CN109111414A - A kind of method of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid - Google Patents
A kind of method of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid Download PDFInfo
- Publication number
- CN109111414A CN109111414A CN201811037716.3A CN201811037716A CN109111414A CN 109111414 A CN109111414 A CN 109111414A CN 201811037716 A CN201811037716 A CN 201811037716A CN 109111414 A CN109111414 A CN 109111414A
- Authority
- CN
- China
- Prior art keywords
- agarose
- coproduction
- conversion
- levulic acid
- hydroxymethyl furfural
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Furan Compounds (AREA)
- Catalysts (AREA)
- Saccharide Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
A kind of method of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid, it is related to a kind of development and utilization method of biomass alternative energy source, a kind of method of the invention discloses agaroses in liquid-phase system catalyzed conversion coproduction 5 hydroxymethyl furfural (5-HMF) and levulic acid (LA), content is related to the chemicals that the preparation of carbohydrate catalyzed conversion has high added value, belongs to the development and utilization field of biomass alternative energy source.This method includes: using agarose as raw material, and by catalyst, fcc raw material is converted into 5-HMF and LA in certain solvent and under certain reaction temperature.The adoptable catalyst type multiplicity of this method, it is cheap and easy to get, 5-HMF and LA can be more quickly obtained, product total recovery is higher.The information that this method provides is the biomass that effective use is rich in agarose, and the especially raw algal biomass in sea provides useful reference.
Description
Technical field
The present invention relates to a kind of development and utilization methods of biomass alternative energy source, convert more particularly to a kind of agarose
The method of coproduction 5 hydroxymethyl furfural and levulic acid.
Background technique
The traditional energies such as petroleum, coal and natural gas play an important role in terms of supporting global evolution.However, with
Science and technology be constantly progressive, the mankind while substantially using traditional energy it has also been found that these resources be it is non-renewable,
And the problems such as environmental pollution can be caused again in use.Therefore, exploitation cleaning and reproducible new energy are increasingly subject to
The concern of countries in the world.Biomass is a kind of rich reserves, pollution-free or low pollution, at low cost, reproducible resource.Biomass
Or unique a kind of reproducible carbon source in nature at present, shows a kind of its great potential as alternative energy source.With biology
Matter is that raw material production of chemicals can realize the substitution for traditional energy to a certain extent, facilitates the sustainable of support society
Development.
In recent years, 5 hydroxymethyl furfural (5-HMF) and levulic acid (LA) have attracted extensive research to pay close attention to, both changes
Close object by reproducible carbohydrate through chemical conversion, can meet sustainable development principle (Biomass Bioenergy 2015, 72, 143; Sci. China Chem2015,58,29.).5-HMF is a kind of important change
Work intermediate by being aoxidized to it, adds the process such as hydrogen, amination, condensation that a variety of downstream product can be obtained, these productions
Product Process Technology of Polymer, fuel oil preparation, medicine intermediate synthesis etc. fields show good application value (Renew. Sust. Energ. Rev.2017,74,230.).LA is generally considered to be 5-HMF by obtained by acid-catalyzed hydration reaction
A kind of five carbon organic acids.LA be listed in the report that U.S. Department of Energy is announced be TOP 12 biology base platform chemicals it
One, a variety of downstream product can also be produced using it, there is important facilitation for the development of related chemical field
(ChemCatChem2012,4,1230.).
Currently, about the research of 5-HMF and LA is prepared mainly using fructose, glucose and their polymer as former
Material.Wherein, the reactivity of fructose is higher, can be converted by many kinds of catalysts and 5-HMF, available catalyst is made
Including inorganic acid, organic acid, metal salt, molecular sieve, acidic resins, ionic liquid and various functionalization materials etc..Compared to
For fructose, the reserves of glucose in nature more horn of plenty, but it is relatively difficult using glucose conversion 5-HMF processed, this is
Because glucose needs to be isomerized to fructose first, the fructose of generation, which further converts, is made 5-HMF.Therefore, for grape
For the conversion of sugar, it usually needs special catalyst, such as chromium chloride, stannic chloride, germanium chloride etc. is added, these catalyst energy
It is enough while being catalyzed the fructose converting of glucose isomerization and generation.Using the fructose such as inulin, starch, cellulose and glucose
Polymer when being raw material, usually can still continue to use the catalyst of corresponding monosaccharide conversion, but need in system to be added suitable quantity of water to
Realize that polymer is hydrolyzed to the link of monosaccharide.5-HMF acts on available LA by acid-catalyzed hydration.Therefore, no matter with fructose
Or it when glucose is that raw material prepares LA, requires to introduce enough water in system, and generallys use higher reaction temperature
Degree.Due to use the polymer conversions such as inulin, starch, cellulose for 5-HMF during need to be added the water of sufficient amount,
LA will coproduction acquisition during the conversion of these raw materials.
