CN102219790B - Green extraction process for artemisinin - Google Patents
Green extraction process for artemisinin Download PDFInfo
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Abstract
The invention discloses a green extraction process for artemisinin, and relates to the field of drug production. The process comprises the following steps: (1) drying of raw materials, that is, putting the raw materials into drying equipment for drying; (2) primary processing of artemisinin, that is, putting the dried raw materials into an extraction tank, adding petroleum ether, heating the extraction tank, carrying out countercurrent extraction, allowing the extract to flow out from the extraction tank, standing the extract to obtain a supernatant, allowing the supernatant to pass through a silica gel column, eluting the silica gel column with petroleum ether, collecting artemisinin fractions, putting the artemisinin fractions into a concentrating tank for concentration until crystals are precipitated, putting the obtained concentrate into a crystallizing tank for crystallization, carrying out filtering to obtain crystals, and drying the crystals so as to obtain crude products of artemisinin; (3) refining of artemisinin, that is, dissolving the crude products of artemisinin in an alcohol precipitating tank with ethanol, wherein the ethanol with a concentration of 93 to 95% is 65 to 75 times the amount of the crude products, standing the solution, taking the supernatant of the solution for secondary filter, concentrating the filtrate in the concentrating tank, standing the concentrate for crystallization, carrying out filtering to obtain crystals, and drying the crystals under vacuum so as to obtain refined products of artemisinin.
Description
Technical field
The present invention relates to the extraction process in drug manufacture field, particularly a kind of Artemisinin.
Background technology
Artemisinin (artemisin) is the artemisinin-based drug that extracts from medicinal plant Herba Artemisiae annuae (artemisia annua L.), for containing the sesquiterpene lactones compound of peroxidation group, being the unique Chinese herbal medicine extract by the Western medicine development that obtains international endorsement of China, is the anti-malarial bulk drug that the World Health Organization's clear replaces quinine.The Artemisinin volume of production and marketing of China accounts for more than 90% of global volume of production and marketing, and the extractive technique of China is also just representing world standard.
The technique of extracting Artemisinin in the present domestic Herba Artemisiae annuae mainly is traditional organic solvent extraction separation, namely adopt organic solvent such as ethanol, acetone, gasoline etc. to Herba Artemisiae annuae extract obtain extracting solution medicinal extract after, obtain the Artemisinin sterling through macroporous resin or silicagel column fractional crystallization again, this technical matters is simply ripe, and domestic most Artemisinin manufacturing enterprise all continues to use the extracting method of this classics.Its main shortcoming is that extraction time is long, and extraction yield is low, and solvent, energy consumption are large, and environmental pollution is large etc.Because the large production application of this method starts from 2004, so far less than ten years, thereby improved space is very large.
Supercritical carbon dioxide extraction method also claims green extraction method, and this method is widely used for the extraction of spices, has that environment is good, operational safety, does not have that pest is residual, product quality is high and can keep the characteristics such as intrinsic smell.After entering the nineties, supercritical carbon dioxide extraction method begins to apply to extract effective medicinal components etc. from medicinal plant, also there is research in China at the supercritical fluid extraction of Artemisinin according to reports, but therefore method exists equipment investment large eventually, throughput is low, running cost is high, the shortcoming that does not have the market competitiveness does not still have an enterprise to carry out large-scale industrial production at home and abroad so far.
Summary of the invention
Purpose of the present invention provides a kind of energy-conservation, consumption reduction, cleaning, significantly reduces the low Green extraction process for artemisinin that is fit to large-scale commercial production of waste discharge, cost.
The technical solution used in the present invention is to achieve the above object of the invention: a kind of Green extraction process for artemisinin, this extraction process may further comprise the steps: (1) raw material drying is processed: the sweet wormwood raw material is put into carried out drying treatment in the microwave energy saving drying plant, the temperature setting of microwave energy saving drying plant is set to 45-65 ℃ in the drying process, the drying treatment time is 25-35 minute, when reducing to 5-7% to the sweet wormwood raw material moisture, take out the pack of sweet wormwood raw material, warehouse-in is preserved;
(2) the first system of Artemisinin: the sweet wormwood raw material after the drying treatment in the step (1) is put in the extractor, close the dog-house of extractor, the fuel charging valve of opening extractor adds sherwood oil in extractor, the heating countercurrent extraction, temperature is controlled in the 55-75 ℃ of scope, after countercurrent extraction liquid emitted extractor, extracting solution is left standstill, getting supernatant liquor after the assorted precipitation in countercurrent extraction liquid makes it pass through silicagel column, use again sherwood oil eluting silica gel post after silicagel column is saturated, containing Artemisinin stream part and putting it in the concentration tank concentrated of coming out taken off in collection from silicagel column, when having crystal to separate out to the concentration tank, concentrated solution was put to the crystallizer crystallization 15-20 hour, crystallizer forces cooling to keep Tc to be controlled at 20 ℃-30 ℃ with water coolant during crystallization, obtain crystal after after crystallization is finished the mother liquor in the concentration tank being filtered, crystal is drying to obtain the Artemisinin crude product;
(3) Artemisinin is refining: leave standstill after placing Alcohol-settling tank with 60-75 times of 93-95% dissolve with ethanol the Artemisinin crude product that obtains in the step (2), get the supernatant liquor secondary filter, after filtrate is placed on the 1/3-3/4 that is concentrated into original volume in the concentration tank, concentrated solution is put in the crystallizer, left standstill spontaneous nucleation 15-20 hour at normal temperatures, obtain crystal after after crystallization is finished the mother liquor suction filtration being fallen, crystal obtains the Artemisinin elaboration after vacuum drying treatment.
