					Embodiment 18	??40％(V/V)	011 gram	??15.7％	??49.5％
Embodiment 19	??60％(V/V)	0.12 gram	??17.1％	??60.8％
					Embodiment 20	??70％(V/V)	0.49 gram	??70.0％	??87.5％

It is relatively poor that the dissolve with ethanol that concentration is lower than 70% (V/V) proposes the ability of sesamin.

Table six: except that the separating resulting more identical than other processing condition the upper column quantity and embodiment 10 as follows:

Numbering	Compare upper column quantity	The extractives color and luster	The sesamin yield	The sesamin rate of recovery	Sesamin purity
						Embodiment 21	????100/60	Yellow	0.22 gram	????31.4％	??84.0％
Embodiment 22	????100/70	Bright orange	0,53 gram	????75.7％	??84.9％
						Embodiment 23	????100/75	Bright orange	0.55 gram	????78.6％	??86.7％
Embodiment 24	????100/80	Bright orange	0.55 gram	????78.6％	??86.1％
						Embodiment 25	????100/90	Bright orange	0.55 gram	????78.6％	??86.9％

Table six reflects that it is better not to be higher than 100/70 effect than upper column quantity, the most remarkable in the 100/75-100/80 effect.

Table seven:: the separating resulting that other processing condition and embodiment 23 are identical except that internal diameter/post height is as follows:

Numbering	Internal diameter/post height	The colour band sharpness	Elution time (hour)
				Embodiment 26	????1/6	Clear	????10
Embodiment 27	????1/5	Clear	????5
				Embodiment 28	????1/4	Clear	????3
Embodiment 29	????1/3	More clear	????1

As seen from the above table internal diameter/post height in the 1/4-1/5 effect for well.

Table eight: the separating resulting that other processing condition and embodiment 29 are identical except that eluent flow rate is as follows:

Numbering	Elution time	The colour band sharpness	The extractives color and luster	The sesamin yield	The sesamin rate of recovery	Sesamin purity
							Embodiment 30	0.5 hour	Fuzzy	Pale brown	0.42 gram	????60.0％	????82.9％
Embodiment 31	1 hour	Clear	Bright orange	0.55 gram	????78.6％	????83.6％
							Embodiment 32	2 hours	Clear	Bright orange	0.55 gram	????78.6％	????83.3％

Elution time is several needed times when identical of volume (milliliter) number and the neutral alumina weight (gram) of chromatography effluent liquid.

Table nine: embodiment 1 and embodiment 2 crystallization situations.Embodiment 1 and 2 resulting extractivess directly are dissolved in the anhydrous diethyl ether, and the consumption of ether is 10 grams, and envrionment temperature is that the crystallization of being separated out behind 23 ℃ of solution left standstills is the sesamin crystal.

Crystallization time	The xln color and luster		Sesamin purity
					Embodiment 1	Embodiment 2	Embodiment 1	Embodiment 2
	??2	Filbert	Pale brown look	????75.4％					????82.1％
??5					Pale brown look	Canescence	????82.3％	????91.3％
	??10	Faint yellow	White	????87.6％					????95.1％
??18					Canescence	White	????92.1％	????96.2％
	??24	Canescence	White	????92.3％					????96.3％

Table nine shows: can increase substantially through the purity after the extractives crystallization behind the chromatography, and the sesamin purity behind the use neutral alumina chromatography is than using the effective of silica gel.

Toward embodiment 1 and embodiment as extractives to add concentration be 5% sodium hydroxide ethanol 5ml, react after 1 hour, add 100ml water, saponification solution is with 30ml ether extraction 3 times, the recovery ether is pressed the crystallization condition crystallization shown in the table nine again.Resulting result is shown in the table following table:

Crystallization time	The xln color and luster		Sesamin purity
					Embodiment 1	Embodiment 2	Embodiment 1	Embodiment 2
	??2	Pale brown look	Pale brown look	????81.9％					????82.1％
??5					Faint yellow	Canescence	????86.7％	????91.4％
	??10	White	White	????94.5％					????95.1％
??18					White	White	????95.1％	????96.2％
	??24	White	White	????95.6％					????96.3％

The crystallization effect of last table explanation sesame oil after the extractives saponification behind the silica gel column chromatography will be got well, and the crystallization effect of sesame oil after the extractives saponification behind the neutral alumina chromatography then do not have considerable change.

Embodiment 27 resulting extractivess directly are dissolved in the anhydrous diethyl ether, the consumption crystallization of the ether of according to the form below, envrionment temperature is 23 ℃, crystallization time 12 hours, resultant crystallization situation is as shown in the table:

Numbering	The ether consumption	The xln color and luster	Xln weight	Sesamin purity
					Embodiment 33	7 grams	White	0.42 gram	????95.4％
Embodiment 34	8 grams	White	0.45 gram	????95.8％
					Embodiment 35	9 grams	White	0.52 gram	????96.5％
Embodiment 35	11 grams	White	0.55 gram	????96.5％

The last ether consumption that shows is that the 8-10% of sesame oil weight is advisable.

Claims (10)

1, a kind of extraction process of sesamin, it is characterized in that: at first for the purge process of sesamin, be sesame oil by loading the column container of chromosorb, cross column shape container wash-out oiliness impurity with fat-soluble elutriant simultaneously, elutriant is washed till column shape container bottom colour band stripping; Be the proposition process of sesamin subsequently: promptly collect the sorbent material colour band layer that occupy the column shape container middle part, utilize the extractives that contains sesamin in the outstanding belt of solvent extraction that dissolves sesamin again.

2, sesamin extraction process according to claim 1 is characterized in that: extractives carries out being dissolved in or directly being dissolved in the sesamin crystallization solution after the saponification, will separate out crystallization behind the solution left standstill.

3, sesamin extraction process according to claim 1 is characterized in that: sorbent material is the neutral alumina powder; Can also be with sesame oil through behind the neutral alumina chromatography, directly be dissolved in the sesamin crystallization solution crystallization through the resulting extractives of proposition process and separate out.

4, according to claim 1 or 3 described sesamin extraction processes, it is characterized in that: occupy the sorbent material colour band layer taking-up of column shape container middle part and place reflux vessel, by reflux extraction extractives in the colour band layer is proposed with the solvent of the dissolving sesamin that is equivalent to 2-5 times of sorbent material colour band layer weight, return time is 2-6 hour, and reflux temperature is not less than the boiling point of the solvent of dissolving sesamin.

5, according to claim 1 or 3 described sesamin extraction processes, it is characterized in that: to flowing out elutriant when detecting following situation, stop wash-out, promptly flow out elutriant and mix vibration with 36% concentrated hydrochloric acid and 2% furfural water solvent solution, scarlet appears in water can stop wash-out

6, according to claim 1 or 3 described sesamin extraction processes, it is characterized in that: elutriant is a sherwood oil.

7, according to claim 1 or 3 described sesamin extraction processes, it is characterized in that: the solvent of dissolving sesamin is the above ethanol of 70% (V/V).

8, according to claim 2 or 3 described sesamin extraction processes, it is characterized in that: the solvent of crystallization sesamin is an ether, and when envrionment temperature was 20-25 ℃, the ether consumption was that the 8-10% of sesame oil weight is the best.

9, sesamin extraction process according to claim 3 is characterized in that: than upper column quantity is that sesame oil/neutral alumina is not higher than 100/70.

10, sesamin extraction process according to claim 9 is that sesame oil/neutral alumina is best than upper column quantity is 100/75-80, and internal diameter/post height=1/4-5, flow velocity are that the gram weight number of the milliliter number of effluent liquid in 1-1.5 hour and used neutral alumina is suitable.