Although preparing the products such as 5-HMF and LA with fructose, glucose, inulin, starch, cellulose etc. for the biomass of representative
Important support is provided for development of chemical industry, but tellurian biomass is many kinds of, reserves are huge, how to realize a variety of lifes
It is the key that support one of energy demand and future development that substance, which effectively converts,.
Agarose is a kind of biomass resource not being fully developed also, and with linear structure, structure is mainly by D-
Galactolipin and 3,6- Anhydrogalactose is by β-Isosorbide-5-Nitrae and α -1, the repetition dissacharide units that 3 glucosides key connections are alternatively formed.However,
Only have considerably less document report at present and is converted into 5-HMF and LA(about agaroseRSC Adv. 2013, 3, 24090;RSC Adv.2015,5,47983.).In fact, agarose is mostly derived from the thalassophytes such as red algae, this kind of marine biomass
Reserves are very huge, have very wide utility value.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid, originally
Reaction raw materials in certain solvent, under certain reaction temperature, can be efficiently converted by invention using halide salt as catalyst
5 hydroxymethyl furfural (5-HMF) and levulic acid (LA).
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of method of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid, the method is using halide salt as catalysis
Agent, in certain solvent, under certain reaction temperature, reaction raw materials can be efficiently converted into 5 hydroxymethyl furfural (5-HMF) and
Levulic acid (LA)；
Including following preparation process:
A. reaction raw materials and catalyst are added in reactor；
B. solvent is added into reactor, and being stirred at room temperature is uniformly mixed reactive material；
C. by heating stirring one in the blender of the reactor merging setting reaction temperature equipped with raw material, catalyst and solvent
It fixes time, it later can coproduction acquisition 5-HMF and LA.
The method of the described a kind of conversion of agarose coproduction 5 hydroxymethyl furfural and levulic acid, the original in the step a
Material include any one of conventional agarose, low melting-point agarose, low electric osmose agarose, high-intensitive agarose or more than one
Combination.
The method of the described a kind of conversion of agarose coproduction 5 hydroxymethyl furfural and levulic acid, urging in the step a
Agent includes zirconium oxychloride (ZrOCl2), zirconium chloride (ZrCl4), stannic chloride (SnCl4), ammonium chloride (NH4Cl), ammonium bromide
(NH4Br), ammonium iodide (NH4Any one of) or more than one combination I.
The method of the described a kind of conversion of agarose coproduction 5 hydroxymethyl furfural and levulic acid, urging in the step a
Proportional region in agent mole and raw material between monosaccharide unit integral molar quantity is 0.01:1 ~ 0.5:1.
The method of the described a kind of conversion of agarose coproduction 5 hydroxymethyl furfural and levulic acid, raw material in the step a
D- galactose units and 3 in middle the referred to agarose of monosaccharide unit, 6- inner ether-L- galactose units.
The method of the described a kind of conversion of agarose coproduction 5 hydroxymethyl furfural and levulic acid, it is molten in the step b
Agent includes the mixture of polar organic solvent and polar organic solvent and water.
The method of the described a kind of conversion of agarose coproduction 5 hydroxymethyl furfural and levulic acid, the pole in the step b
Property organic solvent includes any one of dimethyl sulfoxide, sulfolane, N-Methyl pyrrolidone or more than one combination.
The method of the described a kind of conversion of agarose coproduction 5 hydroxymethyl furfural and levulic acid, the pole in the step b
Property organic solvent and water mixture in volume fraction shared by water be not higher than 85%.
The method of the described a kind of conversion of agarose coproduction 5 hydroxymethyl furfural and levulic acid, in the step c preferably
The reaction temperature of coproduction 5-HMF and LA are 130 ~ 160oC。
The advantages and effects of the present invention are:
1. operation is simple, reaction condition is milder, relatively quickly can obtain 5-HMF and LA, product from agarose
Total recovery is higher.