After the mother liquor that wherein suction filtration goes out from step (3) is concentrated into the 1/3-3/4 of its volume again, left standstill again spontaneous nucleation 15-20 hour at normal temperatures, same method is processed mother liquor three to four times, the gained crystal is the Artemisinin crude product, and the Artemisinin crude product is processed by step (3) and obtained the Artemisinin elaboration.
When wherein getting supernatant liquor by silicagel column in step (2), flow out stream part of silicagel column, part free from foreign meter is directly returned again usefulness of solvent stock, and impure part is by behind the concentration and recovery sherwood oil, and the gained concentrated solution is the material A that contains Herba Artemisiae Annuae oil and sweet wormwood wax; Also collect the part impure, that do not contain the Artemisinin composition that flows out in the eluting silica gel post process and flow part from silicagel column, behind the concentration and recovery sherwood oil, the gained concentrated solution is the material B that contains Herba Artemisiae Annuae oil and sweet wormwood wax.
Wherein also comprise afterwards step (4) recovery and reuse of waste in step (3): the mother liquor that step (2) is leached and gained contain Herba Artemisiae Annuae oil and sweet wormwood wax material A and material B and collect and place extractor to be heated to 60-75 ℃, by reclaiming the sherwood oil of gasification with the tank connected device of extraction, the residue mother liquor passes through steam distillation again, by reclaiming the Herba Artemisiae Annuae oil that gasifies with extracting tank connected device, remaining material sweet wormwood wax in the extractor is also collected in cooling.
Wherein the heating countercurrent extraction need be carried out 3 times in step (2), and extraction time is 2-3 hour for the first time, and extraction time is 1-2 hour for the second time, and extraction time is 0.5-1 hour for the third time.
After wherein in step (2), countercurrent extraction liquid and solvent oil being emitted extractor, also include following technique: close oil drain valve, the steaming valve that rushes of opening extractor rushes steaming to the sweet wormwood slag, and the sherwood oil in the sweet wormwood slag is discharged the sweet wormwood slag outside the extractor after volatilizing reclaim fully.
The sherwood oil that wherein is used for the eluting silica gel post in step (2) contains the 3%-8% ethyl acetate.
After wherein in step (2), using sherwood oil eluting silica gel post, also comprise the technique of cleaning silicagel column with the hot water that reclaims.
Adopt Green extraction process for artemisinin of the present invention to have following beneficial effect:
1, can effectively reduce production costs, increase economic efficiency
Usually one month only sweet wormwood raw material collection period, reach 10 months and add the duration, press the raw material (water content 14%) of state-promulgated pharmacopoeia standard purchase under field conditions (factors) above 90 days, artemislnin content can progressively descend in the raw material, prove through for many years investigation record analysis, the major cause that causes artemislnin content to descend is moisture content and temperature, wherein moisture content accounts for about 70%, temperature accounts for about 30%, the content of Artemisinin on average descends 20% in the raw material that (is generally then June August to next year) within a production cycle, and Green extraction process for artemisinin of the present invention is provided with the step that raw material drying is processed, with free of contamination raw material drying treatment process the raw material water content is dropped to below 7%, delay the decline of raw material artemislnin content in the stock, simultaneously, because extracting solvent is water-fast sherwood oil, sweet wormwood raw material water content descends, can improve sherwood oil and enter deal in the sweet wormwood raw material, so that more Artemisinin is dissolved in the sherwood oil in the sweet wormwood raw material, as when supposing that sweet wormwood raw material moisture content per ton is 14%, just there is the Artemisinin in the 140 ㎏ sweet wormwood raw materials not extract in 1 ton of sweet wormwood raw material, when sweet wormwood raw material moisture content is 7%, just only have the Artemisinin in the 70 ㎏ sweet wormwood raw materials not extract in 1 ton of sweet wormwood raw material, sweet wormwood raw material per ton just can improve the utilization ratio of 70 ㎏ raw materials, put average artemislnin content 7 ‰ calculating in storage with the sweet wormwood material recall, 1 ton of sweet wormwood raw material of traditional extraction technique can extract Artemisinin 4.2 ㎏, adopt in theory 1 ton of sweet wormwood raw material of green extraction process of the present invention can extract Artemisinin 5.33 ㎏, extraction yield is significantly improved, and can effectively reduce production costs, increase economic efficiency.In addition, the sherwood oil in the remaining sweet wormwood slag is reclaimed and step (4) recovery and reuse of waste reclaims sherwood oil, Herba Artemisiae Annuae oil from waste mother liquor, sweet wormwood is cured also can the Effective Raise economic benefit fully after countercurrent extraction.Compare Green extraction process for artemisinin of the present invention with traditional production technique through statistical study and can make production cost can descend 1/3rd, Energy Intensity Reduction 2/3rds, the discharging of the three wastes reduces more than 3/4ths, has the economic results in society of aobvious chopsticks.
