CN1443749A - Method for separating and purifying ephedrine by using weak acid cation exchange resin and macroporous resin - Google Patents
Method for separating and purifying ephedrine by using weak acid cation exchange resin and macroporous resin Download PDFInfo
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- CN1443749A CN1443749A CN 02104402 CN02104402A CN1443749A CN 1443749 A CN1443749 A CN 1443749A CN 02104402 CN02104402 CN 02104402 CN 02104402 A CN02104402 A CN 02104402A CN 1443749 A CN1443749 A CN 1443749A
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- ephedrine
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Abstract
The present invention relates to a method for separating and purifying ephedrine by using weak acid cationc exchange resin and macroporous resin. Said method includes the following steps: pulverizing ephedrae herba, mixing it with solvent to make ultrasonic extraction, filtering leaching liquor, using NaOH solution to regulate pH to 8-14, after filtration, making the filtrate pass through the weak acid cation exchange resin column or macroporous resin column to make exchange and adsorption, then using hydrochloric acid or mixed liquor of hydrochloric acid and organic solvent to make elution, making the eluant undergo the process of reduced pressure concentration to obtain ephedrine hydrochloride crystal, and the resin after elution can be washed with organic solvent and can be reused. Its extraction efficiency can be up to above 95%.
Description
Technical field
The present invention relates to a kind of method of separation and purification ephedrine, particularly relate to a kind of method with weakly acidic cation-exchange resin and macroporous resin separation and purification ephedrine.
Background technology
Chinese ephedra is the traditional herbal medicine that has won fame both at home and abroad, and mainly contains sweating, relievings asthma, Li Shui, removes the wind effect.Can control diseases such as common cold caused by wind-cold, fever with chills, lossless, Whooping cough, bronchitis, bronchial asthma, its main effective constituent is ephedrine.Because the medicine that contains PPA is by after time-out uses both at home and abroad, ephedrine is as the best substitute of PPA, ton surplus only domestic market demand amount just has a net increase of 200, and the world market annual requirement also develops into 1600 tons simultaneously, and can produce the outlet ephedrine of high profit, purity is all more than 90%.
The ephedrine production technique of enterprise's employing is at present carried out solvent extraction with toluene or dimethylbenzene, and toxicity is higher and solvent loss is bigger than normal.Owing to adopt repeatedly refining, decolouring, crystallization, just can obtain pure product, make the production cycle long, complex process, environmental pollution seriously and energy consumption bigger.
In addition, CN1201029A discloses a kind of new process of production that utilizes macroporous resin to prepare Ephedra sinica fine powder and byproduct tannin.This method is on existing Chinese ephedra powder extraction process basis, adds the operation that one vat liquor crossed the macropore resin bed, make the byproduct tannin be adsorbed and obtain enrichment, and other material comprises ephedrine, all through resin, is not adsorbed.Because this technology is only separated the tannin in the Chinese ephedra powder, and other impurity is not had tangible centrifugation.Therefore, the content of ephedrine only brings up to 6～10% from≤4%, and active constituent content is still very low, belongs to the Chinese ephedra meal.As seen, this method has to the Chinese ephedra meal and what mainly obtain is the byproduct tannin, so this method also exists certain defective.
Summary of the invention
The objective of the invention is to overcome the shortcoming that prior art exists, by utilizing the character of macroporous resin adsorption free state ephedrine, both the tannin in the Chinese ephedra powder was separated, again ephedrine is separated with other impurity and extract, extraction efficiency reaches more than 95%; And,, reduce cost in order to improve purity; Thereby provide a kind of method of from the ephedrine extracting solution, extracting the simple and easy to do of ephedrine technology and reducing the weakly acidic cation-exchange resin and the macroporous resin separation and purification ephedrine of environmental pollution.
Purpose of the present invention can realize by following measure:
The method of weakly acidic cation-exchange resin provided by the invention and macroporous resin separation and purification ephedrine, carry out according to the following steps:
1. supersound extraction: the Herba Ephedrae powder is placed in the solvent mixes, mixing solutions is placed in the ultrasonic generator container then, the Herba Ephedrae powder is carried out supersound extraction with ultrasonic wave;
Described solvent comprises water, hydrochloric acid soln or sodium hydroxide; Its solvent mix with Herba Ephedrae count 1: 3 by weight～30; Described lyonium salt acid solutions is 0.0001～1N, and naoh concentration is 0.0001～1N;
Described Herba Ephedrae is a form in small, broken bits, and particle diameter is less than or equal to 5 millimeters;
The ultrasonic frequency of described supersound extraction is 20KHz, and power is 50W～10000W, and the supersound extraction time is 1～120 minute;
2. after the leach liquor that step 1 is obtained filters, transferring pH with sodium hydroxide solution is 8～14, after refiltering, get filtrate and exchange, adsorb through weakly acidic cation-exchange resin post or macroporous resin column, filtrate is 0.5 ml/min～100 ml/min through the flow velocity of resin column exchange, absorption;
3. finish through step 2 exchange, absorption, with the mixed solution of hydrochloric acid or hydrochloric acid and organic solvent as elutriant, (the limit side washing detects with the high performance liquid phase detector to be eluted to terminal point according to a conventional method, just stop to add elutriant in case reach home, the high performance liquid phase detector prints elution curve, as shown in Figure 1), elutriant promptly gets the crystallization of product ephedrine hydrochloride behind conventional concentrating under reduced pressure.