2. a variety of halide salts is used all to have better catalytic effect for catalyst, catalyst Application Range compares
Extensively, price is lower, this provides the space of more wide Catalyst Design for the combination of this technique and other techniques.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Embodiment 1
50 mg agaroses and catalyst Z rOCl2It is added in 1 mL solvent DMSO, ZrOCl2With monosaccharide unit in agarose
The ratio between mole is 0.1:1,140o60 min are reacted under C, after reaction, utilize high performance liquid chromatography test sample, 5-
The total recovery that the yield that the yield of HMF is 17%, LA is 10%, 5-HMF and LA is 27%.
Embodiment 2
50 mg agaroses and ZrOCl2It is added to 200 μ L H2The in the mixed solvent of O and 800 μ L DMSO, ZrOCl2With agar
The ratio between mole of monosaccharide unit is 0.1:1 in sugar, 140o60 min are reacted under C, after reaction, utilize efficient liquid phase
Chromatography test sample, the total recovery that the yield that the yield of 5-HMF is 27%, LA is 25%, 5-HMF and LA are 52%.
Embodiment 3
50 mg agaroses and ZrCl4It is added to 200 μ L H2The in the mixed solvent of O and 800 μ L DMSO, ZrCl4With agarose
The ratio between mole of middle monosaccharide unit is 0.1:1,140o60 min are reacted under C, after reaction, utilize high-efficient liquid phase color
Test sample is composed, the total recovery that the yield that the yield of 5-HMF is 26%, LA is 25%, 5-HMF and LA is 51%.
Embodiment 4
50 mg agaroses and SnCl4It is added to 200 μ L H2The in the mixed solvent of O and 800 μ L DMSO, SnCl4With agarose
The ratio between mole of middle monosaccharide unit is 0.1:1,140o60 min are reacted under C, after reaction, utilize high-efficient liquid phase color
Test sample is composed, the total recovery that the yield that the yield of 5-HMF is 24%, LA is 8%, 5-HMF and LA is 32%.
Embodiment 5
50 mg agaroses and NH4Cl is added to 200 μ L H2The in the mixed solvent of O and 800 μ L DMSO, NH4Cl and agarose
The ratio between mole of middle monosaccharide unit is 0.1:1,140o60 min are reacted under C, after reaction, utilize high-efficient liquid phase color
Test sample is composed, the total recovery that the yield that the yield of 5-HMF is 24%, LA is 12%, 5-HMF and LA is 36%.
Embodiment 6
50 mg agaroses and ZrOCl2It is added to 400 μ L H2The in the mixed solvent of O and 600 μ L DMSO, ZrOCl2With agar
The ratio between mole of monosaccharide unit is 0.1:1 in sugar, 140o60 min are reacted under C, after reaction, utilize efficient liquid phase
Chromatography test sample, the total recovery that the yield that the yield of 5-HMF is 23%, LA is 18%, 5-HMF and LA are 41%.
Embodiment 7
50 mg agaroses and ZrOCl2It is added to 200 μ L H2The in the mixed solvent of O and 800 μ L DMSO, ZrOCl2With agar
The ratio between mole of monosaccharide unit is 0.1:1 in sugar, 150o30 min are reacted under C, after reaction, utilize efficient liquid phase
Chromatography test sample, the total recovery that the yield that the yield of 5-HMF is 23%, LA is 23%, 5-HMF and LA are 46%.
Embodiment 8
50 mg agaroses and ZrOCl2It is added to 200 μ L H2The in the mixed solvent of O and 800 μ L DMSO, ZrOCl2With agar
The ratio between mole of monosaccharide unit is 0.05:1 in sugar, 140o60 min are reacted under C, after reaction, utilize efficient liquid phase
Chromatography test sample, the total recovery that the yield that the yield of 5-HMF is 23%, LA is 17%, 5-HMF and LA are 40%.
Some specific embodiments that the above, the only present invention are listed, but protection scope of the present invention is not limited to
In this, also not because of the succession between each embodiment to the present invention caused by any restrictions, it is any to be familiar with the art
Technical staff in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in should all be covered in this hair
Within bright protection scope.Therefore, protection scope of the present invention should be subject to the protection scope in claims.