2, solve Artemisinin decomposes and affect the problem of yield in leaching process
Artemisinin is heat-sensitive substance, and not only the Artemisinin in the sweet wormwood raw material can decomposes under hot summer days hot conditionss, in leaching process warm-up time grown Artemisinin also can decomposes and affect yield.The present invention affects the problem of yield by shortening extraction time and control temperature technology solution Artemisinin decomposes in leaching process: adopt the countercurrent extraction technology to shorten batch (1000 ㎏) 2 hours extraction times, next selects the good low-boiling extraction solvent of quality, and then control is extracted temperature and delayed Artemisinin decomposes speed and make to greatest extent the Artemisinin yield not be subjected to too much influence.
3, energy-conservation, consumption reduction, cleaning, significantly reduce waste discharge
Solvent consumption index in the traditional mode of production Artemisinin technique is consume petroleum ether 36kg, acetone 2kg of one kilogram of Artemisinin of every production, wherein sherwood oil is taken away by residue in leaching process and tail gas volatilization consumes, and acetone then is to take away with silica gel in the impurity process in the eluting silica gel post.Green extraction process for artemisinin of the present invention adopts the countercurrent extraction technology, reduced the consumption of sherwood oil, recovery part sherwood oil in step (4) recovery and reuse of waste, sherwood oil after countercurrent extraction in the remaining sweet wormwood slag is also reclaimed fully, therefore the consumption of sherwood oil significantly reduces, the present invention uses the impurity in the hot water replacement acetone eluting silica gel that reclaims behind sherwood oil eluting silica gel post in addition, no longer consume acetone, really accomplish energy-conservation, consumption reduction, cleaner production, also can significantly reduce waste discharge.
Below in conjunction with embodiment Green extraction process for artemisinin of the present invention is further described.
Embodiment
Embodiment one:
Green extraction process for artemisinin of the present invention, this extraction process may further comprise the steps:
(1) raw material drying is processed: (the sweet wormwood raw material is firsthand medicinal plant Herba Artemisiae annuae with the sweet wormwood raw material, water content is 14%) put into and carry out drying treatment in the microwave energy saving drying plant, the temperature setting of microwave energy saving drying plant is set to 45 ℃ in the drying process, the drying treatment time is 30 minutes, when reducing to 7% to the sweet wormwood raw material moisture, take out the pack of sweet wormwood raw material, warehouse-in is preserved;
(2) the first system of Artemisinin: the sweet wormwood raw material l000kg after the drying treatment in the step (1) is put in the extractor, close the dog-house of extractor, the fuel charging valve of opening extractor adds sherwood oil in extractor, the heating countercurrent extraction, temperature is controlled to be 60 ℃, in the present embodiment, the heating countercurrent extraction need be carried out 3 times, extraction time is 2 hours for the first time, extraction time is 1.5 hours for the second time, extraction time is 0.5 hour for the third time, after after countercurrent extraction is finished countercurrent extraction liquid and solvent oil being emitted extractor, countercurrent extraction liquid is left standstill, after countercurrent extraction liquid and solvent oil are emitted extractor, close simultaneously oil drain valve, the steaming valve that rushes of opening extractor rushes steaming to the sweet wormwood slag, after sherwood oil in the sweet wormwood slag volatilizees reclaim fully, the sweet wormwood slag is discharged outside the extractor, treat that (impurity is mainly wax for impurity in the countercurrent extraction liquid, moisture etc.) getting supernatant liquor after the precipitation makes it pass through silicagel column, flow out stream part of silicagel column, part free from foreign meter is directly returned again usefulness of solvent stock, and impure part is by behind the concentration and recovery sherwood oil, the gained concentrated solution is the material A that contains Herba Artemisiae Annuae oil and sweet wormwood wax, and material A stays subsequent handling for subsequent use; Use again sherwood oil eluting silica gel post after silicagel column is saturated, the sherwood oil that is used in the present embodiment the eluting silica gel post contains 5% ethyl acetate, collection is taken off the Artemisinin that contains that comes out and is flowed part from silicagel column, be put in the concentration tank Artemisinin stream part that contains of collecting concentrated, when having crystal to separate out to the concentration tank, again concentrated solution was put to the crystallizer crystallization 15 hours, crystallizer forces cooling to keep Tc to be controlled at 25 ℃ with water coolant during crystallization, obtain crystal after after crystallization is finished the mother liquor suction filtration in the concentration tank being fallen, crystal is drying to obtain the Artemisinin crude product; Also collect the part impure, that do not contain the Artemisinin composition that from silicagel column, flows out in the eluting silica gel post process and flow part, behind the concentration and recovery sherwood oil, the gained concentrated solution is the material B that contains Herba Artemisiae Annuae oil and sweet wormwood wax, material B stays subsequent handling for subsequent use, above-mentioned with behind the sherwood oil eluting silica gel post, also comprise the technique of cleaning silicagel column with the hot water that reclaims, water cleans silicagel column has partial impurities not clean up, and the impurity that does not wash clean with silica gel activating the time can be burnt fully;
(3) Artemisinin is refining: leave standstill after placing Alcohol-settling tank with 60 times of 95% dissolve with ethanol the Artemisinin crude product that obtains in the step (2), get the supernatant liquor secondary filter, filtrate be placed on be concentrated in the concentration tank original volume 1/3 after, left standstill at normal temperatures spontaneous nucleation 15 hours, obtain crystal after after crystallization is finished mother liquor being filtered, crystal obtains Artemisinin elaboration 5.33kg after vacuum drying treatment, (adopt European Pharmacopoeia HPLC method to detect) after testing, artemislnin content is 99.5% in the Artemisinin elaboration, related substances and clarity are qualified, and the Artemisinin extraction yield is 85%; The mother liquor that suction filtration goes out again be concentrated into its volume 1/3 after, left standstill again at normal temperatures spontaneous nucleation 15 hours, same method is processed mother liquor three to four times, and the gained crystal is the Artemisinin crude product, and the Artemisinin crude product again extracting method processing of the middle Artemisinin elaboration of repeating step (3) obtains the Artemisinin elaboration;
(4) recovery and reuse of waste: the mother liquor that step (2) is leached and contain Herba Artemisiae Annuae oil and the material A of sweet wormwood wax and material B collect and place extractor to be heated to 75 ℃, by reclaiming the sherwood oil of gasification with the tank connected device of extraction, can obtain pure sherwood oil 20kg free from foreign meter, residue mother liquor (containing Herba Artemisiae Annuae oil and sweet wormwood wax) passes through steam distillation again, by reclaiming the Herba Artemisiae Annuae oil of gasification with the tank connected device of extraction, obtain Herba Artemisiae Annuae oil 1.5kg, cooling is also collected remaining material sweet wormwood wax in the extractor, obtain sweet wormwood wax 9kg, the sweet wormwood slag that produces in the step (2) can utilize in process of production and be used for making fuel for coal after the boiler exhaust gas drying, dried sweet wormwood slag per ton can replace 0.317 ton in raw coal after measured, can substantially satisfy the heat energy needs of one ton of sweet wormwood raw material of processing, the later residual ash of sweet wormwood slag burning can be made farm manure and use.
