CN109574976A - A method of high-purity dihydroquercetin is extracted in industrialization from root of dahurian larch - Google Patents
A method of high-purity dihydroquercetin is extracted in industrialization from root of dahurian larch Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/32—2,3-Dihydro derivatives, e.g. flavanones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/40—Separation, e.g. from natural material; Purification
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Abstract
本发明涉及一种从东北地区落叶松树根工业化提取高纯度二氢槲皮素的方法，该方法以人工林择伐或皆伐废弃的落叶松树根为原料的，通过原材料选定，原材料清理、清洗，提取前原材料处理，提取、浓缩，沉降，二次浓缩，初结晶，一次离心分离，重结晶，二次离心分离，冷冻干燥，粉碎十二个步骤制得纯品二氢槲皮素。该方法利用伐后废弃的落叶松树根(主根和侧根)资源丰富、二氢槲皮素含量较富集(1.5‑1.9％)等条件，节能、环保、二氢槲皮素收率高。The invention relates to a method for industrially extracting high-purity dihydroquercetin from larch roots in Northeast China. Purification, pre-extraction raw material treatment, extraction, concentration, sedimentation, secondary concentration, primary crystallization, primary centrifugation, recrystallization, secondary centrifugation, freeze-drying, and crushing twelve steps to obtain pure dihydroquercetin. The method utilizes the conditions of abundant resources of larch roots (tap root and lateral root) discarded after felling, relatively rich dihydroquercetin content (1.5-1.9%) and other conditions, energy saving, environmental protection and high yield of dihydroquercetin.
Description
Fields
It is specifically a kind of discarded with LARCH PLANTATION selective cutting or clear felling the present invention relates to field of natural product chemistry
Tree root be raw material, therefrom industrialization extract dihydroquercetin method.
Background technique
Larix olgensis is a kind of natural plants that the Northeast, China is widely present, and trunk end is straight, is very suitable for conduct
Timber is applied to the every field such as building, furniture.Its root is often discarded as waste material due to no more use value.
Dihydroquercetin is a kind of natural drug with significant antioxidation, can be used as medical main auxiliary material and food
Bioactive additive and be widely used in drug, in health functional food.Have in medicine, industry and agriculture field and answers extensively
With.
Dihydroquercetin category flavanone kind composition, citrin race are a kind of powerful antioxidants, in natural anti-oxidation
To the absorption of free radical up to 32 μm of ol/mg (dihydroquercetin purity 95%) in agent, nowadays, with mentioning for people's standard of living
Height, people increasingly pay attention to health and longevity, and vitamin p is needed by human as one kind and itself can not synthesize micro-
Secondary element is by people institute widespread need, and dihydroquercetin is thin to extending as a kind of removing of natural inhibitor for free radical
There is remarkable effect in terms of born of the same parents' service life, it is contemplated that dihydroquercetin has stronger bioactivity and medical value.
Researches show that it can influence lipid metaboli by adjusting enzymatic activity；It has a certain impact to lymphopoiesis9；Together
When present certain antitumaous effect and antivirus action；And people to it for desmoenzyme15With cardio-cerebrovascular
Influence also has certain research.
Dihydroquercetin is extracted by Japanese scholars Fukui earliest, and in the U.S., Canada, the ground such as Russia have accordingly
Patent (US2744919A) (CA532804A) (RU84561C1)；Domestic (CN1844095) (CN1858046)
(CN101333203) patents such as (CN101333204) also provide corresponding extracting method.
But it is more low using high toxicity solvent or extraction process complexity or DNA purity to there is extraction process in above method
It is insufficient.
Such as United States Patent (USP) (US2744919A), provide it is a kind of extracted with water or the larger organic solvent of polarity, take later
Concentration, extraction, crystallization and etc. purifying dihydroquercetin extract, but the method is only capable of obtaining dihydroquercetin crude product, miscellaneous
Matter is more and there are many crystallisation times.A kind of hot water is provided in Canadian Patent (CA532804A), and dihydro Mongolian oak is extracted from bark
The method of Pi Su, with low polarity alcohol after concentration, ketone, the extraction such as ether is crystallized after removing solvent with hot water.The organic solvent that this method is used
There is certain toxicity, and inflammable and explosive in production, risk is larger.
Chinese patent (CN1844095) (CN1858046) (CN101863869A) (CN102924420B) etc. is also provided which
The method that dihydroquercetin is extracted in larch, but its some exist and use methyl tertiary butyl ether(MTBE), acetonitrile or chlorinated solvents
Etc. toxic or inflammable disadvantage, and higher cost；Some complex process, are unfavorable for industrial production and yield is lower；Some can only
Crude product is extracted, purity is lower.
In conclusion a kind of efficient and economic industrialization of low toxicity extracts high purity product method for dihydroquercetin
Development and utilization have very great meaning.