Claims (9)
1. a kind of method of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid, which is characterized in that the method is with halogen
Salt dissolving is as catalyst, and in certain solvent, under certain reaction temperature, reaction raw materials can be efficiently converted into 5- methylol chaff
Aldehyde (5-HMF) and levulic acid (LA)；
Including following preparation process:
A. reaction raw materials and catalyst are added in reactor；
B. solvent is added into reactor, and being stirred at room temperature is uniformly mixed reactive material；
C. by heating stirring one in the blender of the reactor merging setting reaction temperature equipped with raw material, catalyst and solvent
It fixes time, it later can coproduction acquisition 5-HMF and LA.
2. the method for a kind of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid according to claim 1, special
Sign is that the raw material in the step a includes conventional agarose, low melting-point agarose, low electric osmose agarose, high-intensitive agarose
Any one of or more than one combination.
3. the method for a kind of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid according to claim 1, special
Sign is that the catalyst in the step a includes zirconium oxychloride (ZrOCl2), zirconium chloride (ZrCl4), stannic chloride (SnCl4), chlorine
Change ammonium (NH4Cl), ammonium bromide (NH4Br), ammonium iodide (NH4Any one of) or more than one combination I.
4. the method for a kind of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid according to claim 1, special
Sign is that the proportional region in the catalyst mole and raw material in the step a between monosaccharide unit integral molar quantity is 0.01:
1~0.5:1。
5. the method for a kind of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid according to claim 1, special
Sign is, D- galactose units and 3,6- inner ether-L- gala in the referred to agarose of monosaccharide unit in raw material in the step a
Sugar unit.
6. the method for a kind of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid according to claim 1, special
Sign is that the solvent in the step b includes the mixture of polar organic solvent and polar organic solvent and water.
7. the method for a kind of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid according to claim 1, special
Sign is, the polar organic solvent in the step b includes dimethyl sulfoxide, sulfolane, any in N-Methyl pyrrolidone
One or more kinds of combinations.
8. the method for a kind of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid according to claim 1, special
Sign is, polar organic solvent in the step b and volume fraction shared by water is not higher than 85% in the mixture of water.
9. the method for a kind of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid according to claim 1, special
Sign is that the reaction temperature of preferred coproduction 5-HMF and LA are 130 ~ 160 in the step coC。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811037716.3A CN109111414B (en) | 2018-09-06 | 2018-09-06 | Method for converting agarose to co-produce 5-hydroxymethylfurfural and levulinic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811037716.3A CN109111414B (en) | 2018-09-06 | 2018-09-06 | Method for converting agarose to co-produce 5-hydroxymethylfurfural and levulinic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109111414A true CN109111414A (en) | 2019-01-01 |
| CN109111414B CN109111414B (en) | 2020-11-06 |
Family
ID=64858735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811037716.3A Active CN109111414B (en) | 2018-09-06 | 2018-09-06 | Method for converting agarose to co-produce 5-hydroxymethylfurfural and levulinic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109111414B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023212999A1 (en) | 2022-05-05 | 2023-11-09 | 中国科学院宁波材料技术与工程研究所 | Composite catalyst and synthesis method for bio-based furan chemicals |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101421259A (en) * | 2006-03-10 | 2009-04-29 | 福兰尼克斯科技公司 | Method for the synthesis of organic acid esters of 5-hydroxymethylfurfural and their use |
| CN102212046A (en) * | 2011-04-19 | 2011-10-12 | 天津理工大学 | Catalytic system for synthesizing 5-hydroxymethylfurfural by dehydration of sugar or polysaccharide |
| WO2017076625A1 (en) * | 2015-11-02 | 2017-05-11 | IFP Energies Nouvelles | Method for producing 5-hydroxymethylfurfural in the presence of a lewis acid catalyst and/or a heterogeneous base catalyst and a homogeneous organic brønsted acid catalyst in the presence of at least one aprotic polar solvent |