Through statistical study, calculate the traditional extraction technique sweet wormwood raw material per ton output value=4.2kg * 2800 yuan=11760 yuan with average price in 2010.Adopt green extraction process of the present invention, dry technology makes raw material per ton have a net increase of on year-on-year basis 3084 yuan behind its Raw; The technique integrated innovation makes raw material per ton have a net increase of on year-on-year basis 255.12 yuan; Comprehensive utilization waste mother liquor and waste residue make raw material per ton have a net increase of on year-on-year basis 484 yuan, and three add up to 3793.12 yuan.Be equivalent to increase economic efficiency 32.25% the traditional extraction technique raw material output value=4.2kg per ton * 2800 yuan=11760 yuan.Add thus the production capacity that increases and the labour cost of reduction, total production cost can descend more than one of three parts.
Above-mentioned data are to calculate according to following method:
(1) dry technology delays the benefit that the content decrease of sweet wormwood material inventory produces behind the raw material
Calculate with material recall warehouse-in average content 7 ‰, water content is that the Artemisinin theoretical content of 1 ton of raw material of 14% is 7 ㎏, and raw material per ton can be received Artemisinin=7 ㎏ * 80%(stock content decrease 20% before processing) * recovery rate 75%=4.2 ㎏;
Raw material water content per ton drops to 7% from 14% after processing, be equivalent to be left 930kg after raw material per ton is deducted 70kg moisture content, but content is constant, still contains Artemisinin 7kg in the 930kg raw material: the artemislnin content after in other words processing in the raw material per ton becomes 7 ㎏ ÷ 930kg=7.53 ‰ from 7 ‰.Theoretical content=7.53 ㎏ * 93%(stock content decrease 7%) remains 7 ㎏; (in order to strengthen the convenience of comparability and cost keeping, remaining 930kg was considered as 1 ton after we still deducted moisture content to 1 ton of raw material);
In order to strengthen comparability, in the situation that traditional technology recovery rate 75% is constant, 1 ton of raw material is through receiving Artemisinin=7kg * 93%(stock content decrease 7% after the drying treatment later) * recovery rate 75%=4.88 ㎏; But novel process has reduced the repulsion of water to oil after because of raw material drying, replace refluxing extraction with countercurrent extraction again, make extraction more abundant more complete, so actual recovery rate is more than 85%, can receive Artemisinin=7kg * 93%(stock content decrease 7%) * recovery rate 85%=5.33 ㎏, increase 1.13 ㎏ than before processing, increase income 3164 yuan by 2800 yuan of Artemisinin contract price per kilograms in 2010,80 yuan of deduction drying costs have a net increase of 3084 yuan;
(2) benefit that produces by the series of processes integrated innovation: by being reduced to 20kg for one kilogram of Artemisinin of the every production of ketone technology ether that consumes petroleum from 36kg with advanced time Wen equipment with water, save sherwood oil 16 ㎏, save acetone 2 ㎏, be equivalent to raw material ratio traditional technology per ton and save sherwood oil=16 ㎏ * (5.33 ㎏-4.2 ㎏) * 9 Yuan/㎏=162 .72 unit, saving acetone=2 ㎏ * 4.2 ㎏ * 11 Yuan/㎏=92.40 yuan, two add up to 255.12 yuan;
(3) economic benefit that produces of comprehensive utilization waste mother liquor and waste residue: the recyclable 1.5kg Herba Artemisiae Annuae oil of mother liquor that sweet wormwood raw material per ton produces, the approximately cured and 20kg sherwood oil of 9kg sweet wormwood; By the like product reference price: 1.5kg Herba Artemisiae Annuae oil * 150 yuan=225 yuan, the 9kg sweet wormwood is cured * 3 yuan=27 yuan, 20kg sherwood oil * 9 yuan=180 yuan; Reduce 240 yuan of cost recovery, rise in value 270 yuan; Utilize the dry sweet wormwood dregs of a decoction of boiler exhaust gas then for the coal technology, dried sweet wormwood slag per ton can replace 0.44 ton in raw coal after measured, can substantially satisfy the heat energy needs of producing one ton of sweet wormwood raw material; By former coal price 800 yuan per ton, dried sweet wormwood slag per ton is worth 352 yuan, 60 yuan of deduction drying costs, and joint 292 yuan, two add up to 484 yuan.
