CN104478680A - Method for extracting methyl heptenone from litsea cubeba - Google Patents
Method for extracting methyl heptenone from litsea cubeba Download PDFInfo
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- CN104478680A CN104478680A CN201410685012.2A CN201410685012A CN104478680A CN 104478680 A CN104478680 A CN 104478680A CN 201410685012 A CN201410685012 A CN 201410685012A CN 104478680 A CN104478680 A CN 104478680A
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Abstract
The invention discloses a method for extracting methyl heptenone from litsea cubeba. According to the method, litsea cubeba is used as a raw material, high-purity and high-yield methyl heptenone is successfully extracted for the first time, and a byproduct limonene can be produced while methyl heptenone is extracted, so that the cost is greatly reduced. Methyl heptenone, of which the purity is over 90% and the yield is over 80%, is extracted from litsea cubeba with low content of methyl heptenone, so that the method has important practical significance and can be used for bringing huge economic benefits.
Description
Technical field
The present invention relates to the extractive technique of Persea cubeba, be specifically related to a kind of method extracting Sulcatone from Persea cubeba.
Background technology
Sulcatone has very strong chemical reaction ability, multiple Chemicals can be derived, be the intermediate of medicine, essence and perfume synthesis, be also the main raw material preparing phantol, citral and citrylideneacetone, the latter can prepare vitamins and multiple essence and flavoring agent further.
In traditional technology, Sulcatone is prepared by chemical synthesis process, as in patent documentation CN103664556A, with chloroisoamylene and acetone for Sulcatone prepared by raw material, in patent documentation CN1539807 with methyl butenol and methoxyl group propylene for Sulcatone prepared by raw material, but these method ubiquity side reactions are many, raw material is poisonous, yield is not high and high in cost of production problem.
In addition, the main component in Persea cubeba is citral, limonene, and also containing a small amount of firpene, amphene etc., wherein, the content of Sulcatone is lower, extracts difficulty large.In the prior art, Persea cubeba is mainly utilized to extract citral, the not yet useful report utilizing Persea cubeba to extract Sulcatone.
Summary of the invention
The object of the present invention is to provide a kind of cost low, the method extracting Sulcatone from Persea cubeba that purity, productive rate are high.
Further object of the present invention is also, by-product limonene extract Sulcatone from Persea cubeba while.
Technical scheme of the present invention:
From Persea cubeba, extract a method for Sulcatone, comprise the following steps: a, by Persea cubeba clean, broken; B, add water and carry out underpressure distillation at 60-100 DEG C, be separated, obtain fluid; C, in fluid, add strong base weak acid salts solution obtain mixed solution, be heated to 50-100 DEG C, stir, layering, obtain Litsea Cubeba oil I; D, Litsea Cubeba oil I is carried out underpressure distillation at temperature 80-105 DEG C, obtain Litsea Cubeba oil II; E, in Litsea Cubeba oil II, add its weight 2-6 propylene glycol, alcohol mixed solvent doubly, the mass ratio of propylene glycol and ethanol is 4-8:1, and stratification after stirring at 40-55 DEG C, obtains upper strata fluid I; F, add in ether solvent by upper strata fluid I, stir evenly, then add ethanolic soln wherein, stratification after stirring, obtains upper strata fluid II; G, temperature 50-68 DEG C, upper strata fluid II is concentrated into no solvent residue, the fluid after must concentrating under the condition of vacuum tightness 15-35kpa; H, the fluid underpressure distillation at 80-120 DEG C after concentrated to be purified, obtain product Sulcatone.
By liquid more than gained in step e through being separated by-product limonene.Described remaining liquid can be separated by underpressure distillation and obtain limonene.
The strong base weak acid salts solution added in fluid in step c is carbonate solution or citrate solution, and the concentration of strong base weak acid salts solution is 8-20 quality %.
The concentration of the strong base weak acid salts solution added in fluid in step c is preferably 8-12 quality %.
The carbonate added in fluid in step c is salt of wormwood or sodium carbonate.
In step c, after adding carbonate solution, the concentration of carbanion in mixed solution is 1.55-3.5mg/10mL; Be preferably 2-2.5mg/10mL.
In step e, the mass ratio of propylene glycol and ethanol is preferably 4-6:1.
