CN104692388A - Method for preparing high-purity nanometer three-dimensional porous structure silicon from rice hulls - Google Patents
Method for preparing high-purity nanometer three-dimensional porous structure silicon from rice hulls Download PDFInfo
- Publication number
- CN104692388A CN104692388A CN201310659818.XA CN201310659818A CN104692388A CN 104692388 A CN104692388 A CN 104692388A CN 201310659818 A CN201310659818 A CN 201310659818A CN 104692388 A CN104692388 A CN 104692388A
- Authority
- CN
- China
- Prior art keywords
- purity
- silicon
- rice husk
- porous structure
- dimensional porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention relates to a method for preparing high-purity nanometer three-dimensional porous structure silicon from rice hulls. The method mainly solves the technical problems that in the prior art, the process is complicated, the cost is high, and the environment pollution is serious. The method is realized through the following process steps that A, rice hull pretreatment is carried out, the rice hulls are boiled by hydrochloric acid and are washed and dried, the dried rice hulls are conveyed into a combustion furnace, and rice hull ash is obtained through combustion; B, high-purity nanometer silicon dioxide is extracted from the rice hull ash; C, thermal reduction is carried out on the silicon dioxide, in an argon atmosphere, magnesium powder and the nanometer silicon dioxide are proportionally and uniformly mixed and placed in a heating furnace, and the high-purity nanometer three-dimensional porous structure silicon is prepared. The method has the characteristics that a heat source can be provided for subsequent heat reaction, the energy source consumption is reduced, the exhaust of greenhouse gas is reduced, the purity of magnesium chloride by-products is high, metal magnesium can be prepared through electrolysis, the method can also be used in the fields of medicine, agriculture and the like, the environment pollution is reduced, meanwhile, the product structure can also be prevented from being destroyed, the cost is low, and the purity is high.
Description
Technical field
The invention belongs to chemical materials preparation and comprehensive utilization of resources field, be specifically related to a kind of method that rice husk prepares high-purity nm three-dimensional porous structure silicon.
Background technology
Lithium ion battery has that voltage is high, specific energy is high, the feature such as memory-less effect and non-environmental-pollution, one of main selection having become 21 century green battery.The lithium ion battery negative material mainly carbon-based negative electrode material that commercialization uses, but the theoretical capacity of carbon only has 372mAh/g, cannot meet the requirement of new type lithium ion battery anticathode material heavy body of future generation.Therefore, the development of development of new non-carbon negative material to lithium ion battery has great importance.
Porous silicon, with its vesicular structure and the feature such as specific surface area is larger, is considered to the preferred material of alternative carbon as high capacity lithium ion cells cathode.At present, the preparation of this porous silicon is mainly raw material with chemical reagent, and complex process, cost is high, and environmental pollution is serious.
The farm crop that paddy rice is extensively planted as a kind of whole world, annual production can reach 4.22 hundred million tons.Rice husk is the waste of paddy rice processing, accounts for 1/5th of paddy rice ultimate production.Directly being abandoned by rice husk, both can cause the destruction to environment, is also the wasting of resources, and some enterprises only achieve the low value-added utilization of rice husk at present, as made nursery ridging, feed etc.Rice husk has the silicon dioxide layer of one deck uniqueness, accounts for the 15-20% of rice husk proportion.In order to protect the inner grain of rice, prevent the intrusion of ladybug and bacterium, sky G&W can be made to pass through, this layer of silicon-dioxide has nanoporous simultaneously.Therefore, the silicon in rice husk is reduced by suitable technique, will have nanometer three-dimensional porous structure.
The people such as the Choi Jang Wook of Korea S propose first, raw material based on rice husk, utilize the series of process such as pyroprocessing, magnesium reduction silicon-dioxide, hydrofluoric acid wash, the silicon with nanometer three-dimensional porous structure can be obtained, and verify bright by experiment, when this silicon is used as lithium ion battery negative material, have that capacity is high, cycle performance and the feature such as electrochemical stability is excellent.Therefore, this excellent property, cheap silicon, can well meet the demand of lithium ion battery for novel non-carbon negative material.