Therefore, adopt green extraction process of the present invention can effectively reduce production costs, increase economic efficiency.
Below table one be that one public jin of Celadon artemisin of the every production of statistical analysis adopts friendly process of the present invention with the traditional technology unit consumption of energy and rolls over the standard coal parameter, calculate with material recall warehouse-in Ping Jun Celadon artemisin content 7 ‰, traditional processing technology raw material per ton is received Artemisinin 4.2 ㎏; Green extraction process raw material per ton is received Artemisinin 5.33 ㎏.
Table one:
| The energy consumption project | Friendly process | The folding standard coal | Traditional technology | The folding standard coal | The signature coefficient |
| Unit power consumption | 34.52 Kwh | 13.95㎏ | 43.81 Kwh | 17.70㎏ | 0.404 |
| Unit water consumption | 2.25 M 3 | 0.58㎏ | 2.86 M 3 | 0.74㎏ | 0.257 |
| The unit coal consumption | 31.52㎏ | 23.21㎏ | 144.76㎏ | 103.36㎏ | 0.714 |
| The sherwood oil consumption | 20.00㎏ | 28.80㎏ | 36.00㎏ | 51.84㎏ | 1.44 |
| Folding standard coal summation | ? | 66.54㎏ | ? | 173.64㎏ | ? |
As seen from the above table: every production one public jin Celadon artemisin, green extraction process reduces energy consumption folding standard coal 107.10 ㎏ than traditional processing technology, and Energy Intensity Reduction is more than 2/3rds.
Significantly environmental contamination reduction-than former technique reduces by 3/4ths environmental pollution: the every production one Gong Jin Celadon artemisin of green extraction process consumes raw coal 31.52 ㎏ (being used for silica gel activating), press one ton of standard coal of the every burning of Industrial Boiler and produce carbonic acid gas 2620 ㎏, sulfurous gas 8.5 ㎏, oxynitride 7.4 ㎏. nest calculate, produce carbonic acid gas 82.58 ㎏, sulfurous gas 0.27 ㎏, oxynitride 0.23 ㎏., add up to 83.08 ㎏, add and take away sherwood oil 20 ㎏ that burn totally 103.08 ㎏ in the residue; And the every production one Gong Jin Celadon artemisin of traditional processing technology consumes raw coal 144.76 ㎏, and the waste of generation is that 4.59 times of green extraction process reach 473.14 ㎏, adds sherwood oil 36 ㎏ that take away in the residue totally 509.14 ㎏.That is to say that green extraction process only is 20.25% of traditional processing technology environmental, namely reduces 3/4ths near 4/5ths environmental pollution.Therefore, adopt green extraction process of the present invention can really accomplish energy-conservation, consumption reduction, cleaner production, significantly reduce waste discharge.
Embodiment two:
The present embodiment technical process is identical with embodiment one, and only the part processing parameter is different, Green extraction process for artemisinin of the present invention, and this extraction process may further comprise the steps:
(1) raw material drying is processed: the sweet wormwood raw material is put into carried out drying treatment in the microwave energy saving drying plant, the temperature setting of microwave energy saving drying plant is set to 60 ℃ in the drying process, the drying treatment time is 35 minutes, when reducing to 6% to the sweet wormwood raw material moisture, take out the pack of sweet wormwood raw material, warehouse-in is preserved;
(2) the first system of Artemisinin: the sweet wormwood raw material l000kg in (1) after the drying treatment puts in the extractor, close the dog-house of extractor, the fuel charging valve of opening extractor adds sherwood oil in extractor, the heating countercurrent extraction, temperature is controlled to be 60 ℃, in the present embodiment, the heating countercurrent extraction need be carried out 3 times, extraction time is 2.5 hours for the first time, extraction time is 1 hour for the second time, extraction time is 0.8 hour for the third time, after after countercurrent extraction is finished countercurrent extraction liquid and solvent oil being emitted extractor, countercurrent extraction liquid is left standstill, after countercurrent extraction liquid and solvent oil are emitted extractor, close simultaneously oil drain valve, the steaming valve that rushes of opening extractor rushes steaming to the sweet wormwood slag, after sherwood oil in the sweet wormwood slag volatilizees reclaim fully, the sweet wormwood slag is discharged outside the extractor, treat that (impurity is mainly wax for impurity in the countercurrent extraction liquid, moisture etc.) getting supernatant liquor after the precipitation makes it pass through silicagel column, flow out stream part of silicagel column, part free from foreign meter is directly returned again usefulness of solvent stock, and impure part is by behind the concentration and recovery sherwood oil, the gained concentrated solution is the material A that contains Herba Artemisiae Annuae oil and sweet wormwood wax, and material A stays subsequent handling for subsequent use; Use again sherwood oil eluting silica gel post after silicagel column is saturated, the sherwood oil that is used in the present embodiment the eluting silica gel post contains 8% ethyl acetate, collection is taken off the Artemisinin that contains that comes out and is flowed part from silicagel column, be put in the concentration tank Artemisinin stream part that contains of collecting concentrated, when having crystal to separate out to the concentration tank, again concentrated solution was put to the crystallizer crystallization 18 hours, crystallizer forces cooling to keep Tc to be controlled at 20 ℃ with water coolant during crystallization, obtain crystal after after crystallization is finished the mother liquor suction filtration in the concentration tank being fallen, crystal is drying to obtain the Artemisinin crude product; Also collect the part impure, that do not contain the Artemisinin composition that flows out in the eluting silica gel post process and flow part from silicagel column, behind the concentration and recovery sherwood oil, the gained concentrated solution is the material B that contains Herba Artemisiae Annuae oil and sweet wormwood wax, and material B stays subsequent handling for subsequent use; Above-mentioned with behind the sherwood oil eluting silica gel post, comprise that also water cleans silicagel column has partial impurities not clean up with the technique of the hot water cleaning silicagel column that reclaims, the impurity that does not wash clean with silica gel activating the time can be burnt fully;