Eluted resins is extremely colourless with the organic solvent flushing, and with multiplexing behind 1～20 bed volume of distilled water flushing.
In above-mentioned steps 3, described concentration of hydrochloric acid is 0.001～1N;
In above-mentioned steps 3, described organic solvent comprises ethanol, methyl alcohol, acetone etc.; The blending ratio of hydrochloric acid and organic solvent is 1: 0.1～10.
Compared with the prior art the present invention has following advantage:
1. ephedrine can be combined into ephedrine hydrochloride with hydrochloric acid, is dissociated into the positively charged ion state in water, and the ephedrine under this state is to be difficult to be held back with the macroporous resin that is adsorbed as main reactive force; On the other hand, macroporous resin is fine to the adsorption effect of free state ephedrine, and ephedrine is also more easily by wash-out simultaneously.
CN1201029A employing hydrochloric acid transfers pH5-8 to make ephedrine form hydrochloride, not by macroporous resin adsorption, therefore sees through resin, and this effluent liquid gets Ephedra sinica fine powder purity behind concentrate drying be 6～10%.Tannin in the extracting solution gets the byproduct tannin with ethanol elution afterwards then by macroporous resin adsorption.
And the present invention transfers pH8-14 to be controlled at free state with NaOH the ephedrine in the Herba Ephedrae extracting solution.Have only the ephedrine under this state to be adsorbed preferably by weakly acidic cation-exchange resin and macroporous resin.Afterwards, adopt the hydrochloric acid wash-out, make the free state ephedrine become ephedrine hydrochloride, not by weakly acidic cation-exchange resin and macroporous resin adsorption, thus desorb from the resin.
In the present invention, before the Herba Ephedrae extracting solution upper prop, the free state Content of Ephedrine With is about 5%, uses the hydrochloric acid wash-out behind the upper prop, and the elutriant drying under reduced pressure obtains purity and be 80% ~ 97% ephedrine hydrochloride crystallization.The salt acidifying of ephedrine and one step of wash-out finish, simply rapidly and efficiently.
2. in CN1201029A, macroporous resin adsorption tannin, make other impurity and ephedrine hydrochloride see through resin together because the decon that do not eliminate, so the Content of Ephedrine With in the gained Ephedra sinica fine powder is lower, content is 6～10%, has improved 1～2 times.
And in the present invention, hydrochloric acid only washes out ephedrine from resin, and most of lipid-soluble substance and other impurity are stayed on the resin, so ephedrine hydrochloride purity is higher, reach more than 90%, with handle before compare and improved 15～19 times.
3. in CN1201029A, how many rate of recovery of not mentioning ephedrine is, and the method that adopts in the present invention is extracted, elution requirement is handled, and the rate of recovery of ephedrine can reach 97%.
4. technology of the present invention is simple, the efficient height, and weak point consuming time, cost is low and environmental pollution is little.
Embodiment
Embodiment 1:
After 25 gram Herba Ephedrae pulverizing, its particle diameter reaches 5 millimeters, adds 100 ml waters and mixes, and mixing solutions is placed in the ultrasonic generator container then, with ultrasonic wave the Herba Ephedrae powder is carried out supersound extraction; Used ultrasonic frequency is 20KHz, and power is the supersound extraction 30 minutes of 50W, removes by filter the dregs of a decoction; It is 9 that filtrate is regulated its pH with 0.5N NaOH, with the D151 weakly acidic cation-exchange resin of filtrate by Chemical Plant of Nankai Univ.'s production, filtrate is 0.5 ml/min through the flow velocity of resin column exchange, absorption: after exchange finishes, carry out wash-out with 0.01N hydrochloric acid, detect with the high performance liquid phase detector in the elution process, be eluted to terminal point and stop to add elutriant (as shown in Figure 1), the elutriant concentrating under reduced pressure is got the ephedrine hydrochloride crystal.