The mass ratio of propylene glycol and ethanol more preferably 4-5:1 in step e.
Wherein, the concrete steps of the underpressure distillation described in h step are: first by the heat-up rate of 6-8 DEG C/min, the fluid after concentrated is heated to 80-90 DEG C, vacuum degree control at 15-45kpa, distillation 50-75min; Then be heated to 95-105 DEG C, vacuum degree control 8-15kpa, control of reflux ratio, at 3/27-3/36, distills 1.5-3.5h; Finally be heated to 110-120 DEG C by the heat-up rate of 6-8 DEG C/min, vacuum degree control is at 3-8kpa, and distillation 50-75min, collects the fluid steamed.
The concrete steps of the underpressure distillation described in Step d are: by Litsea Cubeba oil I at temperature 80-90 DEG C, vacuum tightness 15-25kpa, after carrying out the first step distillation under the condition of reflux ratio 3/12-3/21, at temperature 95-105 DEG C, vacuum tightness 4-10kpa, carry out second step distillation under the condition of reflux ratio 4/8-4/16, obtain Litsea Cubeba oil II.
The distillation concrete steps that add water in b step are: joined by Persea cubeba in the water of 2-6 times of weight, be first heated to 60-75 DEG C by the heat-up rate of 3-4 DEG C/min, vacuum degree control, at 8-20kpa, distills 1.0-2.5h; The water adding 60-75 DEG C again supplements the moisture of distillation loss, then is heated to 90-100 DEG C by the heat-up rate of 2-3 DEG C/min, vacuum degree control 4-8kpa, distillation 1.5-5.0h.
The detailed process of step e is preferably: first add in 2-6 times of weight propylene glycol and alcohol mixed solvent at normal temperatures and pressures by Litsea Cubeba oil II, wherein, the mass ratio of propylene glycol and ethanol is 4-6:1, stirs evenly; Then, heat by the heat-up rate of 1-3 DEG C/min, be elevated to 40-55 DEG C to temperature and stop heating, and keep 1.5-2.5h, the warm water that temperature is 28-45 DEG C is added in material, limit edged stirs, and makes moisture weight account for the 4-8% of total weight of material, then, at room temperature place, cool, layering, filter, collect upper strata fluid I, for subsequent use;
Preferably,
Between Step d and step e, increase following steps: add in the Litsea Cubeba oil II that Step d obtains account for its weight 35-55%, vitriol and/or sulfite solution that concentration is 5.5-8.5%, stir, be heated to 85-100 DEG C, then leave standstill, be cooled to room temperature, stratification, collects upper strata fluid.
By preferably above-mentioned, purity and the higher stay-in-grade Sulcatone product of productive rate can be obtained further.
Wherein, described vitriol and/or sulphite can be enumerated as one or more in S-WAT, sodium sulfate, calcium sulfite etc.
The ether solvent with quality such as upper strata fluid I is preferably added in f step.
Described ether solvent can enumerate sherwood oil, ether, n-butyl ether or methyl tert-butyl ether etc.
Beneficial effect of the present invention
The present invention uses Persea cubeba for raw material, and raw material is natural phant, cheap and easy to get, and the present invention is while isolating limonene, successfully extracts first and obtains the Sulcatone that purity is high, productive rate is high.And Sulcatone is mainly prepared by chemical synthesis process in the prior art, have that side reaction is many, raw material is poisonous, yield is not high and high in cost of production problem.In addition, because in Persea cubeba, the content of Sulcatone is low, extract difficulty very large, therefore, in prior art, also do not carry out this trial.The present inventor is by years of researches, constantly experimental exploring, by strictly controlling the cooperation of each step and experiment parameter, and add strong base weak acid salts solution and effectively eliminate material with aldehyde radical and carboxyl in leaching process, part citral can also be converted into Sulcatone simultaneously; Method of the present invention effectively can eliminate the material such as firpene, amphene and most of limonene, and the limonene of removing is by obtaining high-purity limonene after simple process.Can effective separating impurity by method of the present invention, purification Sulcatone, finally realize object of the present invention, can not only be extracted from the low Persea cubeba of Sulcatone content by the present invention that purity is more than 90%, the Sulcatone of productive rate more than 80%, isolated limonene, by obtaining high-purity limonene after simple subsequent disposal, can reduce costs to a great extent.The present invention has important practical significance, and can bring huge economic benefit.
Accompanying drawing explanation
Fig. 1 is the chromatogram detection figure of the Sulcatone product that embodiment 2 obtains.Wherein Fig. 1 (a) is the full figure of color atlas obtained, and can find out the peak of the Sulcatone near peak height 10.59 from Fig. 1 (a) significantly; The partial enlargement figure that Fig. 1 (b) is Fig. 1 (a), can be more clearly visible peak height and the peak area of Sulcatone of the present invention from Fig. 1 (b); The concrete numerical value that Fig. 1 (c) is each peak; Can be clearly seen that from Fig. 1 (a)-Fig. 1 (c), the purity of the Sulcatone product that embodiment 2 obtains reaches 97.8601%.
Embodiment
Following examples are intended to be further described the present invention, but the present invention is not limited to following embodiment.
Embodiment 1
Extract the method for Sulcatone from Persea cubeba, comprise the following steps:
A, by Sulcatone content be the Persea cubeba 3000kg of 1.5 quality % clean, broken, insert in the reactor of 6.0 tons;
B, add the water of 4 times of weight wherein, be first heated to 68 DEG C by the heat-up rate of 3 DEG C/min, vacuum degree control at 8.5kpa, distillation 2.0h; The water of 68 DEG C is supplemented the moisture of distillation loss in still again, be heated to 94 DEG C, vacuum degree control 5.5kpa by the heat-up rate of 3 DEG C/min, distillation 5.0h, collects distillate, leaves standstill, cools, is separated, obtain the fluid of 120kg, for subsequent use;
C, in fluid, add concentration be 10.5 quality % aqueous sodium carbonates, makes the concentration of carbanion reach 2.45mg/10mL, then be heated to 100 DEG C by the heat-up rate of 2 DEG C/min, stir, then, cooling, layering, separation, obtain 82kg Litsea Cubeba oil I, for subsequent use;
D, the Litsea Cubeba oil I of step c gained is dropped into distillation tower, distills according to the following steps:
(1) the first step distillation: fluid is joined in still kettle, be heated to 86 DEG C by the heat-up rate of 7 DEG C/min, vacuum degree control is at 15kpa, and control of reflux ratio, 3/21, distills 3.5h;
(2) second step distillation: by the heating temperatures to 102 of still kettle DEG C, vacuum degree control 4kpa, control of reflux ratio is 4/16, and distillation 3.0h, collects Litsea Cubeba oil II 68kg that this section steams, for subsequent use;
E, Litsea Cubeba oil II is first added at normal temperatures and pressures propylene glycol, the alcohol mixed solvent of 6 times of weight, wherein, the mass ratio of propylene glycol and ethanol is 4.5:1, stirs evenly; Then, heat by the heat-up rate of 3 DEG C/min, be elevated to 55 DEG C to temperature and stop heating, and keep 2.5h, in material, add the warm water that temperature is 36.5 DEG C simultaneously, limit edged stirs, and makes moisture weight account for 5.5% of total weight of material, then, at room temperature place, cool, layering, filter, collect upper strata fluid I 60kg, for subsequent use;
F, the upper strata fluid I of step e gained to be dropped in the sherwood oil of equivalent weight at normal temperatures and pressures, stir evenly, adding the concentration accounting for fluid weight 14% is more wherein the aqueous ethanolic solution of 35%, mixing, then batch mixing is transferred in beaker and places 50min at bath temperature is 45 DEG C, then material is at room temperature left standstill, cool, layering, filtration, collect upper strata fluid II 55kg, for subsequent use;
G, be 68 DEG C by the upper strata fluid II of f step gained in temperature, vacuum tightness is be concentrated into no solvent residue under the condition of 35kpa, obtains concentrated fluid, for subsequent use;
H, the concentrated fluid of g step gained is dropped into distillation tower, distills according to the following steps:
(1) the first step distillation: fluid is joined in still kettle, be heated to 90 DEG C by the heat-up rate of 8 DEG C/min, vacuum degree control, at 16kpa, distills 75min;
(2) second step distillation: by the heating temperatures to 105 of still kettle DEG C, vacuum degree control 8kpa, control of reflux ratio, 3/36, distills 3.5h;
(3) the 3rd step distillations: joined by fluid in still kettle, be heated to 110 DEG C by the heat-up rate of 6 DEG C/min, vacuum degree control is at 3kpa, and distillation 75min, collects the fluid that this section steams, obtain the Sulcatone 41.5kg that purity is 95.6%.