-
2018
- 2018-09-06 CN CN201811037716.3A patent/CN109111414B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101421259A (en) * | 2006-03-10 | 2009-04-29 | 福兰尼克斯科技公司 | Method for the synthesis of organic acid esters of 5-hydroxymethylfurfural and their use |
| CN102212046A (en) * | 2011-04-19 | 2011-10-12 | 天津理工大学 | Catalytic system for synthesizing 5-hydroxymethylfurfural by dehydration of sugar or polysaccharide |
| WO2017076625A1 (en) * | 2015-11-02 | 2017-05-11 | IFP Energies Nouvelles | Method for producing 5-hydroxymethylfurfural in the presence of a lewis acid catalyst and/or a heterogeneous base catalyst and a homogeneous organic brønsted acid catalyst in the presence of at least one aprotic polar solvent |
Non-Patent Citations (1)
| Title |
|---|
| SANG JIN OH, ET AL.: "Production of 5-hydroxymethylfurfural from agarose by using a solid acid catalyst in dimethyl sulfoxide", 《RSC ADV.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023212999A1 (en) | 2022-05-05 | 2023-11-09 | 中国科学院宁波材料技术与工程研究所 | Composite catalyst and synthesis method for bio-based furan chemicals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109111414B (en) | 2020-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ding et al. | Catalytic conversion of cellulose to 5-hydroxymethyl furfural using acidic ionic liquids and co-catalyst | |
| Hu et al. | Recent advance on the catalytic system for efficient production of biomass-derived 5-hydroxymethylfurfural | |
| Tian et al. | A review on solid acid catalysis for sustainable production of levulinic acid and levulinate esters from biomass derivatives | |
| US20090326286A1 (en) | Process of producing liquid fuel from cellulosic biomass | |
| Fukuoka et al. | Sustainable green catalysis by supported metal nanoparticles | |
| Feng et al. | Synthesis of MCM‐41‐supported metal catalysts in deep eutectic solvent for the conversion of carbohydrates into 5‐hydroxymethylfurfural | |
| CN101402658B (en) | Method for thermal degradation of cellulose with ion liquid solvent catalysis | |
| CN107445925A (en) | A kind of method that protist matter complete utilization prepares furfuran compound and liquid cycloalkane | |
| CN104072450A (en) | Novel method for preparing 5-hydroxymethylfurfural and furfural by adopting biomass raw material | |
| Boonyakarn et al. | Enhanced levulinic acid production from cellulose by combined Brønsted hydrothermal carbon and Lewis acid catalysts | |
| Xu et al. | Recent advances on solid acid catalyic systems for production of 5-Hydroxymethylfurfural from biomass derivatives | |
| Li et al. | Phosphotungstic acid functionalized biochar for furfural production from corncob | |
| CN111423399B (en) | Method for converting holocellulose into furfural platform compound | |
| Mimura et al. | 5‐Hydroxymethylfurfural Production from Glucose, Fructose, Cellulose, or Cellulose–based Waste Material by Using a Calcium Phosphate Catalyst and Water as a Green Solvent | |
| Jiang et al. | “One-pot” conversions of carbohydrates to 5-hydroxymethylfurfural using Sn-ceramic powder and hydrochloric acid | |
| CN110407779B (en) | Method for preparing 5-hydroxymethylfurfural by using biomass as raw material | |
| CN108976185A (en) | A method of it is synchronized using biomass and prepares furfural and 5 hydroxymethyl furfural | |
| Yao et al. | Sustainable approaches to selective conversion of cellulose into 5-hydroxymethylfurfural promoted by heterogeneous acid catalysts: a review | |
| CN110256377B (en) | Method for preparing furfural by ionic liquid catalysis | |
| Jia et al. | Dimethylsulfoxide/Water Mixed Solvent Mediated Synthesis of 5‐Hydroxymethylfurfural from Galactose with Aluminum Salt Catalyst | |
| CN109111414A (en) | A kind of method of agarose conversion coproduction 5 hydroxymethyl furfural and levulic acid | |
| Wei et al. | Facile synthesis of metal-organic frameworks embedded in interconnected macroporous polymer as a dual acid-base bifunctional catalyst for efficient conversion of cellulose to 5-hydroxymethylfurfural | |
| CN109046448A (en) | The Meng Zao race clay-SO of ion liquid functionalization3The preparation method and applications of H-IL composite material | |
| Li et al. | A solid acid-catalyzed depolymerization of pine lignin to obtain guaiacol using a hydrogen-free strategy | |
| CN108863999B (en) | Method for preparing hydroxymethylfurfural under mild condition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |