CN100386301C - Convenient method for producing shikimic acid - Google Patents
Convenient method for producing shikimic acid Download PDFInfo
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- CN100386301C CN100386301C CNB2006100108083A CN200610010808A CN100386301C CN 100386301 C CN100386301 C CN 100386301C CN B2006100108083 A CNB2006100108083 A CN B2006100108083A CN 200610010808 A CN200610010808 A CN 200610010808A CN 100386301 C CN100386301 C CN 100386301C
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Abstract
The present invention provides a convenient method for producing shikimic acid. Through technical processes of subcritical liquefied petroleum gas degreasing, alcohol leaching, water leaching, concentration, water dissolving trash extraction or water containing solvent trash extraction, etc., the problems of ponderous technical process, high consumption and multiple kinds of organic solvents, time consumption, cost consumption, poor quality, etc. existing in the graded trash extraction of a plurality of organic solvents in the prior art are fundamentally solved. A large amount of oil-soluble impurities can be eliminated by one step, and the solubility difference between the shikimic acid and other coexistent aqueous solubility impurities in water and relevant solvent is utilized to further eliminate the impurities for crystallization, and consequently, the extraction technical process is largely simplified, the high price organic solvent is omitted, and thereby, the work efficiency is increased, the production cost is reduced and the workmen's labor strength is relieved. Moreover, the shikimic acid has high yield, good quality and high effective component content, and the purity of the shikimic acid can reach more than 60%. The shikimic acid can be produced under the condition with comparatively primitive equipment.
Description
Technical field
The present invention relates to a kind of production method of shikimic acid, especially a kind of method of from plant, extracting shikimic acid.
Background technology
Shikimic acid is that a kind of natural phant that is present in is as the ring-type organic acid in anistree and some gymnosperms.Through studies show that for many years it has thrombus, analgesia and effect such as antitumor.As the intermediate of chemosynthesis, shikimic acid not only is usually used in synthetic analgesia, anticancer and antithrombotic reagent, also is used for synthetic herbicide and antiseptic-germicide.Along with bird flu in recent years global generally popular, natural shikimic acid becomes synthetic anti-highly pathogenic human bird flu medicine---the essential raw material of Tamiflu, and receives much attention, its price soars.China is the major production areas of world's anise, and the anise of the whole world more than 80% originates from China, and the anistree quality in Yunnan is the hat in the whole nation, and numerous manufacturers use the anistree shikimic acid of producing in Yunnan unexpectedly mutually.
The production method of existing shikimic acid mainly is to adopt traditional organic solvent method of purification.Its main processes is: with sherwood oil anistree dry powder is carried out degreasing, raw material slag alcohol reflux, gained medicinal extract dissolve and removal of impurities successively with several organic solvents in succession, use mixed solvent crystallization afterwards again, and then, obtain the shikimic acid elaboration with mixed solvent recrystallization repeatedly.This traditional production technique exists following many masty problems in production practice: the one, and gained medicinal extract viscosity is very big, not only make organic solvent be difficult to penetrate into lotion and unfavorable removal of impurities, and it is big to stir resistance, often cause equipment power dissipation height, wearing and tearing greatly, thereby influence its work-ing life; The 2nd, in leaching process, to use multiple different organic solvent, not only technological process is tediously long, and production cost increases, and brings bigger potential safety hazard, repeatedly uses different mixed solvents, causes the regeneration difficulty of solvent to increase solvent loss rate height; The 3rd, labor strength is big, and production cost improves, and raw material availability is lower, is unfavorable for expanding the scale of production, and the purity of product is difficult to guarantee.Therefore, be necessary fully prior art is improved.
Summary of the invention
For overcoming the complex technical process that prior art exists, solvent consumption is big, and solvent species is many, the cost height, and deficiencies such as inefficiency the invention provides a kind of convenient method for producing shikimic acid.