Summary of the invention
It is industrialized the object of the present invention is to provide one kind from the Northeast's root of dahurian larch and extracts high-purity dihydroquercetin
Method, this method is resourceful using the root of dahurian larch (taproot and lateral root) discarded after cutting down, dihydroquercetin content is richer
Collect conditions such as (1.5-1.9%), energy-saving and environmental protection, dihydroquercetin high income.
The object of the present invention is achieved like this, and a kind of industrialize from the Northeast's root of dahurian larch extracts high-purity dihydro
The method of Quercetin, method includes the following steps:
1), raw material are selected: the larix olgensis near N41 ° 46 ' 16.72 of north latitude " E126 ° 56 ' 9.73 of east longitude ", the age of tree
45-50, previous year, snowpack was deeper before cutting down, and back slope tree root is first choice, dihydroquercetin content after taproot and lateral root mixing
Between 1.5%-1.9%.
2) it, raw material cleaning, cleaning: amputates, discard fibrous root and diameter less than 60mm lateral root taper, peel off remainder tree
Then skin washes off silt with high pressure water flushing, determine between lateral root without air-drying after entrainment stone, be placed in and meet the storage of GAP regular warehouse
For use.
3) raw material stored in step 2) raw material disposal before, extracting: are ground into sawdust, granularity 2x2x4mm.
4) it, extracts, be concentrated: using cold-maceration, the sawdust of step 3) processing is added in extractor, it is excellent to be then added 95%
Grade n-hexane and purified water, with the pH value for analyzing pure glacial acetic acid tune mixture, sawdust: purified water: n-hexane: glacial acetic acid mass ratio
For 1:1:4:0.001, the cold soaking time is 14h, is completed after extracting (cold soaking) process, and extracting solution is pumped into outside single-action using vacuum and is followed
Ring evaporator is concentrated, vacuum degree 0.06Mpa, and temperature is 65 DEG C, and medicinal extract density receives cream when being 1.15-1.20, while
Achieve the purpose that recycle n-hexane.
5) it, settles: thering is a certain amount of turpentine oil to be leached during the extraction process, so needing to be gone under certain condition
Remove, medicinal extract after concentration be added in material-compound tank, be then added purified water, the ratio of medicinal extract and purified water is 1:3, stirring plus
Mixture is uniformly put into 6 transfer buckets by heat when temperature is 95 DEG C or so in tank, and the volume of bucket is 50L, and bucket put
In water bath, trough inner water temperature is 44 DEG C -46 DEG C, when water temperature is down to 28-30 DEG C, completes liquid and separates with solid, infall process
It completes.
6), secondary concentration: after turpentine oil removal, it is 1.20 that liquid, which concentrates it to density using single effect evaporator, condition
It is vacuum degree for 0.08Mpa, temperature is 65-68 DEG C, and then concentrate is put into primary crystal bucket.
7), primary crystal: being added 95% ethyl alcohol in primary crystal bucket, and concentrate and proportion of ethanol are 1:0.25, stirring
10min, when temperature is down to 20-25 DEG C, placing diameter in a liquid isStud 8-10 root after static 96h-108h, obtains
To primary crystal object, after completing primary crystal process, stud is taken out, is used again next time after cleaning up with setting.
8), primary centrifuge separation: primary crystal object is homogeneously disposed in 4 filter cloth bags, completes solid-liquid using tripod pendulum type batch centrifugal
Separation, centrifuge speed 1500rpm run 20min, and liquid is transferred to alcohol recovering device.
9) it, recrystallizes: being poured into reaction kettle after the crystal in the cloth bag of centrifugal process is weighed, while purifying is added
The ratio of water, crystal and purified water is 1:1, and liquid is put into recrystallization bucket, weight by sealing heating when temperature is 95-97 DEG C
Multiple step 7) primary crystal process.
10), secondary centrifuging separates: weight process 8) the step of.
11) it, is freeze-dried: four disks of the crystal in cloth bag after centrifuge separation point is placed in BLK-FDYY-3 vacuum refrigeration
In drying machine, temperature is -15 DEG C, vacuum degree 1.0pa, and time 16h is arranged, obtains dried object after 16h.
12) it, crushes: dried object is pulverized and sieved, obtain pale powder, i.e. product dihydroquercetin, 200 mesh are qualified.
The present invention has the advantages that:
1, the present invention is a set of energy-saving and environmental protection and the technique suitable for industrial-scale production.The former material used in invention
Material is the root of dahurian larch discarded after artificial forest is cut down, and is the tree root of the gradient≤25 ° LARCH PLANTATION, be ginseng plant with it is artificial
The inevitable outcome of woods 45-50 circulation, and it is extracted after sawdust be new energy materials-biological particles raw material, it is green
Color is economic and environment-friendly, meets sustainable development.As cold soaking, concentration process operate under closing and vacuum condition；That recycles is organic molten
Agent recycles etc. after final minification.