(3) Artemisinin is refining: leave standstill after placing Alcohol-settling tank with 66 times of 93% dissolve with ethanol the Artemisinin crude product that obtains in the step (2), get the supernatant liquor secondary filter, filtrate be placed on be concentrated in the concentration tank original volume 3/4 after, left standstill at normal temperatures spontaneous nucleation 18 hours, obtain crystal after after crystallization is finished mother liquor being filtered, crystal obtains Artemisinin elaboration 5.35kg after vacuum drying treatment, (adopt European Pharmacopoeia HPLC method to detect) after testing, artemislnin content is 99.6% in the Artemisinin elaboration, related substances and clarity are qualified, and the Artemisinin extraction yield is 86.5%; The mother liquor that suction filtration goes out again be concentrated into its volume 3/4 after, left standstill again at normal temperatures spontaneous nucleation 18 hours, same method is processed mother liquor three to four times, and the gained crystal is the Artemisinin crude product, and the Artemisinin crude product again extracting method processing of the middle Artemisinin elaboration of repeating step (3) obtains the Artemisinin elaboration;
(4) recovery and reuse of waste: the mother liquor that step (2) is leached and contain Herba Artemisiae Annuae oil and the material A of sweet wormwood wax and material B collect and place extractor to be heated to 75 ℃, by reclaiming the sherwood oil of gasification with the tank connected device of extraction, can obtain pure sherwood oil 22kg free from foreign meter, residue mother liquor (containing Herba Artemisiae Annuae oil and sweet wormwood wax) passes through steam distillation again, by reclaiming the Herba Artemisiae Annuae oil of gasification with the tank connected device of extraction, obtain Herba Artemisiae Annuae oil 1.8 kg, cooling is also collected remaining material sweet wormwood wax in the extractor, obtains sweet wormwood wax 8kg.
The present embodiment also can reach embodiment one described technique effect, at this repeated description no longer.
Embodiment three:
The present embodiment technical process is identical with embodiment one, and only the part processing parameter is different, Green extraction process for artemisinin of the present invention, and this extraction process may further comprise the steps:
(1) raw material drying is processed: the sweet wormwood raw material is put into carried out drying treatment in the microwave energy saving drying plant, the temperature setting of microwave energy saving drying plant is set to 65 ℃ in the drying process, the drying treatment time is 25 minutes, when reducing to 5% to the sweet wormwood raw material moisture, take out the pack of sweet wormwood raw material, warehouse-in is preserved;
(2) the first system of Artemisinin: the sweet wormwood raw material l000kg in (1) after the drying treatment puts in the extractor, close the dog-house of extractor, the fuel charging valve of opening extractor adds sherwood oil in extractor, the heating countercurrent extraction, temperature is controlled to be 60 ℃, in the present embodiment, the heating countercurrent extraction need be carried out 3 times, extraction time is 2 hours for the first time, extraction time is 1.5 hours for the second time, extraction time is 0.5 hour for the third time, after after countercurrent extraction is finished countercurrent extraction liquid and solvent oil being emitted extractor, countercurrent extraction liquid is left standstill, after countercurrent extraction liquid and solvent oil are emitted extractor, close simultaneously oil drain valve, the steaming valve that rushes of opening extractor rushes steaming to the sweet wormwood slag, after sherwood oil in the sweet wormwood slag volatilizees reclaim fully, the sweet wormwood slag is discharged outside the extractor, treat that the impurity in the countercurrent extraction liquid (is mainly wax, moisture etc.) getting supernatant liquor after the precipitation makes it pass through silicagel column, flow out stream part of silicagel column, part free from foreign meter is directly returned again usefulness of solvent stock, and impure part is by behind the concentration and recovery sherwood oil, the gained concentrated solution is the material A that contains Herba Artemisiae Annuae oil and sweet wormwood wax, and material A stays subsequent handling for subsequent use; Use again sherwood oil eluting silica gel post after silicagel column is saturated, the sherwood oil that is used in the present embodiment the eluting silica gel post contains 4% ethyl acetate, collection is taken off the Artemisinin that contains that comes out and is flowed part from silicagel column, be put in the concentration tank Artemisinin stream part that contains of collecting concentrated, when having crystal to separate out to the concentration tank, again concentrated solution was put to the crystallizer crystallization 20 hours, crystallizer forces cooling to keep Tc to be controlled at 30 ℃ with water coolant during crystallization, obtain crystal after after crystallization is finished the mother liquor suction filtration in the concentration tank being fallen, crystal is drying to obtain the Artemisinin crude product; Also collect the part impure, that do not contain the Artemisinin composition that flows out in the eluting silica gel post process and flow part from silicagel column, behind the concentration and recovery sherwood oil, the gained concentrated solution is the material B that contains Herba Artemisiae Annuae oil and sweet wormwood wax, and material B stays subsequent handling for subsequent use; Above-mentioned with behind the sherwood oil eluting silica gel post, comprise that also water cleans silicagel column has partial impurities not clean up with the technique of the hot water cleaning silicagel column that reclaims, the impurity that does not wash clean with silica gel activating the time can be burnt fully;