But the technique that the people such as Choi Jang Wook utilize rice husk to prepare nanometer three-dimensional porous structure silicon does not consider the recycle of the energy, water etc., and to the pollution of environment, and hydrofluoric acid wash causes the decline of product performance to the destruction of product structure.The present invention fills up the blank that domestic rice husk prepares high-purity nm three-dimensional porous structure silicon, meanwhile, improves external preparation technology, enhances product performance, and reduces costs and destruction to environment.
Summary of the invention
The present invention, for the purpose of solving the problem, mainly solves the complex process that prior art exists, the technical problem that cost is high and environmental pollution is serious.
For achieving the above object, the present invention adopts following technical proposals: a kind of rice husk prepares the method for high-purity nm three-dimensional porous structure silicon, and the method is realized by following processing step:
1, rice husk pre-treatment
A) be that the hydrochloric acid of 1-10% carries out boiling washing to rice husk by concentration.Wherein, the weight quota ratio of hydrochloric acid soln and rice husk is 5-40:1; Boiling time 0.5-2.5h.
B) to the rice husk washing after pickling, drying.
C) dried rice husk is sent into roasting kiln, keep temperature of combustion 650-900 DEG C, combustion time, 20-120 minute, obtained rice hull ash.
2, from rice hull ash, high-purity nm silicon-dioxide is extracted
D) aqueous sodium carbonate of rice hull ash and 10-25wt% is put into reactor in solid-liquid weight quota ratio 1:5-10, be heated to 100-150 DEG C, hydrolysis 0.5-3h, filter carbon slag, filtrate is the raw material preparing silicon-dioxide.
E), after filtrate temperature being down to 80-60 DEG C, passing into the tail gas after purification in step c), reaction times 1-4h, separate out precipitation, filter.
F) filtrate is back to step d) recycle, and filter cake obtains nano silicon through washing, drying.Waste water after washing is back to step b) recycle; Drying source is the heat of combustion tail gas in step c).
3, thermal reduction silicon-dioxide
G) under an argon atmosphere, magnesium powder and nano silicon to be mixed than the ratio uniform of 0.8-1.2:1 with weight quota be placed in process furnace, temperature of reaction 750-850 DEG C, reaction times 2-4h.
H) product in step g) is washed to pH=7, filtration through the hydrochloric acid soln that concentration is 2-10%, obtain filtrate and filter cake.Filtrate can be used for the field such as medicine, agricultural, or obtains magnesium chloride crystal, for the preparation of MAGNESIUM METAL through crystallization treatment.
I) by step h) middle filter cake is washed, dry obtained high-purity nm three-dimensional porous structure silicon, and drying source is the heat of combustion tail gas in step c).
Beneficial effect of the present invention and feature are:
1, the heat that combusting rice hull produces can provide thermal source for follow-up thermal response through reclaiming, and reduces energy consumption, reduces production cost;
2, catalyzer is only, no consumption, reusable edible for dissolving the sodium carbonate of silicon-dioxide in rice hull ash;
3, combusting rice hull tail gas is through purifying treatment, can be used as the precipitation agent of silicon-dioxide, reduces the discharge of greenhouse gases;
4, by-product magnesium chloride purity is high, by electrolytic preparation MAGNESIUM METAL, also can be used for the field such as medicine, agricultural;
5, silicon-dioxide is reduced thoroughly, without the need to through hydrofluoric acid wash, reduces environmental pollution, meanwhile, prevents product structure to be destroyed;
6, low cost product, purity is high.
Embodiment
Embodiment one
1, rice husk pre-treatment
A) by concentration be 1% hydrochloric acid boiling washing is carried out to rice husk.Wherein, the weight quota ratio of hydrochloric acid soln and rice husk is 20:1; Boiling time 0.5h.
B) to the rice husk washing after pickling, drying.