The present invention finishes by following technical proposal: a kind of convenient method for producing shikimic acid comprises the following steps:
Extraction de-oiling fat: plant material is pressed material: the mass ratio of solvent=1: 1～5, in material, feed subcritical liquefied petroleum gas (LPG), extracted at normal temperatures and pressures 40～90 minutes, under 20～70 ℃ of temperature, 0.1～1Mpa pressure, make the subcritical gasifying liquefied petroleum gas in the extract, isolate grease;
The ethanol lixiviate: the raw material after the degreasing is successively by the amount of 2～3L/kg, 1～2L/kg, 1～2L/kg, and with commercially pure alcohol reflux 3 times, each extraction time was followed successively by 3,2,1 hours, united extraction liquid, reclaim ethanol after, must medicinal extract;
Perhaps
The ethanol lixiviate: successively by the amount of 3～4L/kg, 2～3L/kg, 1～2L/kg, with commercially pure alcohol reflux 3 times, each extraction time was followed successively by 3,2,1 hours with plant material, united extraction liquid, reclaim ethanol after, must medicinal extract;
It is characterized in that through following post-order process step:
A, above-mentioned gained medicinal extract is pressed material: the mass ratio of solvent=1: 3～6, with 60～90 ℃ of hot water stirring and dissolving, filter;
B, above-mentioned filter residue is pressed material: the mass ratio of solvent=1: 1～3, with 70～90 ℃ of hot water stirring and dissolving, filter;
C, the above-mentioned secondary filtrate of merging, leave standstill be cooled to room temperature after, refilter once, filtrate temperature be 70～90 ℃, vacuum pressure be-0.06～-be concentrated into proportion 1.1～1.4 under the 0.07MPa condition, under 80～90 ℃ of temperature dry 8～12 hours, pulverize the methyl alcohol removal of impurities that the back adds 1～3 times moisture 10～50% mass ratioes of quality of material, stirring at room 5～10 minutes, filter, insolubles under 60～90 ℃ of temperature dry 4～6 hours, shikimic acid dry powder;
Perhaps
C, the above-mentioned secondary filtrate of merging, leave standstill be cooled to room temperature after, refilter once, filtrate temperature be 70～90 ℃, vacuum pressure be-0.06～-be concentrated into proportion 1.1～1.4 under the 0.07MPa condition, leave standstill be cooled to room temperature after, press material: the mass ratio of water=1: 1～2, in the solidified enriched material, add the water removal of impurities, stirred 5～30 minutes, left standstill 0.5～2 hour, after removing supernatant liquor, drying is 8～12 hours under 60～90 ℃ of temperature, gets shikimic acid dry powder after crushed.
The removal of impurities solvent of described C step also can be selected aqueous ethanol for use, perhaps aqueous third bronze medal, and water content is 10～50% mass ratioes, add-on is 1～3 times of quality of material.
Described shikimic acid dry powder passes through the crystallization treatment of prior art again, and perhaps the substep recrystallization is handled, and can obtain the shikimic acid elaboration.
The technological difficulties that the present invention solves are: at existing during with the organic solvent extraction shikimic acid, should avoid the interference problem of water, the application's inventors, through test and research many times, look for another way, make full use of shikimic acid characteristic soluble in water, with gained medicinal extract behind the extraction using alcohol, use water extraction being lower than under 100 ℃ of temperature, obtained beyond thought effect.
The present invention compared with prior art has following advantage and effect: adopt such scheme, promptly adopt the water-soluble novel technology for extracting of convenient effective pure cream, it is tediously long fundamentally to have solved the technological process that multiple organic solvent gradation removal of impurities exists in the prior art, the organic solvent usage quantity is big, kind is many, consuming time expending, problem such as quality is not good enough, a step can be removed a large amount of oil-soluble impuritieses, and the water-soluble impurity that utilizes shikimic acid and other coexistences reaches the difference of solubleness in the relevant solvent in water, further removal of impurities crystallization, thus the extraction process process simplified greatly, saved the use of high price organic solvent, improved working efficiency, reduce production cost, alleviated working strength of workers, and the yield height, quality better, the active constituent content height, its purity reaches more than 60%, and can comparatively produce under the simple and crude equipment condition.