2, the technology of the present invention can realize the preparation of high-purity high yield dihydroquercetin product.The solvent that extraction process uses
Specific aim is stronger, such as: when traditional handicraft uses water or alcohol as extractant, generate more arabogalactan, rosin, wood
The impurity such as quality, separate the process very complicated of these substances, and are easily reduced final products purity, and this patent use just oneself
Alkane only has turpentine oil generation as solvent extraction process, and separation process is simple, is conducive to the progress of subsequent processing, improves most
The yield and purity of finished product.Final products purity is up to 95% or more, and yield is also up to 5 ‰
3, the present invention participates in crystallization process using the ethyl alcohol of proper proportion, and it is flat to break material with stud (crystallization core) placement
The critical point of weighing apparatus accelerates the speed for tending to crystallization and improves crystalline quality, and product purity is high, and stud can be recycled,
This is main innovation point of the invention.
Detailed description of the invention
Fig. 1 is dihydroquercetin chromatograms obtained in the embodiment of the present invention 1.
Fig. 2 is dihydroquercetin chromatograms obtained in the embodiment of the present invention 2.
Fig. 3 is dihydroquercetin chromatograms obtained in the embodiment of the present invention 3.
Fig. 4 is dihydroquercetin chromatograms obtained in the embodiment of the present invention 4.
Fig. 5 is dihydroquercetin chromatograms obtained in the embodiment of the present invention 5.
Fig. 6, Fig. 7 are the nuclear magnetic spectrogram of the made dihydroquercetin of the present invention.
Fig. 8 is the mass spectrogram of dihydroquercetin obtained by the present invention.
Specific embodiment
Present invention implementation is described in further detail below:
A method of dihydroquercetin is extracted with the industrialization of larch (the Northeast) tree root, it is characterised in that:
A kind of with including the discarded tree root of selective cutting or clear felling is raw material, and by extracting, sedimentation, crystallization was waited
Journey therefrom extracts the method for dihydroquercetin.It is raw material by selecting certain trees tree root, by cleaning, cleans and pre-
Processing and etc., concentration is extracted, is settled later, secondary concentration finally passes through primary crystal, is centrifugated, recrystallization
After secondary separation, method by being freeze-dried and crushing obtains sterling dihydroquercetin.
In the following, the present invention will be further detailed with embodiment, but its any for being not limited to these examples
A or similar example.
Embodiment 1: experimentai batches 201804002
Capital equipment: 6m3 multifunctional extracting pot, 500L/h single-effect external circulation evaporator；300L/h single-effect external circulation evaporator,
500l material-compound tank, 100L reaction kettle, 100L crystallizing tank；5131 water circulation vavuum pump of 2BV-；3 vacuum refrigeration of BLK-FDYY-is dry
Dry machine, 1000 pulverizer of BFY-.
Detecting instrument: Agilent1260
Standard items: sigma 03890585-10MG batch: 201703011
Operating process:
1, the qualified raw material of processing are weighed into 1000kg, puts into 6m3In multifunctional extracting pot, addition 1000kg purified water,
4000kg n-hexane (95%) closing feeding port is added after 1000mg ice ethyl alcohol and closes pipeline valve, after cold soaking 14h, will be mentioned
Take liquid to be pumped into 500L/h single-effect external circulation evaporator using vacuum, be concentrated, vacuum degree 0.06mpa, temperature be 65 DEG C of this
When extractor be added 3000kg purified water, then heating carry out sawdust in n-hexane recycling.When the sampled density 1.18 of concentrate
Blowing, it is weighed to obtain concentrate 114kg.
2, concentrate is poured into material-compound tank, 432kg purified water is then added into tank, when being heated to 95 DEG C, will mix
Object is uniformly put into 6 transfer buckets, and bucket enters in water bath, and 45 DEG C of water temperature, water temperature is 29 DEG C when 13h, is taken out transfer bucket, is removed liquid
Body surface face turpentine oil.
3, liquid in bucket is pumped into 300L/h single-effect external circulation evaporator using vacuum and carries out secondary concentration, vacuum degree is
0.08Mpa, after temperature is 65 DEG C, 45 minutes 2 hours, sampled concentrated solution density is 1.20, stops concentration operation, by concentrate
It is put into primary crystal bucket, is weighed as 45kg.
4,95% ethyl alcohol 11.26kg is added into primary crystal bucket, stirs 10min, sealing is put into water bath cooling.In slot
Coolant-temperature gage is room temperature, and fluid temperature is 22 DEG C in 20 minutes 6 hours survey buckets, takes out stud after placing stud 9,96 hours, really
Recognize crystalline solid to be formed.
5, crystalline solid is uniformly placed in 4 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear turns
1000 revs/min of operation 10min of speed, it is automatic to start 1500 revs/min of operation 10min of top gear revolving speed, filter cloth bag is taken out, after weighing
Solid 15.66kg.
6,15.66kg solid is put into reaction kettle, 15.66kg purified water, capping heating is added, kettle top safety valve opens jump
Afterwards, stopping heating, material in kettle is put into recrystallization bucket, weighing 7.84kg ethyl alcohol (95%) is added in bucket, 10min is stirred,
Bung is sealed, is put into sea water bath, temperature is 20 DEG C in 20 minutes 4 hours survey buckets, is taken out when placing stud 6,100 hours
Stud, confirmation recrystallization are formed.
7, crystalline solid is uniformly placed in 2 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear is low
Fast shelves run 10min, and the automatic top gear that starts runs 10min, takes out cloth bag, solid is placed in 3 basins, is sent into dry
Dry.
8, basin is sent into freeze drier, setting refrigerator working procedure, -15 DEG C of operation temperature, vacuum degree
1.0pa, drying time 16 hours.
9, after the completion of drying process, basin is taken out, material is concentrated, is crushed, be sieved to obtain dihydroquercetin powder, grain
Degree is 200 mesh, is weighed as 5.75kg, and it is 94.45% through detection dihydroquercetin purity that yield, which is 5.75 ‰,.
The detection of dihydroquercetin:
It is detection means by liquid chromatogram, using sigma 03890585-10MG dihydroquercetin standard items as standard items,
Qualitative and quantitative detection dihydroquercetin prepared by 1 through the above steps.
Attached drawing 1 is the chromatograms of dihydroquercetin made from the above method (201804002): the peak You Tuzhong integral area
Ratio can calculate, and dihydroquercetin purity is 94.45%
Embodiment 2: experimentai batches 201805006
Capital equipment: 6m3 multifunctional extracting pot, 500L/h single-effect external circulation evaporator；300L/h single-effect external circulation evaporator,
500l material-compound tank, 100L reaction kettle, 100L crystallizing tank；5131 water circulation vavuum pump of 2BV-；3 vacuum refrigeration of BLK-FDYY-is dry
Dry machine, 1000 pulverizer of BFY-.
Detecting instrument: Agilent1260
Standard items: sigma 03890585-10MG batch: 201703011
Operating process:
1, the qualified raw material of processing are weighed into 1000kg, put into 6m3 multifunctional extracting pot, addition 1000kg purified water,
4000kg n-hexane (95%) closing feeding port is added after 1000mg ice ethyl alcohol and closes pipeline valve, after cold soaking 14h, will be mentioned
Take liquid to be pumped into 500L/h single-effect external circulation evaporator using vacuum, be concentrated, vacuum degree 0.06Mpa, temperature be 65 DEG C of this
When extractor be added 3000kg purified water, then heating carry out sawdust in n-hexane recycling.When the sampled density 1.18 of concentrate
Blowing, it is weighed to obtain concentrate 150kg.
2, concentrate is poured into material-compound tank, 450kg purified water is then added into tank, when being heated to 95 DEG C, will mix
Object is uniformly put into 6 transfer buckets, and bucket enters in water bath, and 45 DEG C of water temperature, water temperature is 30 DEG C when 13h, is taken out transfer bucket, is removed
Liquid surface turpentine oil.
3, liquid in bucket is pumped into 300L/h single-effect external circulation evaporator using vacuum to be concentrated three times, vacuum degree is
0.08Mpa, after temperature is 65 DEG C, 55 minutes 2 hours, sampled concentrated solution density is 1.18, stops concentration operation, by concentrate
It is put into primary crystal bucket, is weighed as 47.6kg.
4,95% ethyl alcohol 11.9kg is added into primary crystal bucket, stirs 10min, sealing is put into water-bath bucket cooling.In slot
Coolant-temperature gage is room temperature, and fluid temperature is 23 DEG C in 28 minutes 6 hours survey buckets, takes out stud after placing stud 9,99 hours, really
Recognize crystalline solid to be formed.
5, crystalline solid is uniformly placed in 4 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear turns
1000 revs/min of operation 10min of speed, it is automatic to start 1500 revs/min of operation 10min of top gear revolving speed, filter cloth bag is taken out, after weighing
Solid 16.3kg.
6,16.3kg solid is put into reaction kettle, 16.3kg purified water, capping heating is added, kettle top safety valve opens jump
Afterwards, stop heating, material in kettle is put into recrystallization bucket, weighing 8.2kg ethyl alcohol (95%) is added in bucket, stirs 10min, will
Bung is sealed, and is put into sea water bath, and temperature is 20 DEG C in 20 minutes 4 hours survey buckets, takes out titanium when placing stud 6,100 hours
Stick, confirmation recrystallization are formed.
7, crystalline solid is uniformly placed in 2 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear fortune
Row 10min, the automatic top gear that starts run 10min, take out cloth bag, solid is placed in 3 basins, be sent into drying room.
8, basin is sent into freeze drier, setting refrigerator working procedure, -15 DEG C of operation temperature, vacuum degree
1.0pa, drying time 16 hours.
9, after the completion of drying process, basin is taken out, material is concentrated, is crushed, be sieved to obtain dihydroquercetin powder, grain
Degree is 200 mesh, is weighed as 7.92kg, and it is 94.32% through detection dihydroquercetin purity that yield, which is 7.92 ‰,.
Attached drawing 2 is the chromatograms of dihydroquercetin made from the above method (201805006): You Tuzhong integral area ratio
Example can calculate, and dihydroquercetin purity is 94.32%
Embodiment 3: experimentai batches 201806001
Capital equipment: 6m3 multifunctional extracting pot, 500L/h single-effect external circulation evaporator；300L/h single-effect external circulation evaporator,
500l material-compound tank, 100L reaction kettle, 100L crystallizing tank；5131 water circulation vavuum pump of 2BV-；3 vacuum refrigeration of BLK-FDYY-is dry
Dry machine, 1000 pulverizer of BFY-.
Detecting instrument: Agilent1260
Standard items: sigma 03890585-10MG batch: 201703011
Operating process:
1, the qualified raw material of processing are weighed into 1000kg, put into 6m3 multifunctional extracting pot, addition 1000kg purified water,
4000kg n-hexane (95%) closing feeding port is added after 1000mg ice ethyl alcohol and closes pipeline valve, after cold soaking 14h, will be mentioned
It takes liquid to be pumped into 500L/h single-effect external circulation evaporator using vacuum, is concentrated, vacuum degree 0.06, Mpa, temperature is 65 DEG C of
At this moment 3000kg purified water is added in extractor, and then heating carries out n-hexane recycling in sawdust.When the sampled density of concentrate
1.19 blowings, it is weighed to obtain concentrate 138kg.
2, concentrate is poured into material-compound tank, 414kg purified water is then added into tank, when being heated to 95 DEG C, will mix
Object is uniformly put into 6 transfer buckets, and bucket enters in water bath, and 45 DEG C of water temperature, water temperature is 30 DEG C when 12h, is taken out transfer bucket, is removed
Liquid surface turpentine oil.
3, liquid in bucket is pumped into 300L/h single-effect external circulation evaporator using vacuum to be concentrated three times, vacuum degree is
0.08Mpa, after temperature is 65 DEG C, 35 minutes 2 hours, sampled concentrated solution density is 1.15, stops concentration operation, by concentrate
It is put into primary crystal bucket, is weighed as 42.6kg.
4,95% ethyl alcohol 10.66kg is added into primary crystal bucket, stirs 10min, sealing is put into water-bath bucket cooling.In slot
Coolant-temperature gage is room temperature, and fluid temperature is 22 DEG C in 20 minutes 6 hours survey buckets, takes out stud after placing stud 9,96 hours, really
Recognize crystalline solid to be formed.
5, crystalline solid is uniformly placed in 4 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear turns
1000 revs/min of operation 10min of speed, it is automatic to start 1500 revs/min of operation 10min of top gear revolving speed, filter cloth bag is taken out, after weighing
Solid 15.36kg.
6,15.36kg solid is put into reaction kettle, 15.36kg purified water, capping heating is added, kettle top safety valve opens jump
Afterwards, stopping heating, material in kettle is put into recrystallization bucket, weighing 7.68kg ethyl alcohol (95%) is added in bucket, 10min is stirred,
Bung is sealed, is put into sea water bath, temperature is 20 DEG C in 20 minutes 4 hours survey buckets, is taken out when placing stud 6,100 hours
Stud, confirmation recrystallization are formed.
7, crystalline solid is uniformly placed in 2 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear fortune
Row 10min, the automatic top gear that starts run 10min, take out cloth bag, solid is placed in 3 basins, be sent into drying room.
8, basin is sent into freeze drier, setting refrigerator working procedure, -15 DEG C of operation temperature, vacuum degree
1.0pa, drying time 16 hours.
9, after the completion of drying process, basin is taken out, material is concentrated, is crushed, be sieved to obtain dihydroquercetin powder, grain
Degree is 200 mesh, is weighed as 7.112kg, and it is 94.98% through detection dihydroquercetin purity that yield, which is 7.112 ‰,.
Attached drawing 3 is the chromatograms of dihydroquercetin made from the above method (201806001): the peak You Tuzhong integral area
Ratio can calculate, and dihydroquercetin purity is 94.98%.
Embodiment 4: experimentai batches 201808014
Capital equipment: 6m3 multifunctional extracting pot, 500L/h single-effect external circulation evaporator；300L/h single-effect external circulation evaporator,
500l material-compound tank, 100L reaction kettle, 100L crystallizing tank；5131 water circulation vavuum pump of 2BV-；3 vacuum refrigeration of BLK-FDYY-is dry
Dry machine, 1000 pulverizer of BFY-.