C) dried rice husk is sent into roasting kiln, keep temperature of combustion 750 DEG C, 90 minutes combustion times, obtain rice hull ash.
2, from rice hull ash, high-purity nm silicon-dioxide is extracted
D) aqueous sodium carbonate of rice hull ash and 20wt% is put into reactor in solid-liquid weight quota ratio 1:8, be heated to 120 DEG C, hydrolysis 2h, filter carbon slag, filtrate is the raw material preparing silicon-dioxide.
E), after filtrate temperature being down to 70 DEG C, passing into the tail gas after purification in step c), reaction times 3h, separate out precipitation, filter.
F) filtrate is back to step d) recycle, and filter cake obtains nano silicon through washing, drying.Waste water after washing is back to step b) recycle; Drying source is the heat of combustion tail gas in step c).
3, thermal reduction silicon-dioxide
G) under an argon atmosphere, magnesium powder and nano silicon to be mixed than the ratio uniform of 1:1 with weight quota be placed in process furnace, temperature of reaction 800 DEG C, reaction times 3h.
H) product in step g) is washed to pH=7, filtration through the hydrochloric acid soln that concentration is 5%, obtain filtrate and filter cake.
I) by step h) middle filter cake is washed, dry obtained high-purity nm three-dimensional porous structure silicon product.Product mean pore size 32nm, purity 99.5%.
Embodiment two
Adjustment rice husk pre-treatment concentration of hydrochloric acid is that 8% pair of rice husk carries out boiling washing, boiling time 2.5h, and other conditions, with embodiment one, prepare mean pore size 28nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.9%.
Embodiment three
The temperature of reaction changing rice hull ash and sodium carbonate is 100 DEG C, and the reaction times is 2h, and other conditions, with embodiment two, prepare mean pore size 33nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.6%.
Embodiment four
The temperature of reaction changing rice hull ash and sodium carbonate is 150 DEG C, and the reaction times is 3h, and other conditions, with embodiment two, prepare mean pore size 40nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.9%.
Embodiment five
Changing magnesium powder with the temperature of reaction of the nano silicon extracted from rice husk is 750 DEG C, reaction times 2h.Other conditions, with embodiment two, prepare mean pore size 29nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.9%.
Embodiment six
Changing magnesium powder with the temperature of reaction of the nano silicon extracted from rice husk is 850 DEG C, reaction times 3h.Other conditions, with embodiment two, prepare mean pore size 51nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.9%.
Claims (7)
1. prepare a method for high-purity nm three-dimensional porous structure silicon with rice husk, the method is realized by following processing step:
A, rice husk pre-treatment
A) be that the hydrochloric acid of 1-10% carries out boiling washing to rice husk by concentration, wherein, the weight quota ratio of hydrochloric acid soln and rice husk is 5-40:1, boiling time 0.5-2.5h;
B) to the rice husk washing after pickling, drying;
C) dried rice husk is sent into roasting kiln, keep temperature of combustion 650-900 DEG C, combustion time, 20-120 minute, obtained rice hull ash;
B, from rice hull ash, extract high-purity nm silicon-dioxide
D) by the aqueous sodium carbonate of rice hull ash and 10-25wt%, put into reactor, be heated to 100-150 DEG C in solid-liquid weight quota ratio 1:5-10, hydrolysis 0.5-3h, filter carbon slag, filtrate is the raw material preparing silicon-dioxide;
E), after filtrate temperature being down to 80-60 DEG C, passing into the tail gas after purification in step c), reaction times 1-4h, separate out precipitation, filter;
F) filtrate is back to step d) recycle, and filter cake obtains nano silicon through washing, drying.Waste water after washing is back to step b) recycle; Drying source is the heat of combustion tail gas in step c);
C, thermal reduction silicon-dioxide
G) under an argon atmosphere, magnesium powder and nano silicon to be mixed than the ratio uniform of 0.8-1.2:1 with weight quota be placed in process furnace, temperature of reaction 750-850 DEG C, reaction times 2-4h;
H) washed to pH=7, filtration through the hydrochloric acid soln that concentration is 2-10% by product in step g), obtain filtrate and filter cake, filtrate can be used for the field such as medicine, agricultural, or obtains magnesium chloride crystal, for the preparation of MAGNESIUM METAL through crystallization treatment;
I) by step h) middle filter cake is washed, dry obtained high-purity nm three-dimensional porous structure silicon, and drying source is the heat of combustion tail gas in step c).
2. rice husk as claimed in claim 1 prepares the method for high-purity nm three-dimensional porous structure silicon, its specific implementation step:
A, rice husk pre-treatment
A) by concentration be 1% hydrochloric acid boiling washing is carried out to rice husk, wherein the weight quota ratio of hydrochloric acid soln and rice husk is 20:1, boiling time 0.5h;
B) to the rice husk washing after pickling, drying;
C) dried rice husk is sent into roasting kiln, keep temperature of combustion 750 DEG C, 90 minutes combustion times, obtain rice hull ash;
B, from rice hull ash, extract high-purity nm silicon-dioxide
D) aqueous sodium carbonate of rice hull ash and 20wt% is put into reactor in solid-liquid weight quota ratio 1:8, be heated to 120 DEG C, hydrolysis 2h, filter carbon slag, filtrate is the raw material preparing silicon-dioxide;
E), after filtrate temperature being down to 70 DEG C, passing into the tail gas after purification in step c), reaction times 3h, separate out precipitation, filter;
F) filtrate is back to step d) recycle, and filter cake obtains nano silicon through washing, drying, and the waste water after washing is back to step b) recycle, and drying source is the heat of combustion tail gas in step c);
C, thermal reduction silicon-dioxide
G) under an argon atmosphere, magnesium powder and nano silicon to be mixed than the ratio uniform of 1:1 with weight quota be placed in process furnace, temperature of reaction 800 DEG C, reaction times 3h;
H) product in step g) is washed to pH=7, filtration through the hydrochloric acid soln that concentration is 5%, obtain filtrate and filter cake;
I) by step h) middle filter cake is washed, dry obtained high-purity nm three-dimensional porous structure silicon product, product mean pore size 32nm, purity 99.5%.
3. rice husk as claimed in claim 2 prepares the method for high-purity nm three-dimensional porous structure silicon, its specific implementation step:
Adjustment rice husk pre-treatment concentration of hydrochloric acid is that 8% pair of rice husk carries out boiling washing, and boiling time 2.5h, prepares mean pore size 28nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.9%.
4. rice husk as claimed in claim 3 prepares the method for high-purity nm three-dimensional porous structure silicon, its specific implementation step:
The temperature of reaction changing rice hull ash and sodium carbonate is 100 DEG C, and the reaction times is 2h, prepares mean pore size 33nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.6%.
5. rice husk as claimed in claim 3 prepares the method for high-purity nm three-dimensional porous structure silicon, its specific implementation step:
The temperature of reaction changing rice hull ash and sodium carbonate is 150 DEG C, and the reaction times is 3h, prepares mean pore size 40nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.9%.
6. rice husk as claimed in claim 3 prepares the method for high-purity nm three-dimensional porous structure silicon, its specific implementation step:
Changing magnesium powder with the temperature of reaction of the nano silicon extracted from rice husk is 750 DEG C, and reaction times 2h, prepares mean pore size 29nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.9%.
