CN103540379A - Solid fuel prepared by hydrothermal carbonization of aqueous phase component of biological oil as well as method thereof - Google Patents
Solid fuel prepared by hydrothermal carbonization of aqueous phase component of biological oil as well as method thereof Download PDFInfo
- Publication number
- CN103540379A CN103540379A CN201310530696.4A CN201310530696A CN103540379A CN 103540379 A CN103540379 A CN 103540379A CN 201310530696 A CN201310530696 A CN 201310530696A CN 103540379 A CN103540379 A CN 103540379A
- Authority
- CN
- China
- Prior art keywords
- phase component
- bio
- solid fuel
- hydrothermal carbonization
- oil phase
- 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.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention relates to a solid fuel prepared by hydrothermal carbonization of an aqueous phase component of biological oil as well as a method thereof. The method comprises the following steps: (1) preparing the aqueous phase component of biological oil; (2) placing the aqueous phase component of biological oil in a high pressure reaction kettle, fastening a kettle cover, and replacing air in the kettle by nitrogen, hydrogen or inert gases; (3) heating to required reaction temperature, stirring, carrying out hydrothermal carbonization at constant temperature for over 2 hours, wherein the hydrothermal carbonization temperature is 100-300 DEG C; and (4) filtering and separating products after reaction, and drying to obtain the solid fuel. Compared with the conventional method for preparing fuels by saccharide and saccharide derivatives of the aqueous phase component of the biological oil, the method provided by the invention has the advantages of low energy consumption, mild reaction condition, simple technical process, easiness in separating reaction products, environment friendliness and the like.
Description
Technical field
The present invention relates to a kind of bio-oil phase component hydrothermal carbonization and prepare solid-fuelled method and solid fuel.
Background technology
At present, fossil oil excessive exploitation and the utilizations such as coal, oil, Sweet natural gas, and the series of problems such as the fossil oil causing thus exhaustion, global warming, environmental pollution, ecological damage has seriously restricted the Sustainable development of modern economy.Now, the energy and environmental problem have been the significant challenge that human society faces, and realize harmony between man and nature coexistence, seek renewable environmental friendliness clean energy, have been subject to various countries scholar's extensive concern.Biomass are unique a kind of storable renewable resourcess, and it utilizes in process self carbon cycle can realize CO
2zero release, is a kind of reproducible carbon source, and biomass reserves are abundant, becomes the focus of current research in energy consumption structure because occupying consequence more and more.
Bio oil is that biomass obtain easy accumulating and original liquid fuel easy to use by thermo-cracking, condensation under comparatively high temps.Biological oil composition and structure are very complicated, the organism of wherein having confirmed reaches 400 kinds more than, the oxygen-bearing organic matter that almost comprises all kinds, immiscible with conventional fossil fuel oil, its fuel characteristic especially thermostability is poor, there is certain corrodibility, under normal temperature condition, polymerization can occur, for the effective transportation of bio oil and follow-up hydrogenation, steam reforming and catalytic cracking, process and make troubles.At present, the composition of bio oil enrichment mainly comprises phenols, carbohydrate (being mainly Levoglucosan), carbohydrate derivative (mainly including machine acid, aldehyde, ketone, furans) and a small amount of alcohol, ether, ester etc.Existing document (Xun Hu, Chun-Zhu Li.Polymerization on Heating up of Bio-Oil:A Model Compound Study[J] .AIChE Journal.2013,59,888-900.) research show, in bio oil, as compounds such as aldehyde, furans there is polymerization in meeting under normal temperature and heating condition to glucide and its ramification, have a strong impact on quality of bio-oil, in hydrogenation, steam reforming and catalytic cracking catalyst surface coking, reduce reactive behavior simultaneously.
Therefore, realize the effective utilization of each component of bio oil and necessitate easily polymeric component is separated with relatively stable component in bio oil.Patent CN102703212A discloses a kind of novel method of bio oil component separation and purification, and bio oil obtains being rich in water component and the oil phase component of glucide and its ramification through washing.While bibliographical information, in water component, glucide and its ramification catalyzed conversion is prepared high valuable chemicals as 5 hydroxymethyl furfural, levulinic acid and ester thereof (Xun Hu, Chun-Zhu Li.Production of value-added chemicals from bio-oilviaacid catalysis coupled with liquid – liquid extraction[J] .RSC Advances.2012,2,9366-9370).But because glucide and its ramification has the polymerizability of height, in reaction process, need to add methyl alcohol stop glucide and its ramification in catalyst surface polymerization.Meanwhile, because the high added value product after the complicated component conversion of bio oil own is difficult to from product water phase component separated.