Embodiment
Embodiment 1
1, the 300kg Fructus Anisi Stellati dried fruit was crushed to 20 purpose granularities, press material: the mass ratio of solvent=1: 1, subcritical liquefied petroleum gas (LPG) is fed in the material, extracted at normal temperatures and pressures 90 minutes, with extract and subcritical liquefied petroleum gas (LPG) under 70 ℃ of temperature, 0.1Mpa under the pressure, make subcritical gasifying liquefied petroleum gas, isolate 36.1kg Fructus Anisi Stellati oil resin;
2, get anistree slag after the 100kg degreasing, press the amount of 300L, 200L, 200L successively, with the alcohol reflux of technical pure (mass percent is 94%) 3 times, each extraction time was followed successively by 3,2,1 hours, merge No. 3 times extracting solution, after reclaiming ethanol, proportion be 1.1, weight is the medicinal extract of 18.5kg;
3, with above-mentioned 18.5kg medicinal extract, be 90 ℃ hot water stirring and dissolving with the 111L temperature, filter;
4, adding the 56L temperature in above-mentioned filter residue is 90 ℃ hot water stirring and dissolving, filters;
5, merge above-mentioned secondary filtrate, leave standstill be cooled to room temperature after, refilter once, to be 90 ℃, vacuum pressure in temperature be concentrated into proportion 1.1 under-the 0.06MPa to filtrate, under 90 ℃ of temperature dry 8 hours again, get 100 purpose dry powder after crushed, the acetone that adds moisture 50% mass ratio of 2 times of quality of material, stirring at room 5 minutes is filtered, insolubles under 90 ℃ of temperature dry 4 hours, purity is 68% shikimic acid dry powder 6.9kg.Gained shikimic acid dry powder after the crystallization processes of prior art is handled, can be got the high-pure shikimic acid elaboration.
Embodiment 2
1, get 4kg and cross 20 purpose star aniseed powders, the amount of pressing 12L, 10L, 8L successively is with the alcohol reflux of technical pure (mass percent is 94%) 3 times, each extraction time was followed successively by 2,1,1 hours, merge No. 3 times extracting solution, reclaim ethanol after, proportion be 1.1, weight is the medicinal extract of 1.05kg;
3, with above-mentioned 1.05kg medicinal extract, be 60 ℃ hot water stirring and dissolving with the 5L temperature, filter;
4, adding the 3L temperature in above-mentioned filter residue is 70 ℃ hot water stirring and dissolving, filters;
5, merge above-mentioned secondary filtrate, leave standstill be cooled to room temperature after, filter once more, remove the grease on filtrate top layer, to be 70 ℃, vacuum pressure in temperature be concentrated into proportion 1.4 under-the 0.07MPa to filtrate, leave standstill be cooled to room temperature after, in enriched material, add water 500ml, stirred 5 minutes, left standstill 2 hours, after removing supernatant liquor, under 60 ℃ of temperature dry 12 hours, after crushed purity is 75% shikimic acid dry powder 0.26kg.Gained shikimic acid dry powder after the substep recrystallizing technology of prior art is handled, can be got the high-pure shikimic acid elaboration.
Embodiment 3
1, the 100kg Fructus Anisi Stellati dried fruit was crushed to 20 purpose granularities, press material: the mass ratio of solvent=1: 5, subcritical liquefied petroleum gas (LPG) is fed in the material, extracted at normal temperatures and pressures 40 minutes, with extract and subcritical liquefied petroleum gas (LPG) under 20 ℃ of temperature, 1Mpa pressure, make subcritical gasifying liquefied petroleum gas, isolate 14.1kg Fructus Anisi Stellati oil resin;
2, get anistree slag after the 10kg degreasing, press the amount of 20L, 10L, 10L successively, with the alcohol reflux of technical pure (mass percent is 94%) 3 times, each extraction time was followed successively by 3,2,1 hours, merge No. 3 times extracting solution, after reclaiming ethanol, proportion be 1.1, weight is the medicinal extract of 1.8kg;
3, with above-mentioned 1.8kg medicinal extract, be 70 ℃ hot water stirring and dissolving with the 5.4L temperature, filter;
4, adding the 2L temperature in above-mentioned filter residue is 80 ℃ hot water stirring and dissolving, filters;
5, merge above-mentioned secondary filtrate, leave standstill be cooled to room temperature after, refilter once, to be 70 ℃, vacuum pressure in temperature be concentrated into proportion 1.4 under-the 0.06MPa to filtrate, under 80 ℃ of temperature dry 12 hours again, get 100 purpose dry powder after crushed, the methyl alcohol removal of impurities that adds 1 times moisture 10% mass ratio of quality of material, stirring at room 10 minutes is filtered, insolubles under 60 ℃ of temperature dry 6 hours, purity is 70% shikimic acid dry powder 0.76kg.Gained shikimic acid dry powder after the crystallization processes of prior art is handled, can be got the high-pure shikimic acid elaboration.
Embodiment 4
1, get 8kg and cross 20 purpose star aniseed powders, the amount of pressing 32L, 24L, 8L successively is with the alcohol reflux of technical pure (mass percent is 94%) 3 times, each extraction time was followed successively by 2,1,1 hours, merge No. 3 times extracting solution, reclaim ethanol after, proportion be 1.4, weight is the medicinal extract of 2kg;
3, with above-mentioned 2kg medicinal extract, be 80 ℃ hot water stirring and dissolving with the 8L temperature, filter;
4, adding the 2L temperature in above-mentioned filter residue is 90 ℃ hot water stirring and dissolving, filters;
5, merge above-mentioned secondary filtrate, leave standstill be cooled to room temperature after, filter once more, remove the grease on filtrate top layer, to be 90 ℃, vacuum pressure in temperature be concentrated into proportion 1.4 under-the 0.06MPa to filtrate, leave standstill be cooled to room temperature after, in enriched material, add water 2L, stirred 30 minutes, left standstill 0.5 hour, after removing supernatant liquor, under 90 ℃ of temperature dry 8 hours, after crushed purity is 72% shikimic acid dry powder 0.49kg.Gained shikimic acid dry powder after the substep recrystallizing technology of prior art is handled, can be got the high-pure shikimic acid elaboration.
Claims (1)
1. a shikimic acid production method comprises the following steps:
Extraction de-oiling fat: the Fructus Anisi Stellati dried fruit that will be crushed to 20 order granularities is by material: the mass ratio of solvent=1: 1～5, in material, feed subcritical liquefied petroleum gas (LPG), extracted at normal temperatures and pressures 40～90 minutes, under 20～70 ℃ of temperature, 0.1～1Mpa pressure, make the subcritical gasifying liquefied petroleum gas in the extract, isolate grease;
The ethanol lixiviate: the raw material after the degreasing is successively by the amount of 2～3L/kg, 1～2L/kg, 1～2L/kg, and with commercially pure alcohol reflux 3 times, each extraction time was followed successively by 3,2,1 hours, united extraction liquid, reclaim ethanol after, must medicinal extract;
Perhaps
The ethanol lixiviate: successively by the amount of 3～4L/kg, 2～3L/kg, 1～2L/kg, with commercially pure alcohol reflux 3 times, each extraction time was followed successively by 3,2,1 hours with star aniseed powder, united extraction liquid, reclaim ethanol after, must medicinal extract;
It is characterized in that through following post-order process step:
A, above-mentioned gained medicinal extract is pressed material: the mass ratio of solvent=1: 3～6, with 60～90 ℃ of hot water stirring and dissolving, filter;
B, above-mentioned filter residue is pressed material: the mass ratio of solvent=1: 1～3, with 70～90 ℃ of hot water stirring and dissolving, filter;
C, the above-mentioned secondary filtrate of merging, leave standstill be cooled to room temperature after, refilter once, filtrate temperature be 70～90 ℃, vacuum pressure be-0.06～-be concentrated into proportion 1.1～1.4 under the 0.07MPa condition, drying is 8～12 hours under 80～90 ℃ of temperature, pulverize the aqueous methanol that the back adds 1～3 times moisture 10～50% mass ratioes of quality of material, perhaps aqueous ethanol, perhaps aqueous acetone, stirring at room 5～10 minutes, filter, insolubles under 60～90 ℃ of temperature dry 4～6 hours, shikimic acid dry powder;
Perhaps
C, the above-mentioned secondary filtrate of merging, leave standstill be cooled to room temperature after, refilter once, filtrate temperature be 70～90 ℃, vacuum pressure be-0.06～-be concentrated into proportion 1.1～1.4 under the 0.07MPa condition, leave standstill be cooled to room temperature after, press material: the mass ratio of water=1: 1～2, in the solidified enriched material, add the water removal of impurities, stirred 5～30 minutes, left standstill 0.5～2 hour, after removing supernatant liquor, drying is 8～12 hours under 60～90 ℃ of temperature, gets shikimic acid dry powder after crushed.
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| CNB2006100108083A CN100386301C (en) | 2006-04-12 | 2006-04-12 | Convenient method for producing shikimic acid |
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| CN101024609B (en) * | 2007-03-30 | 2010-07-07 | 南京农业大学 | Process for producing shikimic acid |
| CN101168503B (en) * | 2007-09-29 | 2010-10-13 | 陕西嘉禾植物化工有限责任公司 | Method for extracting and separating shikimic acid from star anise |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163104A (en) * | 1997-02-03 | 1997-10-29 | 北京中医药大学 | Medicinal preparation containing shikimic acid and its derivatives, and its use in preparing anti-thrombosis and analgesic medicine |
| CN1235151A (en) * | 1998-05-13 | 1999-11-17 | 弗·哈夫曼-拉罗切有限公司 | Process for preparation of shikimic acid and its derivatives |
| JP2000351750A (en) * | 1999-06-09 | 2000-12-19 | Toray Ind Inc | Purification or shikimic acid and shikimic acid derivative |
| WO2002006203A1 (en) * | 2000-07-14 | 2002-01-24 | Dsm N.V. | Process for the recovery of shikimic acid |
| JP2002080421A (en) * | 2000-09-05 | 2002-03-19 | Toray Ind Inc | Method for producing highly pure shikimic acid |
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- 2006-04-12 CN CNB2006100108083A patent/CN100386301C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163104A (en) * | 1997-02-03 | 1997-10-29 | 北京中医药大学 | Medicinal preparation containing shikimic acid and its derivatives, and its use in preparing anti-thrombosis and analgesic medicine |
| CN1235151A (en) * | 1998-05-13 | 1999-11-17 | 弗·哈夫曼-拉罗切有限公司 | Process for preparation of shikimic acid and its derivatives |
| JP2000351750A (en) * | 1999-06-09 | 2000-12-19 | Toray Ind Inc | Purification or shikimic acid and shikimic acid derivative |
| WO2002006203A1 (en) * | 2000-07-14 | 2002-01-24 | Dsm N.V. | Process for the recovery of shikimic acid |
| JP2002080421A (en) * | 2000-09-05 | 2002-03-19 | Toray Ind Inc | Method for producing highly pure shikimic acid |
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Assignee: Yunnan Fulanti Biological Engineering Co.,Ltd. Assignor: Liu Runmin|Gao Yun|Shen Chen| Liu Yichen|Gao Yu Contract record no.: 2011530000023 Denomination of invention: Convenient method for producing shikimic acid Granted publication date: 20080507 License type: Exclusive License Open date: 20060913 Record date: 20110601 |
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