7. rice husk as claimed in claim 3 prepares the method for high-purity nm three-dimensional porous structure silicon, its specific implementation step:
Changing magnesium powder with the temperature of reaction of the nano silicon extracted from rice husk is 850 DEG C, and reaction times 3h, prepares mean pore size 51nm, the high-purity nm three-dimensional porous structure silicon product of purity 99.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310659818.XA CN104692388A (en) | 2013-12-05 | 2013-12-05 | Method for preparing high-purity nanometer three-dimensional porous structure silicon from rice hulls |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310659818.XA CN104692388A (en) | 2013-12-05 | 2013-12-05 | Method for preparing high-purity nanometer three-dimensional porous structure silicon from rice hulls |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104692388A true CN104692388A (en) | 2015-06-10 |
Family
ID=53340008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310659818.XA Pending CN104692388A (en) | 2013-12-05 | 2013-12-05 | Method for preparing high-purity nanometer three-dimensional porous structure silicon from rice hulls |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104692388A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417543A (en) * | 2015-10-26 | 2016-03-23 | 河北民族师范学院 | Process for preparing nano porous silicon electrode material |
| CN105712395A (en) * | 2016-01-21 | 2016-06-29 | 华南理工大学 | Method for preparing large-specific-surface-area mesoporous TiO2 by using SiO2 in biomass |
| CN106430213A (en) * | 2016-09-07 | 2017-02-22 | 扬州大学 | Low-temperature preparation method of rice-hull-based porous silicon material |
| CN107565118A (en) * | 2017-08-30 | 2018-01-09 | 山东大学 | A kind of preparation method of high-performance lithium ion nano-silicon negative material |
| CN109200980A (en) * | 2018-10-12 | 2019-01-15 | 广州市天河外国语学校 | A kind of acidification reaction device of rice husk silica |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449996A (en) * | 2003-05-20 | 2003-10-22 | 吉林大学 | Process for preparing high-purity nano silicon dioxide from rice husk |
| CN1756719A (en) * | 2003-02-18 | 2006-04-05 | 雷吉斯特印度科学院 | Novel method and device from rice husk ash silicon-dioxide |
| CN101417798A (en) * | 2008-11-26 | 2009-04-29 | 吉林大学 | Paddy hull burned gas and waste residue comprehensive utilization method |
| CN101920966A (en) * | 2010-07-21 | 2010-12-22 | 化工部长沙设计研究院 | Method for producing porous nano silica and active carbon by utilizing rice hull ash |
| WO2012153897A1 (en) * | 2011-05-12 | 2012-11-15 | 충남대학교 산학협력단 | Method for producing high-purity porous silica and silicon derived from rice husks |
| CN103204506A (en) * | 2013-04-15 | 2013-07-17 | 上海应用技术学院 | Shape-controlled mesoporous silica nano-material and preparation method thereof |
-
2013
- 2013-12-05 CN CN201310659818.XA patent/CN104692388A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1756719A (en) * | 2003-02-18 | 2006-04-05 | 雷吉斯特印度科学院 | Novel method and device from rice husk ash silicon-dioxide |
| CN1449996A (en) * | 2003-05-20 | 2003-10-22 | 吉林大学 | Process for preparing high-purity nano silicon dioxide from rice husk |
| CN101417798A (en) * | 2008-11-26 | 2009-04-29 | 吉林大学 | Paddy hull burned gas and waste residue comprehensive utilization method |
| CN101920966A (en) * | 2010-07-21 | 2010-12-22 | 化工部长沙设计研究院 | Method for producing porous nano silica and active carbon by utilizing rice hull ash |
| WO2012153897A1 (en) * | 2011-05-12 | 2012-11-15 | 충남대학교 산학협력단 | Method for producing high-purity porous silica and silicon derived from rice husks |
| CN103204506A (en) * | 2013-04-15 | 2013-07-17 | 上海应用技术学院 | Shape-controlled mesoporous silica nano-material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| DAE SOO JUNG ET AL.: "Recycling rice husks for high-capacity lithium battery anodes", 《PNAS》, vol. 110, no. 30, 23 July 2013 (2013-07-23), pages 12229 - 12234 * |