Summary of the invention
The object of the present invention is to provide the method for transformation of glucide and its ramification in a kind of bio-oil phase component, the method not only makes unsettled glucide and its ramification polymerization carbonization in bio oil prepare solid fuel, improve the stability of remaining phase product, simultaneously, the solid fuel that the method obtains is easily separated, process is simple, easily realizes industrialization promotion.
Object of the present invention is achieved through the following technical solutions:
Phase component hydrothermal carbonization is prepared a solid-fuelled method, comprises the steps:
(1) prepare bio-oil phase component
(2) bio-oil phase component is placed in to autoclave, covers tightly the air in nitrogen for kettle cover, hydrogen or inert gas replacement still;
(3) be warming up to required temperature of reaction, stir, incubation water heating carbonization, the temperature of described hydrothermal carbonization is 100～300 ℃, more than constant temperature 2h;
(4) reacted product is passed through to filtering separation, the dry rear solid fuel that obtains.
Described bio-oil phase component be by biomass through 500-700 ℃ of pyrolysis, intercept 120 ℃ of following cuts, condensation obtains.This water component is the water-soluble substances containing 20-30wt% organic constituent.
The volume of described bio-oil phase component is 1/3～3/4 of reactor volume, and in described reactor, the number of times of gas displacement is 4～6 times, to drain the air in still.
Described reactor hydrothermal carbonization temperature is 130～230 ℃.
Described constant temperature time is 4～24h.
The speed of described stirring is 100-1000 rev/min.
Described filtering separation is Büchner funnel separation or centrifugation.
Described biomass are pine, poplar or rice husk.
In bio oil component, be rich in the derivative (as: Low Molecular Weight Aldehydes, 5 hydroxymethyl furfural, hydroxyl acetaldehyde, oxyacetone etc.) of sugar (as: Levoglucosan) and sugar, because the height polymerization property of glucide and its ramification causes stability of bio-oil poor.By adding 120 ℃ of following cuts of water separation or condensation intercepting, can make the enrichment in water of unsettled glucide and its ramification.The present invention utilizes the easy polymerization property of glucide and its ramification, by hydrothermal carbonization method, in autoclave, 100 ℃～300 ℃, the above constant temperature of 2h, by the polymerization of water glucide and its ramification, and further carbonization, filtering separation obtains high heating value solid fuel.Meanwhile, by simple separation, extract and obtain the liquid phase component that is rich in phenols.
Compared with prior art, tool of the present invention has the following advantages:
(1) for the feature of the easy polymerization of glucide and its ramification in bio-oil phase component, utilize hydrothermal carbonization technology to realize glucide and its ramification polymerization carbonization in bio oil, prepare solid fuel.By simple filtering separation, obtain solid fuel and the stable liquid phase component that is rich in phenols of extraction acquisition simultaneously.
(2) the present invention solves in bio oil system because glucide and its ramification exists the bio oil system instability problem causing; Wherein factors of instability glucide and its ramification is also prepared solid fuel by simple separation method by polymerization carbonization; By extracting and separating, obtained the water-phase product that is rich in the stable components such as phenols simultaneously; The method reaction raw materials and process low toxicity, process is simple, energy consumption is low, reaction conditions is gentle.
(3) adopt bio-oil phase component provided by the invention to prepare solid fuel, pyrolysis on one side, on one side separated, equipment and technology flexibly and good economy performance, can be realized the serialization of production process, is applicable to industrialization development.
Accompanying drawing explanation
Fig. 1 is the schema of hydro-thermal reaction product separation.
Fig. 2 is product liquid ethyl acetate extraction GC-MS total ion current spectrogram after embodiment 2 hydrothermal carbonizations.
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited to this, for not dated especially processing parameter, can carry out with reference to routine techniques.
Embodiment 1
Described bio-oil phase component be by biomass through 500-700 ℃ of pyrolysis, intercept 120 ℃ of following cuts, condensation obtains.
In 100ml autoclave, add 60ml bio-oil phase component.Cover tightly kettle cover, with nitrogen, air in reactor is replaced 4 times.Then, open reactor condensing works and power supply, set 130 ℃ of temperature of reaction, 700 revs/min of stirring velocitys.Be warming up to after 130 ℃ constant temperature 2 hours.Reaction terminating, takes out reactor and is cooled to normal temperature, and venting, opens kettle cover.Take out and react the solid coke producing and the water-phase product that is rich in the stable components such as phenols, with Büchner funnel, carry out separation and dry acquisition solid fuel.