Embodiment 2
Following steps are increased between Step d and step e,
Add in the Litsea Cubeba oil II that Step d obtains account for its weight 35-55%, concentration is the metabisulfite solution of 5.5-8.5%, stir evenly, 85-100 DEG C is heated to by the heat-up rate of 4-6 DEG C/min, constant temperature stir process 1.5-3.0h, then leave standstill, be cooled to room temperature, filter after layering obviously, collect upper strata fluid; Except increasing except above-mentioned steps between Step d and step e, all the other carry out same operation according to embodiment 1, obtain the product 42.58kg that the purity shown in Fig. 1 is 97.8601%.。
By increasing above-mentioned steps between Step d and step e, contriver finds, the process after step e is also more easily carried out and controlled, and the stability of the product obtained is better.
Comparative example 1
Step c is changed into:
C, in fluid, add the sodium citrate solution that concentration is 11.2-18.6%, the concentration of sodium ion is made to reach 4.8mg/10ml, 100 DEG C are heated to again by the heat-up rate of 2 DEG C/min, and stir in the direction of the clock, stir speed (S.S.) is 15 times/min, keeps 4.5h, then, cooling, layering, collect to obtain 106kg, for subsequent use;
Step e is changed into:
E, Litsea Cubeba oil II is first added 6 times of weight at normal temperatures and pressures by propylene glycol: in the solvent of ethanol=5.0:2.5 ratio mixed preparing, stir evenly; Then, heat by the heat-up rate of 3 DEG C/min, often raise 10 DEG C and stir 10min in the same direction, speed is 15 times/min, is elevated to 55 DEG C and stops heating, and keep 2.5h to temperature, between soak, stir speed (S.S.) is 40 times/min, and in material, add the warm water that temperature is 36.5 DEG C, limit edged stirs simultaneously, moisture weight is made to account for 5.5% of total weight of material, then, at room temperature place, cool, layering, filter, collect upper strata fluid 69.6kg, for subsequent use;
Except step c and step e are changed into above-mentioned except, all the other, according to the same operation of embodiment 1, finally obtain Sulcatone 32.6kg.Can find out, under the condition described in comparative example 1, the productive rate of Sulcatone reduces greatly.
Claims (10)
1. from Persea cubeba, extract a method for Sulcatone, it is characterized in that, comprise the following steps: a, by Persea cubeba clean, broken; B, add water and carry out underpressure distillation at 60-100 DEG C, be separated, obtain fluid; C, in fluid, add strong base weak acid salts solution obtain mixed solution, be heated to 50-100 DEG C, stir, layering, obtain Litsea Cubeba oil I; D, Litsea Cubeba oil I is carried out underpressure distillation at temperature 80-105 DEG C, obtain Litsea Cubeba oil II; E, in Litsea Cubeba oil II, add its weight 2-6 propylene glycol, alcohol mixed solvent doubly, the mass ratio of propylene glycol and ethanol is 4-8:1, and stratification after stirring at 40-55 DEG C, obtains upper strata fluid I and remaining liquid; F, add in ether solvent by upper strata fluid I, stir evenly, then add ethanolic soln wherein, stratification after stirring, obtains upper strata fluid II; G, temperature 50-68 DEG C, upper strata fluid II is concentrated into no solvent residue, the fluid after must concentrating under the condition of vacuum tightness 15-35kpa; H, the fluid underpressure distillation at 80-120 DEG C after concentrated to be purified, obtain product Sulcatone.
2. method according to claim 1, is characterized in that, by liquid more than gained in step e through being separated by-product limonene.
3. method according to claim 1, is characterized in that, the strong base weak acid salts solution added in fluid in step c is carbonate solution or citrate solution, and the concentration of strong base weak acid salts solution is 8-20 quality %.
4. according to the method that claim 3 is stated, it is characterized in that, described carbonate is salt of wormwood or sodium carbonate.