The exhausted resin column is then with can using repeatedly behind 10% alcohol flushing, but the ethanol reclaim under reduced pressure.Adopt this technology that the content 4.9% of the preceding ephedrine of sample is brought up to more than 90%, purity has improved 18.5 times, and the rate of recovery is 96%.This technology is simple, the efficient height, and weak point consuming time, cost is low and environmental pollution is little.
Embodiment 2:
After 25 gram Herba Ephedrae pulverizing, its particle diameter reaches 3 millimeters, adds 100 milliliters of 0.001N hydrochloric acid solns and mixes, and mixing solutions is placed in the ultrasonic generator container then, with ultrasonic wave the Herba Ephedrae powder is carried out supersound extraction; Used ultrasonic be 20KHz with frequency, power is the supersound extraction 30 minutes of 50W, removes by filter the dregs of a decoction; Regulating leach liquor pH with 0.5N NaOH is 14, and filtrate is passed through Rohm ﹠amp; The Amberlite XAD-7 macroporous resin column of Haas company, filtrate is 100 ml/min through the flow velocity of resin column exchange, absorption; After absorption finishes, carry out wash-out, detect with the high performance liquid phase detector in the elution process, be eluted to terminal point and stop to add elutriant (as shown in Figure 1), the elutriant concentrating under reduced pressure is got the ephedrine hydrochloride crystal with 0.01N hydrochloric acid and 2: 1 mixing solutions of ethanol;
The exhausted resin column is then with can using repeatedly behind 10% alcohol flushing, but the ethanol reclaim under reduced pressure.Adopt this technology that the content 5.5% of the preceding ephedrine of sample is brought up to more than 85%, purity has improved 14.8 times, and the rate of recovery is 97%.
Embodiment 3:
After 25 gram Herba Ephedrae pulverizing, its particle diameter reaches 2 millimeters, adds 100 milliliters of 0.005N sodium hydroxide solutions and mixes, and mixing solutions is placed in the ultrasonic generator container then, with ultrasonic wave the Herba Ephedrae powder is carried out supersound extraction; Used frequency is 20KHz, and power is the supersound extraction 30 minutes of 50W, removes by filter the dregs of a decoction; It is 12 that filtrate is regulated leach liquor pH with 0.5N NaOH, again filtrate is passed through Rohm ﹠amp; The Amberlite XAD-7 macroporous resin column of Haas company, filtrate is 70 ml/min through the flow velocity of resin column exchange, absorption; After exchange finishes, mixed in 1: 0.2 by volume with 0.002N hydrochloric acid and acetone and to carry out wash-out, the detection of usefulness high performance liquid phase detector is eluted to terminal point and stops to add elutriant (as shown in Figure 1) in the elution process, and the elutriant concentrating under reduced pressure is got the ephedrine hydrochloride crystal.
The exhausted resin column is then with can using repeatedly behind 10% alcohol flushing, but the ethanol reclaim under reduced pressure.Adopt this technology that the content 4.1% of the preceding ephedrine of sample is brought up to more than 78%, purity has improved 18.9 times, and the rate of recovery is 95%.
Embodiment 4
After 25 gram Herba Ephedrae pulverizing, its particle diameter reaches 4 millimeters, adds 100 milliliters of 0.01N sodium hydroxide solutions and mixes; Mixing solutions is placed in the ultrasonic generator container then, the Herba Ephedrae powder is carried out supersound extraction with ultrasonic wave; Used frequency is 20KHz, and power is the supersound extraction 30 minutes of 50W, removes by filter the dregs of a decoction; Regulating leach liquor pH with 0.5N NaOH is 14, and filtrate is passed through Rohm ﹠amp; The Amberlite XAD-4 macroporous resin column of Haas company, filtrate is 100 ml/min through the flow velocity of resin column exchange, absorption; After exchange finishes, mixed in 1: 2 by volume with 0.002N hydrochloric acid and acetone and to carry out wash-out, the detection of usefulness high performance liquid phase detector is eluted to terminal point and stops to add elutriant (as shown in Figure 1) in the elution process, and the elutriant concentrating under reduced pressure is got the ephedrine hydrochloride crystal.
The exhausted resin column is then with can using repeatedly behind 10% alcohol flushing, but the ethanol reclaim under reduced pressure.Adopt this technology that the content 5.1% of the preceding ephedrine of sample is brought up to more than 88%, purity has improved 17.3 times, and the rate of recovery is 98%.