(3) Artemisinin is refining: leave standstill after placing Alcohol-settling tank with 75 times of 94% dissolve with ethanol the Artemisinin crude product that obtains in the step (2), get the supernatant liquor secondary filter, filtrate be placed on be concentrated in the concentration tank original volume 1/3 after, left standstill at normal temperatures spontaneous nucleation 20 hours, obtain crystal after after crystallization is finished mother liquor being filtered, crystal obtains Artemisinin elaboration 5.45kg after vacuum drying treatment, (adopt European Pharmacopoeia HPLC method to detect) after testing, artemislnin content is 99.6% in the Artemisinin elaboration, related substances and clarity are qualified, and the Artemisinin extraction yield is 88%; The mother liquor that suction filtration goes out again be concentrated into its volume 1/3 after, left standstill again at normal temperatures spontaneous nucleation 20 hours, same method is processed mother liquor three to four times, and the gained crystal is the Artemisinin crude product, and the Artemisinin crude product again extracting method processing of the middle Artemisinin elaboration of repeating step (3) obtains the Artemisinin elaboration;
(4) recovery and reuse of waste: the mother liquor that step (2) is leached and contain Herba Artemisiae Annuae oil and the material A of sweet wormwood wax and material B collect and place extractor to be heated to 75 ℃, by reclaiming the sherwood oil of gasification with the tank connected device of extraction, can obtain pure sherwood oil 25 kg free from foreign meter, residue mother liquor (containing Herba Artemisiae Annuae oil and sweet wormwood wax) passes through steam distillation again, by reclaiming the Herba Artemisiae Annuae oil of gasification with the tank connected device of extraction, obtain Herba Artemisiae Annuae oil 1.5kg, cooling is also collected remaining material sweet wormwood wax in the extractor, obtains sweet wormwood wax 10kg.
The present embodiment also can reach embodiment one described technique effect, at this repeated description no longer.
As conversion of the present invention: the present invention also can not comprise step (4), and only comprises step (1), (2), (3); Countercurrent extraction in the step (2) also is not limited to comprise 3 extractions, also can suitably increase or reduce; The processing parameter of each step also is not limited to the described value of above-described embodiment, as long as the conversion of doing within the scope of the present invention all belongs to category of the present invention.
Claims (6)
1. a Green extraction process for artemisinin is characterized in that, this extraction process may further comprise the steps:
(1) raw material drying is processed: the sweet wormwood raw material is put into carried out drying treatment in the microwave energy saving drying plant, the temperature setting of microwave energy saving drying plant is set to 45-65 ℃ in the drying process, the drying treatment time is 25-35 minute, when reducing to 5-7% to the sweet wormwood raw material moisture, take out the pack of sweet wormwood raw material, warehouse-in is preserved;
(2) the first system of Artemisinin: the sweet wormwood raw material after the drying treatment in the step (1) is put in the extractor, close the dog-house of extractor, the fuel charging valve of opening extractor adds sherwood oil in extractor, the heating countercurrent extraction, temperature is controlled in the 55-75 ℃ of scope, after countercurrent extraction liquid emitted extractor, extracting solution is left standstill, getting supernatant liquor after the assorted precipitation in countercurrent extraction liquid makes it pass through silicagel column, use again sherwood oil eluting silica gel post after silicagel column is saturated, containing Artemisinin stream part and putting it in the concentration tank concentrated of coming out taken off in collection from silicagel column, when having crystal to separate out to the concentration tank, concentrated solution was put to the crystallizer crystallization 15-20 hour, crystallizer forces cooling to keep Tc to be controlled at 20 ℃-30 ℃ with water coolant during crystallization, obtain crystal after after crystallization is finished the mother liquor in the concentration tank being filtered, crystal is drying to obtain the Artemisinin crude product;
(3) Artemisinin is refining: leave standstill after placing Alcohol-settling tank with 60-75 times of 93-95% dissolve with ethanol the Artemisinin crude product that obtains in the step (2), get the supernatant liquor secondary filter, after filtrate is placed on the 1/3-3/4 that is concentrated into original volume in the concentration tank, concentrated solution is put in the crystallizer, left standstill spontaneous nucleation 15-20 hour at normal temperatures, obtain crystal after after crystallization is finished the mother liquor suction filtration being fallen, crystal obtains the Artemisinin elaboration after vacuum drying treatment;
When getting supernatant liquor by silicagel column in step (2), flow out stream part of silicagel column, part free from foreign meter is directly returned again usefulness of solvent stock, and impure part is by behind the concentration and recovery sherwood oil, and the gained concentrated solution is the material A that contains Herba Artemisiae Annuae oil and sweet wormwood wax; Also collect the part impure, that do not contain the Artemisinin composition that flows out in the eluting silica gel post process and flow part from silicagel column, behind the concentration and recovery sherwood oil, the gained concentrated solution is the material B that contains Herba Artemisiae Annuae oil and sweet wormwood wax;
Also comprise afterwards step (4) recovery and reuse of waste in step (3): the mother liquor that step (2) is leached and gained contain Herba Artemisiae Annuae oil and sweet wormwood wax material A and material B and collect and place extractor to be heated to 60-75 ℃, by reclaiming the sherwood oil of gasification with the tank connected device of extraction, the residue mother liquor passes through steam distillation again, by reclaiming the Herba Artemisiae Annuae oil that gasifies with extracting tank connected device, remaining material sweet wormwood wax in the extractor is also collected in cooling.
2. Green extraction process for artemisinin as claimed in claim 1, it is characterized in that, after the mother liquor that suction filtration goes out from step (3) is concentrated into the 1/3-3/4 of its volume again, left standstill again spontaneous nucleation 15-20 hour at normal temperatures, same method is processed mother liquor three to four times, the gained crystal is the Artemisinin crude product, and the Artemisinin crude product is processed by step (3) and obtained the Artemisinin elaboration.
3. Green extraction process for artemisinin as claimed in claim 1 is characterized in that, the heating countercurrent extraction need be carried out 3 times in step (2), and extraction time is 2-3 hour for the first time, and extraction time is 1-2 hour for the second time, and extraction time is 0.5-1 hour for the third time.
4. Green extraction process for artemisinin as claimed in claim 1, it is characterized in that, after in step (2), countercurrent extraction liquid and solvent oil being emitted extractor, also include following technique: close oil drain valve, the steaming valve that rushes of opening extractor rushes steaming to the sweet wormwood slag, sherwood oil in the sweet wormwood slag is discharged the sweet wormwood slag outside the extractor after volatilizing reclaim fully.
5. Green extraction process for artemisinin as claimed in claim 1 is characterized in that, the sherwood oil that is used for the eluting silica gel post in step (2) contains the 3%-8% ethyl acetate.
6. Green extraction process for artemisinin as claimed in claim 1 is characterized in that, with behind the sherwood oil eluting silica gel post, also comprises the technique of cleaning silicagel column with the hot water that reclaims in step (2).
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| CN102718774B (en) * | 2012-07-10 | 2013-07-03 | 刘志强 | Method for preparing artemisinin |
| CN103059038B (en) * | 2012-12-13 | 2016-02-24 | 大兴安岭林格贝寒带生物科技股份有限公司 | The production technique of enriching and purifying Artemisinin in a kind of Herba Artemisiae annuae |
| CN103073561B (en) * | 2013-02-07 | 2015-01-21 | 湖南威嘉生物科技有限公司 | Process of extracting artemisinin by biological enzyme-percolation method |
| CN103242335A (en) * | 2013-04-28 | 2013-08-14 | 四川省裕通生物技术有限公司 | Method for extracting and purifying artemisinin |
| CN104497002A (en) * | 2013-12-05 | 2015-04-08 | 广西仙草堂制药有限责任公司 | Extraction method of artemisinin |
| CN103664988B (en) * | 2013-12-25 | 2016-01-20 | 吉首大学 | A kind of extraction and separation method of Artemisinin |
| CN105886166B (en) * | 2016-04-22 | 2019-05-07 | 四川蓝伯特生物科技股份有限公司 | A kind of sweet wormwood wax Manual perfumed soap and preparation method thereof |
| CN105779129A (en) * | 2016-04-22 | 2016-07-20 | 四川蓝伯特生物科技有限责任公司 | Method for preparing Artemisia apiacea volatile oil from Artemisia apiacea waste mother liquor, method for preparing byproduct and obtained byproduct |
| CN106496244A (en) * | 2016-08-31 | 2017-03-15 | 重庆华方武陵山制药有限公司 | A kind of method for extracting qinghaosu from the recrystallization mother liquor of production qinghaosu |
| CN107365317A (en) * | 2017-06-30 | 2017-11-21 | 禹州市天源生物科技有限公司 | A kind of preparation technology using organic matter extracting artemisine |
| CN107973805A (en) * | 2017-12-25 | 2018-05-01 | 禹州市天源生物科技有限公司 | A kind of Green extraction process for artemisinin |
| CN112979673A (en) * | 2021-02-26 | 2021-06-18 | 云南群优生物科技有限公司 | Extraction and purification method of artemisinin |
| CN113105947A (en) * | 2021-04-21 | 2021-07-13 | 禹州市天源生物科技有限公司 | Preparation method of sweet wormwood essential oil |
| CN114989171B (en) * | 2022-07-20 | 2024-01-12 | 威胜生物医药(苏州)股份有限公司 | Efficient production process of tabersonine hydrochloride |
| CN115466647A (en) * | 2022-08-12 | 2022-12-13 | 湖南斯依康生物科技有限公司 | Preparation method of itching-relieving essential oil |
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| CN1740176A (en) * | 2005-09-21 | 2006-03-01 | 天津大学 | Process of extracting and separating artemisinin from sweet wormwood plant |
| CN101313928A (en) * | 2007-06-01 | 2008-12-03 | 薛永新 | Southernwood oil and medicine uses of its preparations |
| CN101899055B (en) * | 2010-08-12 | 2011-05-25 | 湖南农业大学 | Method for rapidly extracting artemisinin |
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