Embodiment 2
Described bio-oil phase component be by biomass through 500-700 ℃ of pyrolysis, intercept 120 ℃ of following cuts, condensation obtains.
In 100ml autoclave, add 60ml bio-oil phase component.Cover tightly kettle cover, with nitrogen, air in reactor is replaced 4 times.Then, open reactor condensing works and power supply, set 130 ℃ of temperature of reaction, 700 revs/min of stirring velocitys.Be warming up to after 130 ℃ constant temperature 24 hours.Reaction terminating, takes out reactor and is cooled to normal temperature, and venting, opens kettle cover.Take out and react the solid coke producing and the water-phase product that is rich in the stable components such as phenols, with Büchner funnel, carry out separation and dry acquisition solid fuel.
Embodiment 3
Described bio-oil phase component be by biomass through 500-700 ℃ of pyrolysis, intercept 120 ℃ of following cuts, condensation obtains.
In 100ml autoclave, add 60ml bio-oil phase component.Cover tightly kettle cover, with nitrogen, air in reactor is replaced 4 times.Then, open reactor condensing works and power supply, set 170 ℃ of temperature of reaction, 700 revs/min of stirring velocitys.Be warming up to after 170 ℃ constant temperature 24 hours.Reaction terminating, takes out reactor and is cooled to normal temperature, and venting, opens kettle cover.Take out and react the solid coke producing and the water-phase product that is rich in the stable components such as phenols, with Büchner funnel, carry out separation and dry acquisition solid fuel.
Embodiment 4
Described bio-oil phase component be by biomass through 500-700 ℃ of pyrolysis, intercept 120 ℃ of following cuts, condensation obtains.
In 100ml autoclave, add 60ml bio-oil phase component.Cover tightly kettle cover, with nitrogen, air in reactor is replaced 4 times.Then, open reactor condensing works and power supply, set 230 ℃ of temperature of reaction, 700 revs/min of stirring velocitys.Be warming up to after 230 ℃ constant temperature 24 hours.Reaction terminating, takes out reactor and is cooled to normal temperature, and venting, opens kettle cover.Take out and react the solid coke producing and the water-phase product that is rich in the stable components such as phenols, with Büchner funnel, carry out separation and dry acquisition solid fuel.
Described bio-oil phase component is that existing bio oil obtains water liquid two-phase by adding water (>50wt.%) layering, and separation obtains water.
In 100ml autoclave, add 60ml bio-oil phase component.Cover tightly kettle cover, with nitrogen, air in reactor is replaced 4 times.Then, open reactor condensing works and power supply, set 210 ℃ of temperature of reaction, 700 revs/min of stirring velocitys.Be warming up to after 210 ℃ constant temperature 24 hours.Reaction terminating, takes out reactor and is cooled to normal temperature, and venting, opens kettle cover.Take out and react the solid coke producing and the water-phase product that is rich in the stable components such as phenols, with Büchner funnel, carry out separation and dry acquisition solid fuel.
Table 1 solid fuel productive rate and superior calorific value analysis thereof
Product main ingredient and the relative content of product liquid after ethyl acetate extraction after table 2 embodiment 2 hydrothermal carbonizations
Claims (9)
1. bio-oil phase component hydrothermal carbonization is prepared a solid-fuelled method, it is characterized in that, comprises the steps:
(1) prepare bio-oil phase component;
(2) bio-oil phase component is placed in to autoclave, covers tightly the air in nitrogen for kettle cover, hydrogen or inert gas replacement still;
(3) be warming up to required temperature of reaction, stir, incubation water heating carbonization, described hydrothermal carbonization temperature is 100～300 ℃, more than constant temperature 2h;
(4) reacted product is passed through to filtering separation, the dry rear solid fuel that obtains.
2. method according to claim 1, is characterized in that, described bio-oil phase component be by biomass through 500-700 ℃ of pyrolysis, intercept 120 ℃ of following cuts, condensation obtains.
3. method according to claim 1 and 2, is characterized in that, the volume of described bio-oil phase component is 1/3～3/4 of reactor volume, and in described reactor, the number of times of gas displacement is 4～6 times.
4. method according to claim 1 and 2, is characterized in that, described hydrothermal carbonization temperature is 130～230 ℃.
5. method according to claim 1 and 2, is characterized in that, described constant temperature time is 4～24h.