Claims (8)
1. method with weakly acidic cation-exchange resin and macroporous resin separation and purification ephedrine is characterized in that carrying out according to the following steps:
(1) supersound extraction: the Herba Ephedrae powder is placed in the solvent mixes, this mixing solutions is placed in the ultrasonic generator container, the Herba Ephedrae powder is carried out supersound extraction with ultrasonic wave;
(2) after the leach liquor filtration with supersound extraction, transferring pH with sodium hydroxide solution is 8～14, after refiltering, get filtrate flow and exchange, adsorb through weakly acidic cation-exchange resin post or macroporous resin column, its filtrate flow is 0.5 ml/min～100 ml/min through the resin column flow velocity;
(3) finish through resins exchange, absorption, be washed till terminal point with hydrochloric acid or hydrochloric acid and organic solvent blended elutriant, elutriant behind conventional concentrating under reduced pressure, the ephedrine hydrochloride crystallization, eluted resins is extremely colourless with the organic solvent flushing, and with multiplexing behind 1～20 bed volume of distilled water flushing.
2. by the described method with weakly acidic cation-exchange resin and macroporous resin separation and purification ephedrine of claim 1, it is characterized in that: described Herba Ephedrae powder diameter is less than below 5 millimeters.
3. by the described method with weakly acidic cation-exchange resin and macroporous resin separation and purification ephedrine of claim 1, it is characterized in that: the solvent that uses in the described step 1 comprises: water, hydrochloric acid soln or sodium hydroxide; Wherein solvent mix with Herba Ephedrae count 1: 3 by weight～30.
4. by the described method of claim 1 with weakly acidic cation-exchange resin and macroporous resin separation and purification ephedrine, it is characterized in that: the ultrasonic frequency of described supersound extraction is 20KHz, power is 50W～10000W, and the supersound extraction time is 1～120 minute.
5. by the described method with weakly acidic cation-exchange resin and macroporous resin separation and purification ephedrine of claim 1, it is characterized in that: the hydrochloric acid solvent strength of using in the described step 1 is 0.0001～1N.
6. by the described method with weakly acidic cation-exchange resin and macroporous resin separation and purification ephedrine of claim 1, it is characterized in that: the naoh concentration that uses in the described step 1 is 0.0001～1N.
7. by the described method of claim 1 with weakly acidic cation-exchange resin and macroporous resin separation and purification ephedrine, it is characterized in that: the hydrochloric acid that uses in the described step 3 and the blended elutriant of organic solvent, its mixing is 1: 0.1～10 by volume.
8. by the described method with weakly acidic cation-exchange resin and macroporous resin separation and purification ephedrine of claim 1, it is characterized in that: the organic solvent that described step 3 elutriant is used comprises ethanol, methyl alcohol, acetone.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021044023A CN1186312C (en) | 2002-03-12 | 2002-03-12 | Method for separating and purifying ephedrine by using weak acid cation exchange resin and macroporous resin |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021044023A CN1186312C (en) | 2002-03-12 | 2002-03-12 | Method for separating and purifying ephedrine by using weak acid cation exchange resin and macroporous resin |
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| CN1443749A true CN1443749A (en) | 2003-09-24 |
| CN1186312C CN1186312C (en) | 2005-01-26 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319935C (en) * | 2004-05-26 | 2007-06-06 | 中国科学院过程工程研究所 | Method for one-step purification and separation of ephedrine by cation exchange resin and expanded bed integrated technology |
| CN103800397A (en) * | 2014-02-11 | 2014-05-21 | 浙江中医药大学 | Process for purifying Herba Ephedrae total alkaloids with macroporous resin |
| CN105582042A (en) * | 2015-12-30 | 2016-05-18 | 中国中医科学院中医临床基础医学研究所 | Traditional Chinese medicine composition for treating pollen allergy |
| CN106588677A (en) * | 2016-11-19 | 2017-04-26 | 王丽 | Preparation method of ephedrine hydrochloride |
-
2002
- 2002-03-12 CN CNB021044023A patent/CN1186312C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319935C (en) * | 2004-05-26 | 2007-06-06 | 中国科学院过程工程研究所 | Method for one-step purification and separation of ephedrine by cation exchange resin and expanded bed integrated technology |
| CN103800397A (en) * | 2014-02-11 | 2014-05-21 | 浙江中医药大学 | Process for purifying Herba Ephedrae total alkaloids with macroporous resin |
| CN103800397B (en) * | 2014-02-11 | 2017-06-06 | 浙江中医药大学 | The technique of macroporous resin purification Herba Ephedrae total alkaloids |
| CN105582042A (en) * | 2015-12-30 | 2016-05-18 | 中国中医科学院中医临床基础医学研究所 | Traditional Chinese medicine composition for treating pollen allergy |
| CN106588677A (en) * | 2016-11-19 | 2017-04-26 | 王丽 | Preparation method of ephedrine hydrochloride |
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| CN1186312C (en) | 2005-01-26 |
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