5. method according to claim 3, is characterized in that, in step c, after adding carbonate solution, the concentration of carbanion in mixed solution is 1.55-3.5mg/10mL.
6. method according to claim 1, is characterized in that, in step e, the mass ratio of propylene glycol and ethanol is 4-6:1.
7. method according to claim 1, is characterized in that, the concrete steps of underpressure distillation described in h step are: first by the heat-up rate of 6-8 DEG C/min, the fluid after concentrated is heated to 80-90 DEG C, vacuum degree control at 15-45kpa, distillation 50-75min; Then be heated to 95-105 DEG C, vacuum degree control 8-15kpa, control of reflux ratio, at 3/27-3/36, distills 1.5-3.5h; Finally be heated to 110-120 DEG C by the heat-up rate of 6-8 DEG C/min, vacuum degree control is at 3-8kpa, and distillation 50-75min, collects product Sulcatone.
8. method according to claim 1, it is characterized in that, the concrete steps of the underpressure distillation described in Step d are: by Litsea Cubeba oil I at temperature 80-90 DEG C, vacuum tightness 15-25kpa, after carrying out the first step distillation under the condition of reflux ratio 3/12-3/21, at temperature 95-105 DEG C, vacuum tightness 4-10kpa, carry out second step distillation under the condition of reflux ratio 4/8-4/16, obtain Litsea Cubeba oil II.
9. method according to claim 1, it is characterized in that, the distillation concrete steps that add water in b step are: joined by Persea cubeba in the water of 2-6 times of weight, be first heated to 60-75 DEG C by the heat-up rate of 3-4 DEG C/min, vacuum degree control, at 8-20kpa, distills 1.0-2.5h; The water adding 60-75 DEG C again supplements the moisture of distillation loss, then is heated to 90-100 DEG C by the heat-up rate of 2-3 DEG C/min, vacuum degree control 4-8kpa, distillation 1.5-5.0h.
10. the method according to any one of claim 1-9, it is characterized in that, between Step d and step e, increase following steps: add in the Litsea Cubeba oil II that Step d obtains account for its weight 35-55%, vitriol and/or sulfite solution that concentration is 5.5-8.5%, stir, be heated to 85-100 DEG C by the heat-up rate of 4-6 DEG C/min, constant temperature stir process 1.5-3.0h, then leave standstill, be cooled to room temperature, filter after layering obviously, collect upper strata fluid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237323A (en) * | 2015-10-20 | 2016-01-13 | 永州山香香料有限公司 | Method for extracting limonene from litsea cubeba |
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| CN1358705A (en) * | 2001-11-19 | 2002-07-17 | 天津大学 | Method for extracting citral by rectifying litsea cubeta oil |
| CN101157602A (en) * | 2007-10-22 | 2008-04-09 | 新疆中基天然植物纯化高新技术研究院有限公司 | Method for purifying geranialdehyde |
| CN101845364A (en) * | 2010-04-27 | 2010-09-29 | 郴州市明润生物制品有限公司 | Method for extracting citral from fruit of cubeb litsea tree |
| CN102211986A (en) * | 2011-04-19 | 2011-10-12 | 中南林业科技大学 | Process and device for extracting citral from Litsea cubeba oil |
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2014
- 2014-11-25 CN CN201410685012.2A patent/CN104478680B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358705A (en) * | 2001-11-19 | 2002-07-17 | 天津大学 | Method for extracting citral by rectifying litsea cubeta oil |
| CN101157602A (en) * | 2007-10-22 | 2008-04-09 | 新疆中基天然植物纯化高新技术研究院有限公司 | Method for purifying geranialdehyde |
| CN101845364A (en) * | 2010-04-27 | 2010-09-29 | 郴州市明润生物制品有限公司 | Method for extracting citral from fruit of cubeb litsea tree |
| CN102211986A (en) * | 2011-04-19 | 2011-10-12 | 中南林业科技大学 | Process and device for extracting citral from Litsea cubeba oil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237323A (en) * | 2015-10-20 | 2016-01-13 | 永州山香香料有限公司 | Method for extracting limonene from litsea cubeba |
| CN105237323B (en) * | 2015-10-20 | 2016-11-30 | 永州山香香料有限公司 | A kind of method extracting limonene from Fructus Litseae |
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