| ZHIHAO BAO ET AL.: "Chemical reduction of three-dimensional silica micro-assemblies into microporous silicon replicas", 《NATURE》, vol. 446, 8 March 2007 (2007-03-08), pages 172 - 175, XP 055062828, DOI: doi:10.1038/nature05570 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417543A (en) * | 2015-10-26 | 2016-03-23 | 河北民族师范学院 | Process for preparing nano porous silicon electrode material |
| CN105417543B (en) * | 2015-10-26 | 2020-07-03 | 河北民族师范学院 | Preparation process of nano porous silicon electrode material |
| CN105712395A (en) * | 2016-01-21 | 2016-06-29 | 华南理工大学 | Method for preparing large-specific-surface-area mesoporous TiO2 by using SiO2 in biomass |
| CN105712395B (en) * | 2016-01-21 | 2018-09-14 | 华南理工大学 | It is a kind of to utilize SiO in biomass2Prepare high specific surface area and mesoporous TiO2Method |
| CN106430213A (en) * | 2016-09-07 | 2017-02-22 | 扬州大学 | Low-temperature preparation method of rice-hull-based porous silicon material |
| CN107565118A (en) * | 2017-08-30 | 2018-01-09 | 山东大学 | A kind of preparation method of high-performance lithium ion nano-silicon negative material |
| CN109200980A (en) * | 2018-10-12 | 2019-01-15 | 广州市天河外国语学校 | A kind of acidification reaction device of rice husk silica |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018205539A1 (en) | Three-dimensional lignin porous carbon/zinc oxide composite material, preparation thereof and use thereof in field of photocatalysis | |
| CN104692388A (en) | Method for preparing high-purity nanometer three-dimensional porous structure silicon from rice hulls | |
| JP5756525B2 (en) | Manufacturing method and use of manganese dioxide nanorods | |
| CN107159293A (en) | A kind of NiFe3N/NF electrochemical catalysts and preparation method and application | |
| CN105870422A (en) | C@SiOx material, preparation method thereof and application of C@SiOx material taken as negative electrode material of lithium ion battery | |
| CN105347364A (en) | Method for closed-loop recycling of lithium precipitation mother liquor in lithium carbonate production | |
| CN101941704A (en) | New method for preparing silicon dioxide by utilizing rice hull ash | |
| CN101704526B (en) | Method for producing white carbon black and active carbon by using residual rice hull ash after gasification | |
| CN104150478B (en) | A kind of green circulatory technique of being prepared activated carbon for super capacitors material by rice husk | |
| CN107808958A (en) | Preparation method of ferroso-ferric oxide/nitrogen-doped graphene composite and products thereof and application | |
| CN105126855A (en) | ZnO/ZnFe2O4/C nano-structure hollow spheres and preparation method of same | |
| CN106082210A (en) | A kind of compound active fruit shell carbon and preparation method thereof, application | |
| CN111747442A (en) | Method for producing active zinc oxide by wet process | |
| CN106185929A (en) | A kind of preparation method of the activated carbon with flourishing pore structure | |
| CN105540587A (en) | Method for preparing activated carbon from rice husks | |
| CN110492076B (en) | Preparation method of two-dimensional porous hexagonal metal oxide nanosheet composite material and application of composite material in potassium ion battery | |
| Zhang et al. | Effect of nickel oxide morphology on the nitrogen electrochemical reduction reaction | |
| CN108470904A (en) | A kind of ring plate shape hexagon mangano-manganic oxide lithium cell cathode material and preparation method thereof | |
| CN104051731B (en) | A kind of method that LiFePO4 is prepared in pollution-free zero-emission | |
| CN103165877A (en) | Preparation method and application of negative electrode material of lithium battery | |
| WO2017201911A1 (en) | Method for low temperature manufacturing of fexpo4-containing material using ferrophosphorus | |
| CN101734927B (en) | Method for preparing lithium iron phosphate/carbon nano tube compound material | |
| Liu et al. | Oxygen vacancy modulation in interfacial engineering Fe3O4 over carbon nanofiber boosting ambient electrocatalytic N2 reduction | |
| CN109420487A (en) | A kind of preparation method of bamboo charcoal-zinc oxide photocatalysis material | |
| Zhang et al. | Simplified attainment of porous carbon materials from nature's gifts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150610 |