Detecting instrument: Agilent1260
Standard items: sigma 03890585-10MG batch: 201703011
Operating process:
1, the qualified raw material of processing are weighed into 1000kg, put into 6m3 multifunctional extracting pot, addition 1000kg purified water,
4000kg n-hexane (95%) closing feeding port is added after 1000mg ice ethyl alcohol and closes pipeline valve, after cold soaking 14h, will be mentioned
It takes liquid to be pumped into 500L/h single-effect external circulation evaporator using vacuum, is concentrated, vacuum degree 0.06, Mpa, temperature is 65 DEG C of
At this moment 3000kg purified water is added in extractor, and then heating carries out n-hexane recycling in sawdust.When the sampled density of concentrate
1.15 blowings, it is weighed to obtain concentrate 152kg.
2, concentrate is poured into material-compound tank, 456kg purified water is then added into tank, when being heated to 95 DEG C, will mix
Object is uniformly put into 6 transfer buckets, and bucket enters in water bath, and 45 DEG C of water temperature, water temperature is 28 DEG C when 14h, is taken out transfer bucket, is removed
Liquid surface turpentine oil.
3, liquid in bucket is pumped into 300L/h single-effect external circulation evaporator using vacuum to be concentrated three times, vacuum degree is
0.08Mpa, after temperature is 68 DEG C, 25 minutes 2 hours, sampled concentrated solution density is 1.16, stops concentration operation, by concentrate
It is put into primary crystal bucket, is weighed as 45.6kg.
4,95% ethyl alcohol 11.4kg is added into primary crystal bucket, stirs 10min, sealing is put into water-bath bucket cooling.In slot
Coolant-temperature gage is room temperature, and fluid temperature is 23 DEG C in 30 minutes 6 hours survey buckets, takes out stud after placing stud 9,96 hours, really
Recognize crystalline solid to be formed.
5, crystalline solid is uniformly placed in 4 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear turns
1000 revs/min of operation 10min of speed, it is automatic to start 1500 revs/min of operation 10min of top gear revolving speed, filter cloth bag is taken out, after weighing
Solid 16.24kg.
6,16.24kg solid is put into reaction kettle, 16.24kg purified water, capping heating is added, kettle top safety valve opens jump
Afterwards, stopping heating, material in kettle is put into recrystallization bucket, weighing 8.12kg ethyl alcohol (95%) is added in bucket, 10min is stirred,
Bung is sealed, is put into sea water bath, temperature is 24 DEG C in 30 minutes 4 hours survey buckets, is taken out when placing stud 6,100 hours
Stud, confirmation recrystallization are formed.
7, crystalline solid is uniformly placed in 2 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear fortune
Row 10min, the automatic top gear that starts run 10min, take out cloth bag, solid is placed in 3 basins, be sent into drying room.
8, basin is sent into freeze drier, setting refrigerator working procedure, -15 DEG C of operation temperature, vacuum degree
1.0pa, drying time 16 hours.
9, after the completion of drying process, basin is taken out, material is concentrated, is crushed, be sieved to obtain dihydroquercetin powder, grain
Degree is 200 mesh, is weighed as 8.34kg, and it is 94.56% through detection dihydroquercetin purity that yield, which is 8.34 ‰,.
Attached drawing 4 is the chromatograms of dihydroquercetin made from the above method (201808014): the peak You Tuzhong integral area
Ratio can calculate, and dihydroquercetin purity is 94.56%.
Embodiment 5: experimentai batches 201809007
Capital equipment: 6m3 multifunctional extracting pot, 500L/h single-effect external circulation evaporator；300L/h single-effect external circulation evaporator,
500l material-compound tank, 100L reaction kettle, 100L crystallizing tank；5131 water circulation vavuum pump of 2BV-；3 vacuum refrigeration of BLK-FDYY-is dry
Dry machine, 1000 pulverizer of BFY-.
Detecting instrument: Agilent1260
Standard items: sigma 03890585-10MG batch: 201703011
Operating process:
1, the qualified raw material of processing are weighed into 1000kg, put into 6m3 multifunctional extracting pot, addition 1000kg purified water,
4000kg n-hexane (95%) closing feeding port is added after 1000mg ice ethyl alcohol and closes pipeline valve, after cold soaking 14h, will be mentioned
It takes liquid to be pumped into 500L/h single-effect external circulation evaporator using vacuum, is concentrated, vacuum degree 0.06, Mpa, temperature is 65 DEG C of
At this moment 3000kg purified water is added in extractor, and then heating carries out n-hexane recycling in sawdust.When the sampled density of concentrate
1.18 blowings, it is weighed to obtain concentrate 116kg.