6. method according to claim 1 and 2, is characterized in that, the speed of described stirring is 100-1000 rev/min.
7. method according to claim 1 and 2, is characterized in that, described filtering separation is Büchner funnel separation or centrifugation.
8. method according to claim 2, is characterized in that, described biomass are pine, poplar or rice husk.
9. the solid fuel that prepared by claim 1～8 any one method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310530696.4A CN103540379B (en) | 2013-10-31 | 2013-10-31 | Solid fuel prepared by hydrothermal carbonization of aqueous phase component of biological oil as well as method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310530696.4A CN103540379B (en) | 2013-10-31 | 2013-10-31 | Solid fuel prepared by hydrothermal carbonization of aqueous phase component of biological oil as well as method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103540379A true CN103540379A (en) | 2014-01-29 |
| CN103540379B CN103540379B (en) | 2015-03-11 |
Family
ID=49964252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310530696.4A Active CN103540379B (en) | 2013-10-31 | 2013-10-31 | Solid fuel prepared by hydrothermal carbonization of aqueous phase component of biological oil as well as method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103540379B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105900984A (en) * | 2016-04-26 | 2016-08-31 | 华南理工大学 | Method for preparing pesticide by using biomass hydrothermal carbonization liquid phase and preparing organic fertilizers by using solid phase |
| CN108342213A (en) * | 2018-01-16 | 2018-07-31 | 华中科技大学 | A kind of device and method preparing Nano carbon ball using biomass |
| CN108342220A (en) * | 2018-01-22 | 2018-07-31 | 华中科技大学 | A kind of system that the bio oil based on component separation is used using method with it |
| CN109666494A (en) * | 2019-01-24 | 2019-04-23 | 华中科技大学 | A kind of biomass pyrolysis oil prepares the method and product of spongy Carbon Materials |
| US10457882B2 (en) * | 2016-05-06 | 2019-10-29 | Iowa State University Research Foundation, Inc. | Methods of producing solid fuel using low ash, low sulfur coal replacement from fast pyrolysis of biomass |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238374A (en) * | 1998-06-05 | 1999-12-15 | 李永付 | Synthetic briquette and its production technology |
| WO2010102145A1 (en) * | 2009-03-04 | 2010-09-10 | Washington State University | Systems and processes for producing bio-fuels from lignocellulosic materials |
| CN101870881A (en) * | 2010-06-21 | 2010-10-27 | 中国科学院广州能源研究所 | Method for preparing liquid alkane fuel by upgrading bio-oil in aqueous phase catalytic mode |
| CN102250664A (en) * | 2011-06-23 | 2011-11-23 | 天津市东庄生物能源科技有限公司 | Formed carbon fuel particles, and preparation method and application thereof |
| CN102603498A (en) * | 2012-02-08 | 2012-07-25 | 厦门大学 | Method for extracting phenolic compounds from biological oil |
| US20120203044A1 (en) * | 2009-08-21 | 2012-08-09 | Total Raffinage Marketing | Process for upgrading a pyrolysis oil, in particular in a refinery |
| CN103304249A (en) * | 2013-05-31 | 2013-09-18 | 陕西科技大学 | Method for preparing carbon/carbon composite material |
-
2013
- 2013-10-31 CN CN201310530696.4A patent/CN103540379B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238374A (en) * | 1998-06-05 | 1999-12-15 | 李永付 | Synthetic briquette and its production technology |
| WO2010102145A1 (en) * | 2009-03-04 | 2010-09-10 | Washington State University | Systems and processes for producing bio-fuels from lignocellulosic materials |
| US20120203044A1 (en) * | 2009-08-21 | 2012-08-09 | Total Raffinage Marketing | Process for upgrading a pyrolysis oil, in particular in a refinery |
| CN101870881A (en) * | 2010-06-21 | 2010-10-27 | 中国科学院广州能源研究所 | Method for preparing liquid alkane fuel by upgrading bio-oil in aqueous phase catalytic mode |
| CN102250664A (en) * | 2011-06-23 | 2011-11-23 | 天津市东庄生物能源科技有限公司 | Formed carbon fuel particles, and preparation method and application thereof |
| CN102603498A (en) * | 2012-02-08 | 2012-07-25 | 厦门大学 | Method for extracting phenolic compounds from biological oil |
| CN103304249A (en) * | 2013-05-31 | 2013-09-18 | 陕西科技大学 | Method for preparing carbon/carbon composite material |
Non-Patent Citations (4)