2, concentrate is poured into material-compound tank, 438kg purified water is then added into tank, when being heated to 95 DEG C, will mix
Object is uniformly put into 6 transfer buckets, and bucket enters in water bath, and 45 DEG C of water temperature, water temperature is 29 DEG C when 13h, is taken out transfer bucket, is removed
Liquid surface turpentine oil.
3, liquid in bucket is pumped into 300L/h single-effect external circulation evaporator using vacuum to be concentrated three times, vacuum degree is
0.08Mpa, after temperature is 65 DEG C, 45 minutes 2 hours, sampled concentrated solution density is 1.20, stops concentration operation, by concentrate
It is put into primary crystal bucket, is weighed as 45.8kg.
4,95% ethyl alcohol 11.48kg is added into primary crystal bucket, stirs 10min, sealing is put into water-bath bucket cooling.In slot
Coolant-temperature gage is room temperature, and fluid temperature is 22 DEG C in 20 minutes 6 hours survey buckets, takes out stud after placing stud 9,96 hours, really
Recognize crystalline solid to be formed.
5, crystalline solid is uniformly placed in 4 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear turns
1000 revs/min of operation 10min of speed, it is automatic to start 1500 revs/min of operation 10min of top gear revolving speed, filter cloth bag is taken out, after weighing
Solid 15.76kg.
6,15.76kg solid is put into reaction kettle, 15.76kg purified water, capping heating is added, kettle top safety valve opens jump
Afterwards, stopping heating, material in kettle is put into recrystallization bucket, weighing 7.88kg ethyl alcohol (95%) is added in bucket, 10min is stirred,
Bung is sealed, is put into sea water bath, temperature is 20 DEG C in 20 minutes 4 hours survey buckets, is taken out when placing stud 6,100 hours
Stud, confirmation recrystallization are formed.
7, crystalline solid is uniformly placed in 2 filter cloth bags, is symmetrically put into a centrifuge, start centrifuge, low or first gear fortune
Row 10min, the automatic top gear that starts run 10min, take out cloth bag, solid is placed in 3 basins, be sent into drying room.
8, basin is sent into freeze drier, setting refrigerator working procedure, -15 DEG C of operation temperature, vacuum degree
1.0pa, drying time 16 hours.
9, after the completion of drying process, basin is taken out, material is concentrated, is crushed, be sieved to obtain dihydroquercetin powder, grain
Degree is 200 mesh, is weighed as 7.62kg, and it is 94.85% through detection dihydroquercetin purity that yield, which is 7.62 ‰,.
Attached drawing 5 is the chromatograms of dihydroquercetin made from the above method (201809007): the peak You Tuzhong integral area
Ratio can calculate, and dihydroquercetin purity is 94.85%.
In conclusion we are raw material using discarded larix olgensis root sawdust, the extracting solution used be water and
The n-hexane that widely applied low toxicity easily recycles in soybean oil extract, subsequent separation process only use nontoxic ethyl alcohol and
Water finally carries out out-phase crystallization with stud, and entire process flow is easy to operate, production safety, can industrialized production, single treatment
Raw material reaches 1000kg, and the dihydroquercetin product yield of output is up to 5 ‰, is higher by reported various technological levels, purity is high
Up to 95%, no objectionable impurities can be used for biomedical products.It is (attached that products obtained therefrom through nuclear-magnetism and mass spectrum is verified as dihydroquercetin
Fig. 6,7,8), and by high performance liquid chromatography it is verified as the dihydroquercetin of high-purity.In conclusion this technique is a kind of industry
Change and effective technique of high yield dihydroquercetin production is provided under the premise of high-purity.
Claims (2)
1. it is a kind of from root of dahurian larch industrialization extract high-purity dihydroquercetin method, it is characterised in that: this method with
The root of dahurian larch that selective cutting or clear felling are discarded is raw material, selected by raw material, raw material cleaning, cleaning, extraction
Preceding raw material disposal, is extracted, concentration, sedimentation, secondary concentration, and primary crystal is primary to be centrifugated, recrystallization, secondary centrifuging separation,
Freeze-drying crushes 12 steps and sterling dihydroquercetin is made.
2. the side that high-purity dihydroquercetin is extracted in a kind of industrialization from root of dahurian larch according to claim 1
Method, it is characterised in that: this method is that specific step is as follows:
1), raw material are selected: the larix olgensis near N41 ° 46 ' 16.72 of north latitude " E126 ° 56 ' 9.73 of east longitude ", age of tree 45-
50 years, previous year, snowpack was deeper before cutting down, and back slope tree root is first choice, and dihydroquercetin content is after taproot and lateral root mixing
Between 1.5%-1.9%；
2), raw material cleaning, cleaning: amputating, discard fibrous root and diameter less than 60mm lateral root taper, peel off remainder bark,
Then wash off silt with high pressure water flushing, determine between lateral root without being air-dried after entrainment stone, be placed in meet the storage of GAP regular warehouse to
With；
3) raw material stored in step 2) raw material disposal before, extracting: are ground into sawdust, granularity 2x2x4mm；
4) it, extracts, be concentrated: using cold-maceration, the sawdust of step 3) processing is added in extractor, 95% top grade is then being added just
Hexane and purified water, with the pH value for analyzing pure glacial acetic acid tune mixture, sawdust: purified water: n-hexane: glacial acetic acid mass ratio is 1:
1:4:0.001, cold soaking time are 14h, are completed after extracting (cold soaking) process, and extracting solution is pumped into single-effect external circulation using vacuum and is steamed
Hair device is concentrated, vacuum degree 0.06Mpa, and temperature is 65 DEG C, and medicinal extract density receives cream when being 1.15-1.20, while also reaching
The purpose of recycling n-hexane；
5) it, settles: thering is a certain amount of turpentine oil to be leached during the extraction process, so need to remove it under certain condition,
Medicinal extract after concentration is added in material-compound tank, is then added purified water, the ratio of medicinal extract and purified water is 1:3, agitating and heating, when
When temperature is 95 DEG C or so in tank, mixture is uniformly put into 6 transfer buckets, the volume of bucket is 50L, and bucket is put middle water bath
In, trough inner water temperature is 44 DEG C -46 DEG C, when water temperature is down to 28-30 DEG C, completes liquid and separates with solid, infall process is completed；
6), secondary concentration: after turpentine oil removal, it is 1.20 that liquid, which concentrates it to density using single effect evaporator, and condition is true
Reciprocal of duty cycle is 0.08Mpa, and temperature is 65-68 DEG C, and then concentrate is put into primary crystal bucket；
7), primary crystal: being added 95% ethyl alcohol in primary crystal bucket, and concentrate and proportion of ethanol are 1:0.25, stirs 10min, when
When temperature is down to 20-25 DEG C, placing diameter in a liquid isStud 8-10 root after static 96h-108h, obtains primary crystal
Object after completing primary crystal process, takes out stud, is used again next time after cleaning up with setting；
8), primary centrifuge separation: primary crystal object is homogeneously disposed in 4 filter cloth bags, completes solid-liquid point using tripod pendulum type batch centrifugal
From centrifuge speed 1500rpm runs 20min, and liquid is transferred to alcohol recovering device；
9) it, recrystallizes: being poured into reaction kettle after the crystal in the cloth bag of centrifugal process is weighed, while purified water is added, tie
The ratio of brilliant object and purified water is 1:1, and liquid is put into recrystallization bucket when temperature is 95-97 DEG C, repeats step by sealing heating
7) primary crystal process；
10), secondary centrifuging separates: repetitive process 8) the step of；
11) it, is freeze-dried: four disks of the crystal in cloth bag after centrifuge separation point is placed in BLK-FDYY-3 vacuum freeze drying
In machine, temperature is -15 DEG C, vacuum degree 1.0pa, and time 16h is arranged, obtains dried object after 16h；
12) it, crushes: dried object is pulverized and sieved, obtain pale powder, i.e. product dihydroquercetin, 200 mesh are qualified.
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| RU2318528C2 (en) * | 2006-04-03 | 2008-03-10 | Евгений Викентьевич Лифанов | Method for preparing dihydroqurcetin |
| CN101993429A (en) * | 2010-12-08 | 2011-03-30 | 天津市尖峰天然产物研究开发有限公司 | Method for extracting dihydroquercetin from larch sawdust |
| CN102924420A (en) * | 2012-10-25 | 2013-02-13 | 沈立乾 | Method for extracting dihydroquercetin from root of dahurian larch |
| CN103951645A (en) * | 2013-07-18 | 2014-07-30 | 郑毅男 | Preparation method and medicinal purpose of Larix olgensis extractive |
| CN108285440A (en) * | 2017-05-20 | 2018-07-17 | 郑毅男 | A kind of preparation method for extracting dihydroquercetin extract in larch using ultra-high pressure apparatus |
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2018
- 2018-12-10 CN CN201811502285.3A patent/CN109574976B/en active Active
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| RU2318528C2 (en) * | 2006-04-03 | 2008-03-10 | Евгений Викентьевич Лифанов | Method for preparing dihydroqurcetin |
| CN101993429A (en) * | 2010-12-08 | 2011-03-30 | 天津市尖峰天然产物研究开发有限公司 | Method for extracting dihydroquercetin from larch sawdust |
| CN102924420A (en) * | 2012-10-25 | 2013-02-13 | 沈立乾 | Method for extracting dihydroquercetin from root of dahurian larch |
| CN103951645A (en) * | 2013-07-18 | 2014-07-30 | 郑毅男 | Preparation method and medicinal purpose of Larix olgensis extractive |
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