| Title |
|---|
| 吕东灿等: "生物油的分离及其产品应用", 《林产化学与工业》 * |
| 姚燕等: "生物油轻质馏分加氢试验研究", 《工程热物理学报》 * |
| 王后雄: "《教材完全解读：人教版.九年级化学.下》", 31 October 2009, 中国青年出版社 * |
| 王曾辉等: "《碳素材料》", 31 December 1991, 华东化工学院出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105900984A (en) * | 2016-04-26 | 2016-08-31 | 华南理工大学 | Method for preparing pesticide by using biomass hydrothermal carbonization liquid phase and preparing organic fertilizers by using solid phase |
| US10457882B2 (en) * | 2016-05-06 | 2019-10-29 | Iowa State University Research Foundation, Inc. | Methods of producing solid fuel using low ash, low sulfur coal replacement from fast pyrolysis of biomass |
| CN108342213A (en) * | 2018-01-16 | 2018-07-31 | 华中科技大学 | A kind of device and method preparing Nano carbon ball using biomass |
| CN108342213B (en) * | 2018-01-16 | 2019-11-08 | 华中科技大学 | A kind of device and method preparing Nano carbon ball using biomass |
| CN108342220A (en) * | 2018-01-22 | 2018-07-31 | 华中科技大学 | A kind of system that the bio oil based on component separation is used using method with it |
| CN109666494A (en) * | 2019-01-24 | 2019-04-23 | 华中科技大学 | A kind of biomass pyrolysis oil prepares the method and product of spongy Carbon Materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103540379B (en) | 2015-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cao et al. | Hydrothermal liquefaction of agricultural and forestry wastes: state-of-the-art review and future prospects | |
| Tekin et al. | A review of hydrothermal biomass processing | |
| CN103540379B (en) | Solid fuel prepared by hydrothermal carbonization of aqueous phase component of biological oil as well as method thereof | |
| WO2010033512A1 (en) | Improved process for preparing bio-oils from biomass | |
| CN102976906B (en) | Method for separating phenols from bio-oil | |
| Elliott et al. | Conversion of a wet waste feedstock to biocrude by hydrothermal processing in a continuous-flow reactor: Grape pomace | |
| Wang et al. | Co-pyrolysis and catalytic co-pyrolysis of Enteromorpha clathrata and rice husk: Toward high-quality products | |
| MX2013013555A (en) | Method to convert fermentation mixture into fuels. | |
| CN101407727A (en) | Method for preparing biomass liquefied oil by biomass catalytic liquefaction | |
| CN102266864A (en) | Method for thermal decomposition refining and grading directional transformation of biomasses | |
| CN103361166A (en) | Method for preparing bio-oil from microalgae through direct liquidation | |
| CN104031012B (en) | A kind of living beings segmentation cracking is for the method for chemicals | |
| CN105154129B (en) | A kind of method that biomass platform chemicals and ABE tunning acetoin catalyzed conversion prepare liquid fuel | |
| CN105950274A (en) | Method for preparation of bio-oil by hydroxyl donor coordinated sub/super-critical ethanol liquefaction of straw cellulose | |
| Babatabar et al. | Pyrolysis of lignocellulosic and algal biomasses in a fixed‐bed reactor: A comparative study on the composition and application potential of bioproducts | |
| Bhatnagar et al. | Potential of stepwise pyrolysis for on-site treatment of agro-residues and enrichment of value-added chemicals | |
| El-Hefnawy et al. | Endogenous bioethanol production by solid-state prefermentation for enhanced crude bio-oil recovery through integrated hydrothermal liquefaction of seaweeds | |
| CN102199435B (en) | Method for preparing guaiacol-enriched biological oil by catalytic pyrolysis of biomass | |
| CN103305252A (en) | Method for preparing liquid fuel through coliquefaction of coal and alage | |
| CN113549467A (en) | System for preparing aromatic small-molecule chemicals from salix mongolica biomass | |
| CN103980929B (en) | Method for preparing biological fuel oil by fast pyrolyzing biomass | |
| CN109851689B (en) | Method for preparing levoglucosan by using agricultural and forestry waste | |
| CN105331387A (en) | Technological method for preparing aviation fuel through biomass thermal catalytic conversion and refining | |
| CN102321489A (en) | Method for catalyzing and liquefying agricultural wastes by using ion liquid | |
| CN101691494A (en) | Method for circulating and liquefying the mixture of plant biomass and waste polyester in supercritical fluid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |